最新刊期
卷 ， 期 2 ， 2013
- 摘要：Each mature science contains inevitably a paradigm,it gives expression to the special structure,the basic theoretical frame and the study range of this science.But a paradigm for the condensed matter physics of polymers is so far not formed.In this paper the important successes of condensed matter physics of polymers in recent 20~30 years were summarized; a series of notions e.g. soft matter,self similarity,fractal,scaling laws,correlative effect,lyotropic condensation,entropy induced phase transition,Brownian movement,multi-body effects,symmetry breaking and their importance were interpreted and emphasized.And it is indicated,that the summarizing of paradigm of condensed matter physics of polymers becomes already an urgent work for polymer physicists.关键词：Macromolecule;Condensed matter physics;Paradigm
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发布时间：2021-03-19
Feature Articles
- 摘要：Polyimide (PI-HQDPA) derived from 2,6-bis(p-aminophenyl)-benzo［1,2-d;5,4-d'］bisoxazole and 1,4-bis(3,4-dicarbosyphenoxy) benzene dianhydride (HQDPA) was synthesized via a conventional two-stage method. The intermediate poly(amic acid) had inherent viscosities of 1.70 dL/g and could be thermally converted into light yellow polyimide film.The thermal degradation of the polyimide was studied by thermogravimetric analysis (TGA) using four different methods in order to determine the actual reaction mechanisms of the decomposition process.The apparent activation energy (E) of the solid-state process was determined using Flynn-Wall-Ozawa and Friedman methods,which do not require the knowledge of the reaction mechanism.And the apparent activation energies were resulted to be 356.36 and 370.54 kJ/mol,respectively.So the average activation energy of the polyimide was 363.45 kJ/mol.The reaction order (n) and pre-exponential factor (A) were determined by Friedman method,and the results were 4.22 and 6.441016 s-1,respectively.The activation energies of different mechanism models were determined by Coats-Redfern and Phadnis-Deshpande methods,the most probably results were 370.66 and 367.80 kJ/mol,respectively.Compared with the value obtained from the Ozawa method and Friedman method,the actual reaction mechanism of PI-HQDPA obeyed the nucleation and growth model,and could be described by the Avrami-Erofeev function (A3) with an integral form of g(X)=［-ln(1-X)］3.关键词：Benzobisoxazole;Polyimide;Decomposition reaction mechanism;Activation energies
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发布时间：2021-03-19 - 摘要：The 1/N expansion,as a rigorous basis of the Mean Field Theory (MFT),is discussed in several typical polymer systems.It shows that MFT can be applied well in polymer physics only if the system has certain symmetries.In neutral polymer solutions,MFT is suitable for concentrated solutions and melts,in which N is no less than six,but not suitable for dilute and very dilute solutions whose N is less than six.Moreover,MFT is a good description in polyelectrolyte solutions if the polymer chains are very weakly-charged.However,for the case of strongly-charged systems,MFT is no longer the right way due to the low symmetries of the system,then maybe the scaling theory will be a good choice.关键词：Mean field theory;1/N Expansion;Symmetry;Polymer physics
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发布时间：2021-03-19 - 摘要：A high melting temperature phosphorus flame retardant,hydroquinol bis(diphenyl phosphate) (HDP),was synthesized in a novel process.First,the intermediate product was synthesized from hydroquinone and phosphoryl oxychloride,and then it was reacted with phenol,at last,HDP was isolated and purified.The obtained HDP was a kind of white solid,and the yield exceeded 90%.The structure of HDP was characterized by 1H-NMR,31P-NMR and MS.The flame retardance of HDP was discussed,and compared with resorcinol bis(diphenyl phosphate) (HDP) in acrylonitrile-butadiene-styrene (ABS) composites.When HDP or RDP was added into ABS resin with char former Novolac phenol (NP) in the ratio of HDP (RDP)/NP (20/10),it was very effective in enhancing the LOI value and improving the flame retardation in condensation phase.The thermal degradation properties were was investigated by thermogravimetric analysis (TGA) and cone calorimeter test,and the results showed that the incorporation of HDP or RDP increased its thermal stability and char formation. The smoke suppression of ABS/HDP/NP composites is better than that of ABS/RDP/NP composites.The morphological structures and element distribution of the chars were investigated by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS).Compared with ABS/RDP/NP composites,the cavities and holes were more uniform,and the distribution phosphorus was more uniform in the char of ABS/HDP/NP composites.The above analysis showed that,when HDP was added to ABS resin with NP,HDP had better flame retardancy in condensation phase than RDP.关键词：Hydroquinol bis(diphenyl phosphate);Flame retardant;Condensation phase;Acrylonitrile-butadiene-styrene
