最新刊期
卷 ， 期 3 ， 2010
- 摘要：Oxyanion-initiated polymerization has been greatly developed in recent years. The monomers have been expanded from methacrylate monomers with a β-positioned donor group in the ester moiety to oxetane monomers and methacrylate monomers with hydroxyl group, and some novel hybranched polymers are obtained.The new progress of oxyanion-initiated polymerization, and its mechanisms and applications in the synthesis of hybranched polymers are summarized in detail
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发布时间：2021-03-19
Reviews
- 摘要：A series of sulfonated poly(phthalazinone ether sulfone ketone) copolymers, SPPESK-DMs, with different degree of sulfonation (SD) were synthesized by polycondensation of 4-(3,5-dimethyl-4-hydroxyphenyl)-2,3-phthalazinone, 3,3′-disulfonate-4,4′-difluorobenzophenone and 4,4′-dichlorodiphenylsulfone, which were potentially utilized as membranes in proton exchange membrane fuel cells (PEMFC). The high molecular weight sulfonated polymers (SPPESKDMs) with the inherent viscosity ranged from 1.36 dL/g to 6.04 dL/g were obtained when the sulfonation degree of samples varied from 0.2 to 1.0.The yellow transparent membranes cast from N-methyl-2-pyrrolidone solutions of SPPESK.DMs were obtained. The chemical structure of the sulfonated polymers was characterized by FTIR and 1H-NMR, the thermobehavior of polymers was also investigated by TGA, and the properties of the membranes were investigated too.The results indicated that the decomposition temperatures of the sulfonic group and the main chain in the SPPESK-DMs copolymers were above 260℃ and 410℃ respectively, which demonstrated the copolymers had excellent thermal stability.The water uptake, swelling ratio, ion exchange capacity and proton conductivity increased with increasing of temperature and SD The proton conductivity of the SPPESK-DM50 with the SD of 1.0 was 1.08×10-2 S/cm at 85℃, which was considerably lower than that of Nafion 117, but would meet the lowest requirement in PEMFC application.The methanol permeability values of SPPEK-DMs membranes were lower than that of Nafion117. The oxidative stability of the SPPESK-DMs membranes was better than that of SPPEK or SPPESK membranes, and the expended time that membranes started to break into pieces at 80℃ in Fenton’s reagent was longer than 4.33 h.
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发布时间：2021-03-19 - 摘要：A series of core-shell microgels with a poly-(N-isopropylacrylamide) (PNIPAM) core and a poly-(N-isopropylacrylamide-co-acrylic acid) (P(NIPAM-co-AA)) shell were synthesized. The shell thickness increases with the increasing feeding of the shell solution. The thermosensitive phase transition behavior of these microgels was studied at pH=3.5. Only one phase transition was observed because the volume phase transition temperature (VPTT) of the core was close to that of the shell. Phenylboronic acid (PBA) groups were introduced by EDC coupling of 3-aminophenylboronic acid with carboxylic acid in the shell of the microgel. Three phase transitions were observed in the PBA-modified core-shell microgels. The first one was attributed to the transition of the shell, while the second and the third transitions reflected a heterogeneous structure of the core which originated from the fast incorporation of the BIS crosslinker during precipitation polymerization. The VPTT difference between the BISrich “core” and the BIS-poor “shell” was enlarged by the coverage of the hydrophobic P(NIPAM-co-AMPBA) shell. The glucose-sensitivity of the PBAmodified core-shell microgels was revealed by their increasing hydrodynamic radii in the presence of glucose, however, the increase in particle size was limited because of the non-glucose-sensitive core. The phase transition behavior of the PBA-modified core-shell microgels in the presence of glucose was also studied. With increasing glucose concentration, the VPTT of the shell increased and approached to that of the core. As a result, the coreshell microgels presented only one transition at high glucose concentrations.
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发布时间：2021-03-19 - 摘要：For application in direct methanol fuel cells, a series of SPEEK (sulfonated polyether ether ketone) membranes with different sulfonation degrees were tested, and a novel acid-base composite proton exchange membrane was prepared- SPEEK and chitosan were chosen as acidic and basic polyelectrolytes respectively. The properties of composite membranes, such as proton conductivity, methanol permeability, water uptake, membrane swelling and thermal stability, were tested- Although the proton conductivity reduced to some extent and the methanol permeability wasn’t improved, the water uptake and membrane swelling were significantly improved-Particularly, after chitosan was blended with SPEEK (sulfonation degree=71.4%) at a molar ratio of 1∶5, the prepared composite membrane exhibited comparable performances with Nafion 117, and such membranes are thus promising for application in fuel cells.
