最新刊期
卷 ， 期 2 ， 2000
- 摘要：Using poly(styrene-co-maleic anhydride) as the backbone and poly(ethylene glycol) methyl ether as side chains,three kinds of comblike polymers of different side chain length were synthesized.The Lisalt complexes and their films were prepared.The dynamic mechanical properties were investigated.It was found that the main chain was rigid and the side chain was flexible in this comblike polymer system. Based on the time temperature equivalence principle,a master curve was constructed.By selecting Tα as reference temperature,Arrhenius plotrs of shift factor and iso-free-volume polts were attained.The values of WLF parameters C1 and C2 increase with increasing salt concentration. By reference to T0=50℃,the relation between the average relaxation time lgτn and Mw of side chains is also linear. And the master curves are movable with the change of salts.It shows the effect of different kinds of salt on relaxation time.
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发布时间：2021-03-19 - 摘要：The thermo oxidative degradation of polyamide 6 (PA 6) was investigated by means of detailed analysis of the reaction products. The changes in the contents of main groups produced in PA 6 during thermo oxidation were determined by chemical methods. The volatile products of PA 6 during thermo oxidation were collected and characterized by GC-MS. The hydrolysis products of oxidized PA 6 were also characterized by GC—MS.Experimental results showed that the hydroperoxide was the initial oxidation product of PA 6, and through its decomposition and further reactions,various oxidation products were formed,such as keton group and carboxylic group.From the analysis of hydrolysis products of oxidized PA 6,is was shown that a large amount of imide group was formed on the main chain.But at the same time some keton amide group[—CO—NH—（CH2）4—CO—CO—NH—] was also formed on the main chain.It means that although hydrogen-abstracting reaction by radicals mainly occurs at the methylene group adjacent to the nitrogen atom,is can occur at the methylene group adjacent to the carbonyl group of amide group as well.From the analysis of the volatile products,of great interest is that a lot of cyclic compounds,which had not been reported yet,were formed during thermo-oxidation of PA6.It indicates that some cyclization reactions should be included in the oxidation process of PA 6.On the basis of all the obtained experimental results a complete mechanism of PA thermo-oxidative degradation was suggested. The mechanism contains the hydrogen-abstracting reaction by radicals at the methylene group adjacent to nitrogen atom and at the methylene group adjacent to the carbonyl of amide group, a series of radical-addition-cyclization reactions,and radical induced chain-scission reactions.It can well explain the results of the product analysis.
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发布时间：2021-03-19 - 摘要：Metallocene, a newer generation of commercial polymerization catalysts for polyolefins, is best known for its “single sitednss”, and the intermolecular structural homogeneity of metallocene polyethylene copolymer is a very interesting research issue. The molecular segregation effects on the crystallization, melting and crystal morphologies of metallocene SCBPE have been investigated with DSC and TEM.The multiple endothermic peaks were observed in the DSC thermograms during heating experiments. The heterogeneity increases as branching content increases, the lamellae becomes thinner, and lamellae distribution becomes broder. Both macroscopic segregation (between two crystal aggregates) and microscopic setreation (between two lamellae)have been observed when SCBPE crystallized from phase separated melt.
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发布时间：2021-03-19 - 摘要：The aqueous solution polymerization of diallyl dimethyl ammonium chloride (DADMAC) with 2,2′-azobis(2-aminopropane) dihydrochloride as initiator was studied by means of adiabatic calorimetry in a well adiabatic 1.5L Dewar reactor equipped with an anchor stirrer.The temperature of the polymerization medium and the surroundings of the reactor was measured by temperature sensors (Pt-100) and online transmitted to a computer for further data processing.At first, a series of experiments were designed to prove the reliability of adiabatic calorimetry.The homopolymerization of methylmethacrylate(MMA) or styrene (St) initiated by dimethyl 2,2'-azobis(isobutyrate)in toluene was chosen because the polymerization mechanism of this system has been thoroughly studied and all data are already well known (the reaction order of monomers,MMA or St,was considered as m=1,and the reaction order of AZO-initiator used in this study was considered as n=0.5,ist decomposition was a first-order reaction without any by-reaction,so that p=1,γ=0).At 40～60℃ and in the atmosphere of helium,the monomer was polymerized,and the curves of fluid temperature versus time were obtained online,from which Eef,the overall activation energy of the reaction,can be simulated by the adiabatic calorimeter,the the kinetic and thermodynamic parameters Aef and (-△HR) can be calculated by numerical method with the help of the experimental parameters. The comparison between the simulated vaues and the published data proved that the method was easy and reliable.Thereafter,the polymerization of DADMAC system was further investigated,a series of temperature versus time curves were experimentally obtained by changing the initial cncentrations of monomer ([M])0=2.06～2.46mol/L)and the initial temperatures (T0=50～60℃).According to the adiabatic calorimetry the kinetic parameters were easily simulated:m,the order of monomer polymerization was 2.05,and Eef was 108.83kJ/mol,other parameters Aefand (-△HR)were obtained in the same way above. The results showed that the calculated values depending on the simulated kinetic and thermodynamic parameters were coincident with the experimental data.