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发布时间：2021-03-19 - 摘要：Supercritical carbon dioxide (SC-CO2) foaming technology was applied to fabricate highly porous poly(lactic acid-co-glycolic acid) (PLGA) scaffolds.The effects of polymer chemical composition (the mole percentage of glycolic acid in the polymer was 15 and 50 respectively),molecular weight (50 kDa and 200 kDa) and the processing parameters including foaming pressure (from 10 MPa to 25 MPa),temperature (from 35℃ to 85℃) and depressurization rate (0.05 MPa/s and 0.20 MPa/s) on the scaffold structure were investigated in detail.Morphologies of the scaffolds were characterized by scanning electron microscopy (SEM) and pore size distribution was obtained via analysis of SEM images.Porosity and interconnectivity of the scaffolds were measured by pycnometer (Archimedes principle) and mercury intrusion technique,respectively.The results showed that the pore size and interconnectivity increased while increasing the lactic acid content of the polymer.Higher pressure led to higher cell density and smaller pores,and pore coalescence occurred at low depressurizing rates.Glass transition temperature (Tg) of the polymer decreased under SC-CO2,and large polygonal cells were formed when the foaming temperature was set below 45℃.Differently,higher foaming temperature resulted in globular cells,with cell size decreased sharply.However,further increasing the temperature led to slightly larger pore sizes.Supercritical carbon dioxide foaming method makes it possible to fabricate the macro-cellular and micro-cellular foams of PLGA without using organic solvents and high temperature,which provide a way to fabricate porous polymer scaffolds for potential applications in tissue engineering.关键词：Poly(lactic acid-co-glycolic acid);Supercritical carbon dioxide;Foaming;Porous tissue engineering scaffolds
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发布时间：2021-03-19 - 摘要：The ternary blend films composed of low polymerization degree poly［2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta［2,1-b;3,4-b'］dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)］ (LDP-PCPDTBT),［6,6］-phenyl-C61-butyric acid methyl ester (PC61BM),and polymethylmethacrylate (PMMA) were fabricated with and without using 1,8-dibromooctane (DBO) as solvent additive.The role of PMMA was to enable the formation of the smooth and continuous thin films spun from the solution onto the conducting substrate.In addition,the good stability of the PMMA against the heat,oxygen and water attacks was useful for achieving the long lifetime of organic solar cells.The LDP-PCPDTBT and PC61BM phases in the PMMA matrix were amorphous and crystalline,respectively,regardless of the additive processing.The crystalline aggregation of the LDP-PCPDTBT was hampered by the PC61BM molecules,though the additive processing was able to promote the degree of crystallinity of the LDP-PCPDTBT.However,with the additive processing the phase separation of the LDP-PCPDTBT and PC61BM components in the PMMA matrix was optimized,leading to the improved electron-transporting property and thereby an increase of 32.4% in the power conversion efficiency of solar cell,compared to without the additive processing.The current research indicates that the low polymerization degree alternating copolymers can be recycled as efficient electron donors in association with PMMA,helpful for reducing the material cost of organic solar cells.关键词：Organic solar cells;Ternary blend films;LDP-PCPDTBT;PMMA;1,8-Dibromooctane
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发布时间：2021-03-19 - 摘要：A novel strategy was proposed and then verified to graft poly(methyl methacrylate) chains from TiO2 nanoparticle surface (the TiO2-PMMA hybrid nanoparticles) via Cu2+-amine redox-initiated conventional radical polymerization.CuSO4-catalyzed surface-initiated radical polymerization of methyl methacrylate (MMA) was carried out in dimethylsufoxide (DMSO) from the TiO2 nanoparticles surface functionanlized with amine layers (the TiO2-NH2 nanoparticles) to prepare the TiO2-PMMA hybrid nanoparticles.The results from infrared spectroscopy,thermogravimetric analysis and electron microscopy showed that PMMA was successfully immobilized onto the TiO2 nanoparticle surface,the grafting yield increased with the reaction time,and the presence of PMMA chains hindered the further agglomeration and accordingly improved the dispersion stability in organic media.As there was no free PMMA chains in the reacting mixture,our strategy provided a facile and universal route to the hybrid nanoparticles of application potentials.关键词：TiO2;Methyl methacrylate;Hybrid nanoparticle;Cu2+-amine redox initiation;Surface-initiated radical polymerization