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发布时间：2021-03-19 - 摘要：The molecular rheological characteristics of branched polymer melts (low density polyethylene, LDPE) are described by the extended Pom-Pom (XPP) model based on the tube theory, which results in the bridging scale simulation from the molecular-scale structure to macroscopic flow responses. The finite increment calculus (FIC) procedure is introduced to reformulate the mass conservation equation and to overcome spurious oscillations of pressure field due to incompressibility of fluids. In order to retain an elliptic contribution in the weak form of the momentum equation in the absence of a purely viscous contribution or as the viscous contribution is negligible in comparison with the viscoelastic contribution, the discrete elastic viscous stress splitting (DEVSS) technique is employed. Inconsistent streamline-upwind (SU) method is applied to spatially discretize the constitutive equation of the XPP model with modified stretch dynamics. Moreover, mass, momentum and constitutive equations are discretized and solved by the iterative stabilized fractional step algorithm based on Crank-Nicolson implicit difference scheme. Thus the finite elements with equal low-order interpolation approximation for velocitypressurestress variables are adopted to calculate the 4∶1 planar contraction transient viscoelastic flows. The influences of Weissenberg number, the amount of branched-arms (q) at the end of the Pom-Pom molecule and the molecularscale structure parameters on the rheological behavior generated in this complex flow are discussed. Numerical results demonstrate good agreement with those given in the literatures.
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发布时间：2021-03-19 - 摘要：A novel polyester P(DHCA-co-LA) based on 3，4-dihydroxycinnamic acid (DHCA) and D，L-Lactic acid (LA) was synthesized by the thermal polycondensation method.The structures and molecular weight of P(DHCA-co-LA) copolymers were characterized by Flourier transform infrared spectroscopy (FTIR)，nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC). Obvious changes of molecular weight and molecular weight distribution could not be observed when the ratio of DHCA to LA was varied.The thermal and optical properties of the copolymers were investigated by differential scanning calorimetry (DSC)，UV spectroscopy and fluorescence spectroscopy.It was found that the P(DHCA-co-LA) copolymers showed evident glass transition temperature (Tg).Tg of the copolymers decreased from 132.3℃ to 99.1℃ as the LA content increased from 0 to 50 mol%.The fluorescence spectroscopy indicated that P(DHCA-co-LA) copolymers had the strongest fluorescence emission at LA content of 20 mol%.The copolymer solutions exhibited a maximum absorption at 302 nm due to cinnamoyl groups, and the absorption decreased with increasing the UV-irradiation time，indicating that the cinnamoyl group could undergo a photochemical reaction.But the rate of cross-linking reaction is low，which would be responsible for the branched polymer chains.The cross-linked particles with diameter of about 20 μm still have good fluorescence after 65 min UV-irradiation.The X-ray diffraction (XRD) results showed that P(DHCA-co-LA) copolymers were amorphous and these copolymers may have good biodegradable performance.Copolymer rectangular samples，which were buried in soil for 5 months degradation experiments showed that the more LA contents in copolymer，the slower degradation rate of the copolymer，so the speed of copolymer degradation could be controlled.