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发布时间：2021-03-19 - 摘要：Plastic rods with gradient refractive index were successfully fabricated by the interfacial-gel polymerization technique,in which two kinds of dopants were used for their higher refractive index and different molecular volume.The effects of dopant concentration, the molecular volume and the temperature of polymerization on the refractive index profile of the preform rods were investigated in detail.Experimental results showed that the difference of the refractive index between the center and the periphery of the preform rod increased with increasing temperature due to the increase of the gel effect and polymerization rate at a higher temperature.The parabolic refractive index ditribution was slightly flatted at lower temperature mainly due to decreasing rate of polymerization,therefore there is more time for the dopants to diffuse into the gel.
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发布时间：2021-03-19 - 摘要：The sample chains of polyethylene were set up by Monte Carlo simulation according to the real bond length and bond angle of PE and the conditional probabilities of a certain segment staying in one or another rotational isomeric state under θ conditions. The conformational number, the mean square end-to-end distance and its components of tail chains were calculated and compared with those from exact enumeration and theoretical deduction. The results indicated that:1) the method of Monte Carlo simulation is more accurate and converges much faster,2) the ratio of R2∥>/R2⊥>approaches 1/2 when the number of segments is large. It is in accordance with the theoretical deduction of half-space lattice model.The variation of conformational numbers and components of mean square end-to-end distance with number of chain segments and bond angle was also discussed. With the increase of bond angle,the number of conformation also increases,but the ratio of R2∥>/R2⊥> does not change much.
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发布时间：2021-03-19 - 摘要：A π-conjugated soluble oligomer of propargyl acetate(OPAT) was synthesized with a novel palladium acetylide catalyst [Pd(C≡CCH2OOCCH3)2(PPh3)2](PPA). Its molecular weight (Mw) is 4500. Some features and kinetic behavior of PAT polymerization with PPA catalyst are described and discussed. The overall polymerization activation energy was found to be 110.2kJ/mol and the rate equation can be expressed as Rp=kp[PAT]1.5[PPA]1.5,where kp=6.58×10-4L2mol-2s-1.The oligomer (OPAT) doped with a solution of FeCl3 in THF exhibits humi-sensitivity. The impedance of doped OPAT (DOPAT) varis about two orders of magnitude (106～104Ω),when relative humidity (RH%) changes from 11% to 96%.
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发布时间：2021-03-19 - 摘要：A curing reaction model suitable for a novel liquid crystalline expoxy resin 4,4′-diglycidyl ether of azobisphenol/4,4′-diaminodiphenyl methane (DGEAP/DDM) system was established on the base of the principle of diffusion-controlled reactions. The reaction radius of the reactive group in DGEAP/DDM curing decreased with the increase of the extent of the reaction, which was the same as that in the curing of traditional epoxy resins. Because of the effect of orientation orders on the distribution of the reactive group,which was called the "pseudo-concentration effect",the concentration of the reactive group in the ordered domain was higher than that in the siotropic domain. It was confirmed by the comparison of the DGEAP/DDM system with the ordinary epoxy resin system that the pseudo-concentration effect does exist and affect the diffusion-controlled reaction kinetics.