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发布时间：2021-03-19 - 摘要：The silane compounds including dicyclohexyldimethoxysilane (Donor-H) and dipiperidinedimethoxysilane (Donor-Py) were first synthesized.Then they and the industrial external donor cyclohexylmethyldimethoxysilane (Donor-C) were employed for propylene polymerization with MgCl2-supported Ziegler-Natta catalyst,respectively.The effects of the changeable substitutes of the three external donors on the catalytic activity,hydrogen response,molecular weight distribution,crystalline ability,isotactic sequence length and isotactic sequence length distribution were studied by differential scanning calorimetry (DSC),gel permeation chromatography (GPC),self-nucleation and annealing (SSA) and 13C-NMR.The results indicated that the electron-donating ability of the external electron donors was enhanced with the increase of the bulkiness of the changeable substituted groups in the external donors.Compared with the external donor Donor-C,the synthesized external donors Donor-H and Donor-Py had the excellent performance in the catalytic activity,crystallization ability and isospecificity of polypropylene for propylene polymerization with the increase of the bulkiness of the substituted groups in the external donors Donor-H and Donor-Py.Especially,when the Donor-Py was used as external donor,the catalyst showed the highest catalytic activity,and the prepared polypropylene exhibited the highest isotacticity,the strongest crystallization ability and the widest melt index.The GPC data also showed the external donor Donor-Py was benefit for obtaining broad molecular weight distribution polypropylene than the other two external donors Donor-H and Donor-C.The SSA results showed that the polypropylene prepared by the external donor Donor-Py had the largest relative content of higher isotactic components and the longest isotactic sequence length of polypropylene,and the narrowest isotactic sequence length distribution.The 13C-NMR results also showed that the increase of the bulkiness of the substituted groups in the external donors was benefit for improving the average meso isotactic sequence length and the molecular chain stereoregularity of polypropylene.关键词：Ziegler-Natta catalyst;External electron donor;Dipiperidinedimethoxysilane;Self-nucleation and annealing
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发布时间：2021-03-19 - 摘要：The polymer crystallization process and mechanism were studied by computer simulation method.It is benefit to understand the crystallization kinetics by comparing the simulated results with the experimental results.Based on a nonconserved spatiotemporal Ginzburg-Landau equation TDGL model,a novel three dimensional phase field model was established by combining the cellular automaton method with the general phase field model.For simulating the real three dimensional polymer crystallization process,the cellular automaton method was modified by the different steric structures and discretization methods.The different steric structures or discretization methods are related to the lattice parameters of syndiotactic polypropylene single crystals and the crystal growth faces of polymer single crystals.It was suggested that the novel method is a way of building bridges between the diffusion equation and polymer characterization.Moreover,the diffusion equations are discretized according to the diffusion coefficient of every lattice site in various crystal growth faces,and the shape of lattice is selected based on the real proportion of the unit cell dimensions.Especially,the other physics parameters of syndiotactic polypropylene also were introduced into the phase field model.The spatio-temporal growth of syndiotactic polypropylene single crystals during isothermal crystallization was simulated by the novel three dimensional phase field model.Three dimensional numerical calculations are performed to elucidate the faceted single crystal growth including square,rectangular,lozenge-shaped,and hexagonal single crystals.The corresponding three dimensional results were illustrated by the MatLab.Our simulated patterns are in good agreement with the experimental morphologies,and the physical origin of polymer single crystal growth is discussed.关键词：Phase field model;Polymer single crystals;Three dimensional simulation