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发布时间：2021-03-19 - 摘要：Thermal sensitive polyurethane (TSPU) membranes were prepared by wet phase inversion technique，and used for selective separation of substances with different molecular sizes.According to differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analysis，it was found that the TSPU showed segmented structure and separate phase transition temperatures of soft segment phase and hard segment phase (the phase transition temperature of the soft segment phase was defined as the switch temperature，Ts).Polarizing optical microscope (POM) analysis showed that the soft segments of TSPU had a clear spherulite morphology at low temperatures (Ts).However，when the temperature exceeded Ts，the crystall of soft segments melted gradually and disappeared.The morphological structure of membranes was observed by scanning electron microscope (SEM) and atom force microscope (AFM)，the results indicated that the membrane showed relatively dense surfaces (or skin) and porous cross sections.The porosity of membranes measured by the mass loss of wet membranes after drying revealed that when the temperature increased from Ts-10℃ up to Ts+10℃，the porosity of membranes increased from 46.7% to 65.3%，showing a significant feature of thermal stimulation.When this TSPU membrane was used for separation of substances with different molecular sizes，we found that the ions of Na+ and Cl－(with small size) could permeate the TSPU membrane at any temperature，and higher temperature resulted in higher penetration rate.Whilst the penetration of glycin (with moderate molecular size) relied on the temperature variation.To be specified，at lower temperatures (T＜Ts)，the glycin permeation flux was very low，but when the temperature exceeded Ts，the permeation flux of glycin increased markedly，showing sensitivity to thermal stimuli.Collagen，due to its large molecular size，could not permeate the TSPU membrane in all temperature range.As a result，substances with different sizes could be selectively separated by the TSPU membrane under temperature controlling.
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发布时间：2021-03-19 - 摘要：The crystallization and the phase morphology of polypropylene/poly(methy methacrylate)(PP/PMMA) incompatible blends were studied by using polarizing microscopy and discrepancy microscopy.Polypropylene-g-malaie anhydride(PP-g-MAH) was used as a compatibilizer for PP/PMMA blends，the results from the polarized micrographs showed that PP crystalline form became incomplete and PP crystal size decreased because of the crystallization of PP conquering more energy barrier. The results showed that the compatibility of PP and PMMA phases became better，and the interface areas between PP and PMMA phases became unclear in the PP/PMMA/PP-g-MAH blends.When the MAH graft yield of PP-g-MAH was increased，the size distribution of PMMA phase became uniform and the size of PMMA phase decreased.When the graft yield of PP-g-MAH was 2.41 wt% and the concentration of PP-g-MAH in PP/PMMA/PP-g-MAH blends was 4.71 wt%，the size of PMMA dispersed phase showed a minimum value.PP-g-MAH was a reactive compatibilizer，on the one hand，PP segments of PP-g-MAH and PP homopolymer were crystallized together; on the other hand，the acid anhydride groups of MAH were linkaged with the ester groups of PMMA by covalence.The conformation of PP-g-MAH in the interface between PP and PMMA phases decreased the whole system entropy and improved the compatibility of PP/PMMA blends.PP/PMMA and PP/PMMA/PP-g-MAH blend was isothermal crystallized at 130℃.The polarized micrographs showed that the PP crystallization for the PP/PMMA blend exhibited the characteristics of homogeneous nucleation; and PP crystal size for PP/PMMA blends was larger than that for PP/PMMA/PP-g-MAH blend.PMMA phase size for PP/PMMA blend after isothermal crystallization at 130℃ was obviously larger than the corresponding PMMA phase size under non-isothermal crystallization.
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发布时间：2021-03-19 - 摘要：The relaxation behavior of neat PET and PET/SiO2 nanocomposites was investigated by using methods of internal friction and DSC.The activation energy of β relaxation was calculated by Arrhenius equation because it was a Debye peak，but the α relaxation didn’t follow the Arrhenius equation，so its activation parameter was calculated by VFT equation.The heights of the α and β peaks were obtained by the results of internal friction measurements.The results showed that the heights of peak，activation parameters of the α relaxation and activation energy of the β relaxation increased with increasing the content of filler.On one hand，SiO2 nanoparticles had grafting reaction with carboxyl，so the motion of polymer chains and groups was more and more difficult with increasing the content of filler.On the other hand，the nanoparticles acted as nucleating point，so they could promote the nucleation and crystallization of PET, and the amorphous regions decreased.The peak heights of the α and β relaxations were related to the normal amorphous regions，so both of them obviously decreased with increasing the content of filler.Hence the relaxation properties of PET chains and groups were changed by addition of SiO2 nanoparticles.