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发布时间：2021-03-19 - 摘要：By using the method of transmission electron microscope (TEM) the fractal structures were found in the colloid aggregates and colloidal particles of the highly sulfonated polyaniline,which is an important processable conductive polymer.In the present paper the concept and the mathematical model of fractal have been introduced into the studies of conjugated polymers.The colloid aggregates appear as an open dendritic structure and its growing process can be analoged by the diffusion limited cluster aggregate (DLCA) model. The analog pattern by computer and the theoretic fractal dimension are consistent with the experimental results.Since the colloidal particle is generated in the flatterning field of the dispersion media,the screening effect is weakened,and the colloidal particle is a spheroidal structure,which is deser than the colloid aggregates.The random rain(RR)model can be applied here and the analog gragh is in agreement with the TEM image.
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发布时间：2021-03-19 - 摘要：The solution property of polyethylene grafted maleic anhydride in extremely dilute and dilute solutions is studied by the method of viscosity at high temperatures.A very sharp crossover is observed in the variation of the reduced viscosity.ηsp/C as a function of the concentration for polyethylene grafted maleic anhydride.This crossover is correlated with the critical concentraion of the polymer C** in which the macromolecular coils start their contacts.For extremely dilute solutions (CC**)ηsp/C changes lineary with concentration in a greater slope than that for dilute solutions (C>C**),This shows the different morphologies and interactions of macromolecular coils in the two regions.The reduced viscosity also increases when the grafted rate and the temperature increase,but C** inclines to lowr concentration with the increase of temperature.
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发布时间：2021-03-19 - 摘要：It was discovered that nano-Cu particles possessed high activity in acetylene polymerization.The composite which consisted of nano-Cu and acetylene-polymer was a kind of microfiber.According to the IR analysis,the molecular structure of nanometer fiber contained both conjugate —C＝C and saturated —CH2—, —CH3 groups.Nanometer fibers were easily oxidized in air,and there existed —C＝O and —OH groups in the molecular structure,which was consistent with the mechanism of traditional polyacetylene oxidation.Acetylene could grow orientedly on certain crystal surface or active sites of nao-Cu particles.Nano-Cu particles could be located at both ends and the middle of fibers based on TEM observations.
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发布时间：2021-03-19 - 摘要：Miniemulsion of styrene and butyl acrylate with sodium dodecyl sulfate (SDS) as surfactant and hexadecane (HDE) as cosurfactant was prepared under ultrasonification,then the miniemulsion copolymerization was carried out with a redox initiator ((NH4)2S2O8/NaHSO3) at lower temperature.The effects of temperature and concentrations of surfactant,cosurfactant,and initiator on the polymerization rate and conversion were determined.Under the same conditions,the polymerization rate of miniemulsion was lower than that of conventional emulsion and the initiation period was much longer.Polymerization rate increased with the increase of recreation temperature and the concentration of initiator,and surfactant.In a certain range,the polymerization rate increased with increasing HDE concentration.However,beyond that range,it decreased with increasing HDE concentration.By using computer treatment of the experimental data,a mathematical model was established for miniemulsion kinetics,then studied the kinetics characters in detail.By comparing with the results of conventional emulsion,a"monomer droplet nucleation"mechanism of miniemulsion was proposed.
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发布时间：2021-03-19 - 摘要：A ultraviolet spectrophotometric method for determination of molecular weight of macromonomer containing methylacryloyloxy end group was established,λ max was located at 213nm,95% alcohol∶THF(volume rate 7∶3) was used as the solvent and the molecular extinction coefficient of methylacryloyloxy end group was 6510L·mol-1·cm-1 .A series of macromonomer containing methylacryloyloxy end group (MA-PTHF-OH) was determined by two methods,the UV spectrophotometric method and the titration method.The relative error was less than ±5% between these two methods.The results of the two methods were also contrasted by statistical test.There was no significant difference between them.This method gives a convenient way for characterization of macromonomer containing methylacryloyloxy end group.