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发布时间：2021-03-19 - 摘要：A series of star comb polybutadiene-g-poly(methyl methacrylate) graft copolymers (SC-(PB-g-PMMA)) with various chain lengths were synthesized with the combination of living anionic polymerization and atom transfer radical polymerization (ATRP) in sequence.First,star-shaped polybutadiene with predetermined molecular weight and microstructure was synthesized by anionic polymerization of butadiene with n-butyllithium initiator in the solvent of cyclohexane at 50℃ for 3 h.Then the in-chain living functionalized star-shaped initiator containing bromine (SPB-Brn)s was obtained after expoxidated with performic acid in situ from hydrogen peroxide and formic acid,and esterification reaction with in situ 2-bromoisobutyrate.Finally,SC-(PB-g-PMMA)s were prepared from the polymerization of methyl methacrylate (MMA) and SPB-Brn with SPB-Brn as initiator and CuCl/CuCl2/N,N,N',N,N-pentamethyldiethylenetriamine (PMDETA) as catalyst and ligand by atom transfer radical polymerization in the solvent of CHCl3 at 60℃ for 8 h.A series of star comb polybutadiene-g-poly(methyl methacrylate) graft copolymers (SC-(PB-g-PMMA)) with various chain lengths were synthesized by changing the monomer ratio.The properties of the SPB-Brn and the series of star-comb graft copolymers polybutadiene-g-poly(methyl methacrylate) were characterized by 1H-NMR,FTIR,GPC and DSC.The SC-(PB-g-PMMA)s in solution were also examined and their thermotropic behavior were discussed.All in all,the results show that well-defined target products with controlled molecular weight and low disperisity were obtained.The phase separation and branching parameters of the copolymers varied with chain lengths.关键词：Living anionic polymerization;ATRP;Mechanism transferormation;Star-comb polymers
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发布时间：2021-03-19 - 摘要：Homogeneous braided tube reinforced polyacrylonitrile (PAN) hollow fiber membranes which contained hollow braided tube and separation surface were prepared by concentric circles spinning method.The braided tube was prepared by the two-dimensional braided technique using PAN fibers.While the separation surface was obtained by non-solvent induced phase separation method with PAN as the polymer matrix,dimethyl sulfoxide (DMSO) as the solvent,and polyethylene glycol (PEG) as the pore-forming agent.Results showed that the structure of separation surface was similar to asymmetric membrane.The casting solution would penetrate into the voids among fiber bundles of the braided tube.As the braided pitch increasing,the thickness of separation surface decreased,which induced the promotion of the membrane water flux.There was no obvious influence of casting solution penetration on the membrane permeability.The breaking strength of braided tube was up to 100 MPa.Water bath vibration,ultrasonic vibration and the same axial tension force were utilized to investigate the interfacial adhesion between separation surface and braided tube of homogeneous and heterogeneous braided tube reinforced hollow fiber membranes.The results showed that the interfacial adhesion of the homogeneous one was superior to that of the heterogeneous one.关键词：Homogeneous reinforced;Two-dimensional braided tube;PAN;Hollow fiber membrane
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发布时间：2021-03-19 - 摘要：The alkali lignin was modified by laccase,followed by sulfomethylation.To study the mechanism of laccase modification on the influence of sulfomethylation reactivity,the control and laccase modified alkali lignins were characterized by chemical,spectroscopic and chromatographic methods.The molecular weight of sulfomethylated lignins was measured by gel permeation chromatography (GPC),and the structural changes in laccase modified lignins were characterized by functional groups measurements,headspace gas chromatography (GC),infrared spectroscopy (IR) and nuclear magnetic resonance (NMR).It is proposed that laccase was able to promote both polymerization and depolymerisation.The molecular weight (Mw) changed a little,but the polydispersity was larger than that of the control.The demethylation by laccase oxidation made the increase of the content of phenolic group,while the content of syringyl decreased.At the