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发布时间：2021-03-19 - 摘要：A novel approach to prepare pH- and thermo-sensitive hollow spheres based on a precipitation polymerization method has been demonstrated.The poly(Nisopropylacrylamide) (PNIPAM) nuclei formed in the nucleation stage played the role of non-cross-linked templates，on which cross-linked poly(N-isopropylacrylamide-co-acid) (P(NIPAM-co-AA)) shells were formed by adding a cross-linker N,N′-methylene-bisacrylamide and acrylic acid to the aqueous solution during the following nucleus-growing stage.A “selfremoving” process was found to take place when the temperature of the reaction solution was reduced below the LCST，where the non-cross-linked PNIPAM nuclei spontaneously penetrated through the cross-linked shells to form the hollow spheres.The hollow structure was confirmed by TEM analysis.The zeta potential analysis indicated that，the shells of these hollow spheres contained carboxylic groups derived from the polymerized acrylic acid.These hollow spheres were characterized by light scattering analysis at various pH and temperatures.The results indicated that these hollow spheres could well respond to the change of pH and temperatures.As the pH increased from 2 to 7，the volume of the hollow spheres with 4.76% and 9.09% AA contents increased by about 12 and 18 times，respectively.As the temperature increased from 25℃ to 40℃，the volume of the hollow spheres with 476% AA content decreased by about 12 times.
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发布时间：2021-03-19 - 摘要：A conductive polymer, the conductive master batch, was prepared by melt blending of poly-(ethylene glycol) (PEG) with KI and poly(ethylene terephthalate) (PET).The specific resistance of the conductive polymer was about 105Ω・cm at normal temperatures, and the value of specific resistance decreased with increase of temperature.It shows the characteristics of ionic conductivity.The conductive polymer was measured by FTIR,DSC and polarized optical microscope. The PEG and PET were uncompatible in crystalline regions.In amorphous regions they were partially compatibille.In the cooling process after melt blending,KI/PEG formed a continuous phase by reason of phase separation.The conducting fiber was made by melt spinning the blends of PET with different amounts of the conductive master batch.When the content of the conductive master batch was over 10 wt% in fiber,the specific resistance of the fiber was about 106 Ω・cm and the wash-fast property was good.In this conducting fiber，the conductive master batch and PET form a co-continuous phase. The continuous banded structure formed by the conductive master batch endows the fiber with conductive property，and the PET matrix vests the fiber good mechanical properties.
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发布时间：2021-03-19 - 摘要：A novel kind of biodegradable glucose-sensitive polyphosphazene hydrogel has been prepared basing on both the chemical crosslinking and the specific interaction between polymerbound glucose and concanavalin A (Con A).Glucosyl-co-methoxyethoxyl-co-2-(2-aminoethoxy)ethoxyl substituted polyorgano-phosphazene was synthesized by subsequently nucleophilic substitution of polydichlorophosphazene with 2-［2-((tert-butoxycarbony1)amino)ethoxy］ethanol，diisopropylidene D-glucose and methoxyethanol，which was followed by deprotection treatment with trifluoroacetic acid to restore glycosyl and free amino groups.A chemical crosslinked hydrogel was obtained by reacting the above polymer with glutaraldehyde.The polyphazene hydrogel showed good swelling behavior in phosphate buffer solutions，and exhibited glucose-sensitive water absorption after Con A being loaded.No macroscopic deformation could be observed by immersing the Con A-loaded polyphoaphzene hydrogel into aqueous solution with high content of glucose for the presence of chemical crosslinking.The release rate of insulin from this polyphosphazene hydrogel depended on the concentration of free glucose in medium obviously.As the glucose concentration was increased from 1 mg/mL to 4 mg/mL，the release rate of insulin from the hydrogel increased，whereas，the release rate decreased when the glucose concentration was reduced to 1 mg/mL.The results demonstrated the possibility of using chemical crosslinked glucose-bearing polyphosphazene to prepare glucose-sensitive hydrogels in combination with Con A and to regulate the insulin release as a function of the free glucose concentration in the environment.