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发布时间：2021-03-19 - 摘要：A system for measuring nonlinear dielectric permittivity was set up. The nonlinear dielectric permittivities of thick PT/P[VDF(70)-TrFE(30)] 0-3 ferroelectric composite films have been measured at 1kHz at applied electric field ranging from 1 to 10MV/m.When PT volume fraction ∮ is greater thn 0.3,the dielectric permittivity ε1 of composites shows a distinct dependence on electric field.The Maxwell-Garnett equation is suitable for predication of ε1 when ∮ is less than 0.1.The Yamada model can be usedm to best fit the experimental results,while Bruggeman equation can only be used to predict ε1 at low electric field.The absolute value of the second order dielectric permittivity ε2 increases with increasing PT volume fraction.ε2 of the composites with both the ceramic and copolymer phase being poled (B2) is higher than that of composites with only the ceramic phase being poled (B1).The results show that the magnitude and direction of the remnant polarization of composite films can be determined by measuring ε2. In addition,ε2 is independent of electric field.The third order dielectric permittivity ε3 of composites also shows adependence on electric field.A higher electric field produces a lower ε3.The ε3 value of B1 is always higher than that of B2 for every PT concentration.
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发布时间：2021-03-19 - 摘要：The title graft copolymer was synthesized by a two-step polymerization process. In the first step the monomer of 2-ethyl-2-oxazoline (EOX) was polymerized by cationic ring-opening polymerization with MeOTs as initiator in toluene. The prepolymer of poly(N-propionyl-ethylenimine) (PEOX) having living propagating end of oxazolinium ion in toluene was obtained with average molecular weight less than 10,000g/mol .Then the EAA (ethylene-acrylic acid copolymer) was grafted through the reaction of pendant carboxy group of EAA with the terminated living oxazolinium ion of PEOX in toluene.The effect of various parameters such as reaction condition of cationic polymerization,grafting reaction time and temperature,reactive group in EAA and PEOX molar ratio,and carboxy group content in EAA on grafting degree and average degree of polymerization in the graft chain were evaluated.It was found that there was a maximum grafting degree of graft copolymers,when the EAA/PEOX molar ratio is in the range of 5～6.The graft copolymer EAA-g-PEOX with grafting degree>25% can be obtained under some specific conditions,such copolymer can be used as compatiblizer in PBT/PP blends to improve the compatibility of the two phases and the mechanical properties.
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发布时间：2021-03-19 - 摘要：To synthesize novel modified fibers from waste silk fibroin, gamma-ray induced graft of acrylonitrile onto silk fibroin in the solution of 60% ZnCl2 was carried out. The effects of absorbed dose, dose rate, copper ion, silk fibroin contents, monomer concentrations and “post effect” on monomer conversion, percentage grafting, grafting efficiency and average molecular weight of grafting polymer were examined. The grafting products were characterized with IR,TGA,DTA and other methods.It was found and discussed that the initial grafting efficiency is mainly determined by [S]/[S]+[M],where [S] and [M] are the concentrations of silk fibroin and monomer,respectively.Futhermore,the graft efficiency increases with the increase of absorbed dose.It was noticed that the existence of Cu2+ has a staong inhibition effect on the molecular weight of grafted chain,and almost no effect on percentage grafting and grafting efficiency.The thermodynamic properties of grafting products were much better than those of natural silk.
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发布时间：2021-03-19 - 摘要：A bromine capped polystyrene (PS-Br) with an Mn of around 5,000 was synthesized by using Cu(phen)2Br/1-PEBr as catalyst and initiator to polymerize styrene (St) according to atom transfer radical polymerization (ATRP) mechanism.Then, by using such a PS-Br as a macro-initiator,some block copolymers [P(St-b-MMA) and P(St-b-BA)] were also prepared through phen-ATRP.These block copolymers have been characterized by means of GPC,IR, 1H-NMR and DSC,respectively. It was found that there were no any homopolymers in these block copolymer systems and P(St-b-BA) exhibited a compatible system due to the short length of both blocks,although the miscibility between these two blcks was poor. By using phen/CuCl/RCl as catalyst and initiator,the explosive polymerization phenomenon of methacrylate (MA) was observed.However,the copolymerization of MA and iso-butyl vinyl ether (IBVE) could be controlled in ATRP.The obtained poly(MA-co-IBVE) was characterized and discussed by using DSC and 1H-NMR.