same time,laccase could oxidise the phenolic end-groups into stabilized radicals that subsequently undergo radical-radical coupling.The charge density of lignin model compounds was calculated by molecular simulation.It was indicated that why demethylation benefited the sulfomethylation.According to structural changes in lignin,the mechanism of the influence laccase modification on the sulfomethylation reactivity was deduced.The sulfomethylation reactivity,measured by the content of sulfonic groups,was increased by 35% after laccase modification.It was mainly due to the increase of the content of phenolic groups and the decrease of steric hindrance.In addition,the dispersion efficiency of sulfomethlated alkali lignin with laccase modification on the TiO2 slurry improved significantly.关键词：Laccase;Alkali lignin;Sulfomethylation reactivity;Dispersion efficiency
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发布时间：2021-03-19 - 摘要：High scattering composite sheets are prepared using melt blending processing,with outstanding advantages of high transmittance and high haze.Bisphenol A polycarbonate (PC) is treated as matrix and poly-(styrene-co-acrylonitrile) (SAN) is dispersed phase.The effect of SAN content on the light scattering properties is investigated and the microstructure is analyzed through SEM.Both transmittance and haze increase simultaneously with the increase of SAN content,which is rarely reported before.The shape of dispersed phase is spherical when SAN content is less than 30%,and then the average particle diameter increases and the number concentration decreases with the increasing SAN content.Both transmittance and haze increase with the increasing content of SAN and reach a maximum value at an SAN content of 30%,where transmittance is 89.1% and haze is 91.7%.Mie scattering theory is used to analyze the influence of the scattering particle diameter and number concentration on the light scattering properties.With the further increasing of SAN content,the dispersed phase tends to have large size with irregular shape,and the light scattering property decreases,which cannot be analyzed using Mie scattering theory because the particle diameter is much greater than the incident light wavelength.关键词：Polycarbonate (PC);Poly(styrene-co-acrylonitrile) (SAN);High transmittance;High haze;Mie scattering theory
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发布时间：2021-03-19 - 摘要：Porous polyacrylonitrile (PAN) ultrathin fibers with nanopore structures were prepared by electrospinning a ternary system of PAN/dimethyl sulphoxide (DMSO)/N,N'-dimethylformamide (DMF) using a water bath at 3℃.We investigated the effects of proportion of DMSO to DMF,collection medium,PAN concentration,applied voltage and needle to collector distance on the diameter and surface porosity of PAN ultrathin fibers.The optimum electrospinning parameters are given as PAN concentration of 15 wt%,DMSO/DMF proportion of 1 ∶1 (W/W),applied voltage of 16 kV,needle to collector distance of 5 cm,solution flow rate of 0.7 mL/h,relative humidity of 40%~70% and room temperature of 25℃.The diameter,morphology and porosity of porous PAN ultrathin fibers were characterized by scanning electron microscope,showing the fibers,which were obtained under the optimum conditions,were porous throughout with a diameter ranging from 420 nm to 490 nm,an average diameter of 468 nm and surface porosity of 3.4%.The BET specific surface area was measured by nitrogen adsorption and desorption isotherms.It can reach 43.86 m2/g,which is 5 times higher than the theoretical surface area of smooth and nonporous 468 nm PAN fibers.Moreover,nonsolvent induced phase separation has been proposed to be the main mechanism for the formation of porous PAN fibers,which is confirmed by the ternary phase diagram of PAN/(DMSO+DMF)/H2O.关键词：Polyacrylonitrile;Electrospinning;Porous structures;Nonsolvent induced phase separation
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发布时间：2021-03-19 - 摘要：The influences of the glass transition temperature,the crystallization behavior and the hydrogen bond strength on the thermal expansion behavior of four types of aliphatic polyamides were studied in details by thermal expansion test,differential scanning calorimetry (DSC),wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR).DSC and X-ray diffraction results showed that the coefficient of linear thermal expansion (CLTE) of crystalline part is lower than that of amorphous part for different types of aliphatic polyamides.However,the influences of the melting temperature and crystallinity of the aliphatic polyamide on