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发布时间：2021-03-19 - 摘要：In order to eliminate the disadvantageous effect of surfactant on relative molecular mass and post-treatment in preparing fluorinated hydrophobically associating polyacrylamide (FPAM) by free radical micellar copolymerization and to increase compatibility of fluorinated monomer and AM,fluorinated surfaceactive monomer (FSM) was synthesized by IPDI,dodecafluoroheptanol (FOH) and allyl polyethylene glycol (APEG) and copolymerized with AM by aqueous solution polymerization,then FPAM was achieved without post-treatment.The micellization of FSM was determined by surface tension.Rheometer,dynamic laser scattering (DLS) and atomic force microscope (AFM) were used to characterize rheological behaviors,size and morphology of the associative structure in FPAM solution,respectively.The results show that the critical micelle concentration (CMC) of FSM is 1.28 g・L-1 at 25℃,and the according surface tension γCMC is 26.77 mN・m-1 which displays that FSM possesses higher surface activity.FPAM solutions are belong to pseudoplastic fluid and have salt resistance to some extent.At the same time,the critical associating concentration of FPAM solution is 0.660%.Indicated by DLS and AFM,there exists an associative structure in FPAM solutions,even the concentration is lower than the critical associating concentration.Therefore,the FPAM molecules have strong hydrophobic association.
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发布时间：2021-03-19 - 摘要：A CTV (cyclotriveratrylene) derivative with 11-hydroxyl-undecyloxide group as peripheral group (CTV-H) was synthesized by trimerization Then another CTV derivative with single methacrylate group as peripheral group (CTVM) was synthesized and purfied by silica gel column chromatography, purification is the key step of this synthesis. Their chemical structures were verified by 1H-NMR, 13C-NMR, element analysis and mass spectroscopy- Both CTV-H and CTV-M are new thermotropic bowlic liquid crystals. They all demonstrated liquid crystalline textures under polarized optical microscope (POM) at room temperature.The DSC determination showed the glass transition temperature, and the clearing point of CTV-H was -20℃ and 49℃, respectively. But a wide endo-thermal DSC peak of -16~78℃ mixed up the contributions of the glass transition temperature, clearing point and curing temperature of CTV-M. Their SAXS and WAXD peaks appeared at 2θ=3.0°, 5.0°, 6.0°, 21.0° and 2θ=2.7°, 4.6°, 5.5°, 20.5°, respectively.The results indicated that their mesophase all belongs to hexagonal columnar phase （Φh）. The diameter of the column was 4.4 nm and 4.8 nm，respectively, which agreed with the results of theoretical calculation. CTV-M was used as a monomer to synthesize polymethacrylate containing bowlic CTV side groups （BPM）by means of bulk polymerization.The number average molecular weight of BPM (GPC) was 14900, and the glass transition temperature of polymethacrylate main chain and β relaxation temperature of CTV side groups were measured to be 104℃ and 6℃, respectively-However, BPM had no liquid crystalline behavior, which presented amorphous state
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发布时间：2021-03-19 - 摘要：Trinitrotoluene (TNT) molecularly imprinted polymer microspheres were prepared by precipitation polymerization with TNT as template and ethylene glycol dimethylacrylate (EDMA) as crosslinker. The influences of reaction conditions，including the amount of solvent and template and the category of the functional monomer on morphology and adsorption properties of molecularly imprinted microspheres were studied. The interactions of the binding sites were determined by UV-Visible absorption spectrum, and the structure of the cavities in the microspheres was studied by BET method. The adsorption and recognition ability of the molecularly imprinted polymer microspheres were detected by equilibrium adsorption experiments and selective adsorption experiments. The result revealed that the molecularly imprinted polymer with acrylamide as functional monomer had the shape of regular microspheres with molecularly imprinted cavities inside, and the diameters of the microspheres were about 1 μm to 2 μm. The molecularly imprinted microspheres showed fast adsorption speed, high adsorption capacity and good recognition property. The adsorption equilibrium can be reached within 30 min, the equilibrium adsorption amount in 1 mmol/L TNT solution was 32.5 mmol/kg, and the partition coefficient of the microspheres adsorbing TNT was 25.19.