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发布时间：2021-03-19 - 摘要：Phase separation during the curing reaction in blends of diglycidly ether of bisphenol A,polysulfone and diaminodiphenylsulfone(DDS,curing agent) was studied. Effects of epoxy resins with different molecular weight on phase structure of the blends were investigated. The relation between the degree of conversion and reaction time revealed that vitrification and gelation greatly affected the formation of phase structure in the low molecular weight epxoy systems. When Tg of the epoxy-rich phase went up to the reaction temperature,both reaction and phase separation were suppressed.While in the high molecular weight epoxy systems, the viscosity increasing of epoxy resins played an important role. Although the degree of conversion of the epoxy-rich phase did not reach the gel point after 24h precure,phase separation was suppressed due to the high viscosity of the systems. SEM results showed that the desired phase structure could be achieced by using epoxy resins with different molecular weight.
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发布时间：2021-03-19 - 摘要：The pulverizing of polypropylene (PP) and the solid phase grafting of hydroxylmethyl-acrylamide (HMA) onto PP during Pan-milling were studied by means of fractal geometry.The particle size distribution of milled PP was determined by particle size analyzer,and the obtained data were analyzed by fractal theory.The results showed that there was a non-scaling region in PP particle size distribution,a feature of linear fractal.Pan-milling affected the fractal behavior of PP particle size distribution quite a lot.The fractal dimension value of PP particles in creased with increase of milling cycles,and the size reduction of PP particles became more pronounced with the larger particles.Also the experimental results of the solid phase grafting of hydroxymethyl-acrylamide (HMA) onto PP revealed that the grafting rate increased with increase of milling cycles and was,therefore,related with the change of the fractal dimension value.Obviously,fractal geometry is useful for study of the quite complicated process of solid state mechanochemical reactions of polymers such as pulverization of PP particles and solid phase grafting of HMA onto PP during pan-milling.
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发布时间：2021-03-19 - 摘要：The poria cocos mycelia samples were cultured in media at 25℃ for one week.Four polysaccharides coded as PCM1,PCM2,PCM3 and PCM4 were isolated from the poria cocos mycelia by using 0.9% NaCl aqueous solution,hot water,0.5mol/L NaOH aqueous solution and 88% formic acid,respectively.The components and structure of the polysaccharides were analyzed by infrared,gas chromatography,high performance liquid chromatography and 13C nuclear magnetic resonance.The results show that PCM1 and PCM2 consist of D-rhamnose,D-fucose,D-xylose,D-mannose,D-galactose,D-glucose and D-glucuronic acid,and the D-glucose content increases with the progress of isolation.PCM3 is mainly linear β-(1→3)-D-glucan and the major fraction of polysaccharides fron the poria cocos mycelia (yield 55.8%).PCM4 is composed of D-glucose with a few glucuronic acids.It is summarized that the coomponent and structure of the polysaccharides from poria cocos mycelia are similar to those from poria cocos sclerotium.
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发布时间：2021-03-19 - 摘要：Thermal stimulated current/relaxation map analysis (TSC/RMA) is applied to study 2′-thiazole-4-(N,N-dimethyl)amino azobenzene/polycarbonate (TDAA/PC) system in an attempt to understand the influence of the dye doping content on the glass transition of the system.When the doping level increases to 4% (weight percent),the low temperature tail of glass transition extends to 95℃ and the temperature range of glass transition increases to 35℃.The observation of the cooperative relaxation in a quite wide temperatue range indicates that the dipolar relaxation of the dye is principally controlled by the glass transition at temperature tens degrees below Tg.
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发布时间：2021-03-19
Research Article
- 摘要：The synthesis of polymer complex based on sodium polyacrylate (PAS) with different mean degree of polymerization and polycation derived from poly(styrene-4-vinyl pyridine).The effects of the ratio of charge quantum between polycation and polyanion,charge density of polycation,molecular weight of PAS,added inorganic electrolyte such as sodium chloride on the formation of complex were studied.The interaction between the polycation and polyanion was studied by spectrophotometry and conductometric titration.