CLTE are not clear.Polyamide 56 (PA56) owning a higher glass transition temperature and a lower ratio of methylene/amide groups (CH2/CONH) shows a much lower CLTE value than other aliphatic polyamides.Further experimental results showed that when all of these specimens were prepared under the same procedure and conditions,a linear relationship between CH2/CONH ratio or glass transition temperature and CLTE could be obtained for the aliphatic polyamide systems.It was found that a further decrease in CLTE could be achieved either by increasing Tg or by decreasing the CH2/CONH ratio of the polyamide chains.FTIR results confirmed that the density and strength of hydrogen bonds are the key factors influencing the thermal expansion behavior of aliphatic polyamides.关键词：Polyamides;Thermal expansion;Hydrogen bond
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发布时间：2021-03-19 - 摘要：Molecular chain heterogeneity of the copolymer of L-lactide and -caprolactone(PLC) was investigated using the preparative temperature rising elution fractionation (TREF) technique and successive self-nucleation/annealing (SSA) thermal fractionation.Two PLC samples with -caprolactone compositions of 5 mol% and 10 mol% were prepared and fractionated by using TREF.For both samples,three fractions were collected and characterized with nuclear magnetic resonance spectroscopy (1H-NMR) and gel permeation chromatography (GPC).The 1H-NMR results showed that there exists obvious differences in the caproyl content among the fractions.It was also found,with GPC method,that for the fraction of higher elution temperature,the number average molecular weight (Mn) is higher and the distribution is narrower.The data obtained suggest that the fractionation is mainly the result of the difference of the chain tacticity.The chain heterogeneity of TREF fractions was further analyzed with SSA thermal fractionation.The first Ts to be used in the SSA method was carefully chosen in Domain II for all fractions.After SSA treatment,the appearance of multiple melting behavior for each fraction indicates that a heterogeneous intramolecular distribution of defects still exsits in the chains of fractionated sample.On the other hand,the intermolecular heterogeneity is evident in the different melting ranges of each fraction.关键词：Copolymer;Heterogeneity;TREF;SSA
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发布时间：2021-03-19 - 摘要：A linear-dendron-like polyampholyte was synthesized via the combination of ring-opening polymerization (ROP),divergent synthesis procedure and click chemistry.First,azide-terminated poly(-benzyl-L-glutamate) (PBLG-N3) and the second generation PAMAM (D2) with alkyne focal group and four terminal primary amine groups were synthesized by the ROP of -benzyl-L-glutamate N-carboxyanhydride (BLG-NCA) and divergent synthesis procedure,respectively.Subsequently,PBLG-N3 was click conjugated with alkyne focal group of D2 to generate primary amine-terminated linear-dendron-like PBLG-b-D2,which was then used as the microinitiator for the ROP of -benzyloxycarbonyl-L-lysine N-carboxyanhydride (ZLL-NCA) to produce the linear-dendron-like copolymer PBLG-b-D2-(PZLL)4.The targeted linear-dendron-like polyampholyte,PLGA50-b-D2-(PLL9)4,where PLGA is poly(L-glutamic acid) and PLL is poly(L-lysine),was obtained by the hydrolysis of protecting benzyl and benzyloxycarbonyl groups of PBLG and PZLL,respectively.The molecular structures of the intermediates and the final polyampholyte were characterized by 1H-NMR,Fourier transform-infrared spectroscopy (FTIR) and gel permeation chromatograph (GPC).The physical properties and pH-responsive behavior in aqueous solution were investigated via potentiometric and conductometric titration,1H-NMR,zeta potential measurement,laser light scattering (LLS),scanning electron microscopy (SEM) and circular dichroism spectroscopy (CD).The results show that PLGA50-b-D2-(PLL9)4 can self-assemble into schizophrenic micelles which can be reversibly produced as a function of pH in pure water,i.e.,it can self-assemble into spherical micelles with PLGA-core at acidic pH and rod-like micelles with PLL-core at alkaline pH,accompanied with the coil-to-helix conformational transition of PLGA and PLL.The linear-dendron-like asymmetrical topological structure is believed to play an impotent role in the morphology formation of self-assembly nanostructures.关键词：Polyampholyte;Poly(amino acid);Dendron;pH responsible;Schizophrenic micellization
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发布时间：2021-03-19
Research Article
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