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发布时间：2021-03-19 - 摘要：Polyamide/polypropylene (PA1010/PP) blends were prepared by melt mixing using maleic anhydride-grafted ethylene-octene copolymer (POE-g-PMAH) as a reactive compatibilizer.The compatibilizing effects of POE-g-PMAH on PA1010/PP blends were investigated by means of scaning electron microscopy (SEM), mechanical testing, Fourier transform infrared spectroscopy (FTIR) and differential scaning calorimetry (DSC), respectively. It was found that the addition of POE-g-PMAH could decrease the size of the dispersed PP particles, when the mass ratio of PA1010/PP/POE-g-PMAH = 70/30/15, the domains showed a fine and uniform dispersion in the matrix. FTIR results showed that the anhydride carbonyl groups of POE-g-PMAH reacted with the end groups of PA1010 in the blending process. DSC results showed that addition of POE-g-PMAH decreased the crystallization temperature and crystallinity of PA1010 and PP in the blends, indicating that POE-g-PMAH had an inhibition effect on the crystallization of PA1010 and PP. Mechanical testing indicated that with increasing the POE-g-PMAH content, the Izod impact strength of dried samples increased gradually, when the content of POE-g-PMAH was 15%, the Izod impact strength of dried samples was 21.13 kJ/m2 , which is 3.1 times that for the binary PA1010/PP blend. Meanwhile, the flexural strength, tensile strength and modulus can be maintained at a relatively high level.The compatibilization mechanism of POE-g-PMAH lied in the chemical interactions occuring between the terminal amino groups of PA1010 and anhydride of MAH in POE-g-PMAH during the melt mixing, and the compatibility between PP and ethyleneoctene of POE in POE-g-PMAH. Hense the addition of POE-g-PMAH decreased the interfacial tension and the domain size dramatically, improved the mechanical properties greatly.
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发布时间：2021-03-19 - 摘要：The isothermal flow induced crystallization (FIC) of isotactic polypropylene (iPP) under large amplitude oscillation shear fields was studied by rotational rheometer. The sinusoidal-strain dynamic shear flow of different amplitudes was performed on the undercooling iPP melts. Experimental results showed that, in comparison with the case for a small amplitude oscillation, the storage modulus of the melt would increase within a short period when a large amplitude oscillation was performed on the melts. This fact is attributed to that the large amplitude oscillation shear field is able to accelerate the crystallization kinetics of iPP significantly. Moreover, the larger strain performed on the melts would inevitably result in a more prominent acceleration of the iPP’s crystallization kinetics. Thus the rapid rise of the crystallinity of the melt directly gives rise to a more evident change of storage modulus. The Fourier transformation method was employed to analysis the stress waveform during the crystallization of iPP melts under large amplitude oscillation shear. It was found that the transition change of the ratio (I3/I1) of the peak value at triple-fundamental frequency I3 to the peak value at fundamental frequency I1 was sensitive in characterizing the FIC process of iPP melts when the change of the non-linear mechanical property occurred in the melt during crystallization. In addition, at a crystallization temperature of 140℃, the onset time corresponding to the abrupt increase in I3/I1, a little longer than the time when the storage modulus increased remarkably, decreased from 2500 s to 600 s as the amplitude of strain increased from 10% to 30%.
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发布时间：2021-03-19 - 摘要：The design and preparation of organic soft ferromagtnets by sol-gel processing is reported in this paper. ［γ-(2-Thiazole-ureido)propyl］methyldiethoxysilane (TUPMDES) was firstly sythesized. Polysiloxane (PTUPMDES) and complexes (PTUPMDES-Cu, PTUPMDES-Ni) were prepared via sol-gel process, respectively . They were characterized by IR, 1H-NMR, SEM and MS. The structure of the complexes was characterized by FTIR, which suggested that chelation had taken place and was demonstrated by the shift of the characteristic absorption bands. The magnetic properties of these complexes were measured using a physical property measurement system (PPMS 29), which included magnetization versus temperature, magnetization versus applied field, magnetic susceptibility versus temperature and magnetic hysteresis. The temperature was ranged from 5 K to 300 K, and the intensity of magnetic field was in the range of -4×106 ~ 4×106 A/m. It was found that these complexes were organic soft magnets and had typical “S” shaped magnetic hysteresis loops. The saturation magnetization of PTUPMDESCu, PTUPMDESNi and PTUPMDES-DMS-Ni was 4.39 emu/g, 5.75 emu/g, 5.27 emu/g, and their remanence magnetization and coercivity were 0002 emu/g, 0.003 emu/g, 0.002 emu/g and 1510 A/m, 1565 A/m, 1293 A/m, respectively. While the paramagnetic Curie temperature was 168 K, 163 K, 263 K. It was discovered that the Curie-Weiss temperature almost increased twice, when the dimethylsiloxane segments were introduced into the polysiloxane chains containing thiazole groups.
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发布时间：2021-03-19
Research Article
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