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发布时间：2021-03-19 - 摘要：The kinetics of acrylamide (AAM) polymerization initiated by diperiodatonickelate(Ⅳ) periodate complex was studied in aqueous alkaline medium.The results indicate that the equation of the polymerization rate is as follows:Rp=k[Ni(Ⅳ)]0.72 [AM]1.41 and the overall activation energy of AAM polymerization is 41.33kJ/mol.The polymer molecular weight decreases with increasing [Ni(Ⅳ)] and increases with increasing [AAM].The effects of various reaction conditions on the polymerization rate were also studied.The initiation mechanism was proposed.
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发布时间：2021-03-19 - 摘要：Calix[4]titanium in combination with Al(iBu)3 formed a homogeneous catalyst system.This homogeneous catalyst system was found to be an active catalyst system for the polymerization of ethylene.The effects of Al/Ti molar ratio,solvent,concentration of catalyst and polymerization temperature on the polymerization were studied in detail.Polyethylene having Mw of 9.4×105 is obtained under following conditions:[Ti]=5×10-4 mol/L,Al/Ti=20,T=35℃,t=1h,ethylene pressure=1.0MPa.The catalytic activity is 60.7kg PE/mol Ti·h. Other alkyl aluminums as cocatalysts were also investigated.For various alkyl aluminums the catalytic activity decreased in the following order: AlEt3>Al(iBu)3>AlEt2Cl>Al(iBu)2Cl.
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发布时间：2021-03-19 - 摘要：The thermal decomposition behaviors of four chemically modified polyethylene were investigated by high resolution pyrolysis gas chromatography-mass spectrometry (HR PyGC-MS).The results revealed that substituents attached to maleated polyethylene as amides formed from secondary amines are significantly less stable than imides formed from primary amines.N-methylaniline amide-derivatives of maleated polyethylene undergo significant decomposition at 160℃ and substantial decomposition at 200℃.In contrast,the imides (except aniline imide) derivatives of maleated polyethylene are stable for long periods of time at 160℃,and the decomposition of phenethylamine imide-,9-aminomethylphenanthrene imide-derivatives in initiated slowly at 255℃ and 280℃,respectively.The effect of different modified groups on thermal stability of the polymers was discussed based on the qualitative and quantitative determination of the products.The thermal degradation pathways for the above chemically modified polyethylene were suggested.
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发布时间：2021-03-19 - 摘要：Surface analysis of a H2O2-bleached thermomechanical pulp (BTMP) exposed to light irradiation were carried out by using X-ray photoelectron spectroscopy (XPS) to characterize the photochemical reactions on surfaces of the pulps.The XPS analysis revealed that the formation of the quinonoid structures and the richment of extractives onto the outermost surface of the pulps were responsible for the discoloration.The photochemical reactions mainly occurred on the outermost surfaces(less than 10nm) of the plant fibers.
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发布时间：2021-03-19 - 摘要：Scanning electron microscopy and transmission electron microscopy were employed to study the two-phase morphology of the conductive polyaniline/Nylon-11 fibers.By analyzing the transverse cross section,the axial section and the surface micrographs of the monofilament with 20% polyaniline,it was shown that the two blend components were incompatible and partly stripped.Comparison was made for polyaniline/Nylon-11 and carbon black/PET systems.The former had higher electric conductivity and lower percolation threshold than the latter.The formation of fibril morphology of polyaniline in the conductive fibers was valuable for producing more perfct conductive channels.Nylon-11 was the continuous phase and contributed to the mechanical properties of the fiber.
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发布时间：2021-03-19 - 摘要：Mesogen-Jacketed liquid crystalline polymers were synthesized in various chiral conditions using 1) (-)-menthol as a reaction solvent (additive),2) (-)-dimenthyl peroxydicarbonate as a chiral free radical initiator,3) menthyl methacrylate as a comonomer for copolymerization,4) (-)-sparteine-fluorenyllithium as a chiral anionic initiator and 5) a chiral monomer.In the polymerization using a chiral initiator or a chiral solvent,the helix-sense-selection was not found.In the case of the copolymerization,the chiral monomeric unit incorporated into the polymer chain was found to induce liquid crystallinity.Chiral mesogen-Jacketed polymer was also synthesized from chiral monomer 5.However,this polymer did not form a liquid crystal phase although it met the model of Mesogen-Jacketed liquid crystalline polymers.
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发布时间：2021-03-19
Research Bulletin
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