最新刊期
卷 ， 期 1 ， 2002
- 摘要：A novel hydrophobic comonomer diallyllaurylamine(DALA) has been prepared by tertiary amination of laurylamine and allylchloride in THF,and a series of the hydrophobically-modified amphoteric cellulosic graft copolymers(CGAL) of carboxymethylcellulose (CMC) with acrylamide (AM) and DALA have been synthesized employing potassium persulfate and dimethylaminoethyl 2-methacrylate as initiators in the mixed solvent of distilled water and DMF for the first time．DALA was characterized by means of FTIR,1H-NMR,MS and elemental analysis．The graft copolymerizations were investigated as a function of degree of substitution and concentration of CMC,concentration of AM,DALA and initiators,temperature and pH．CGAL was analyzed through FTIR．The composition and molecular weight of CGAL were determined making use of colorimetric titration,elemental analysis and gel permeation chromatography．Thermostability of CGAL and its aqueous solution was studied by thermogravimetry and viscometry．It has been shown that CGAL is biodegradable．
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发布时间：2021-03-19 - 摘要：Free radical melt-grafting of the multi-monomer system of maleic anhydride(MAH)／styrene(St) onto polypropylene(PP) has been studied by means of a single-screw extruder．It has been proved that the grafting degree and the melt flow rate (MFR) of the grafted PP both reached maximum points when molar ratio of the two monomer was 1:1．Monomer concentration and DCP content were found to have different effects on grafting level of the grafted PP obtained in systems with different concentration ratio of MAH to St．Besides,the MFR values of the grafted PP decreased with increasing monomer concentration and increased with increasing DCP content．The multi-monomers melt grafted PP,i．e．PP-g-(MAH-co-St) was investigated for its properties．Excellent mechanical properties were obtained when suitable monomer concentration ratio,monomer concentration and DCP content were applied to the grafting system．
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发布时间：2021-03-19 - 摘要：The isothermal and nonisothermal crystallizations of glycidyl methacrylate／styrene (GMA／St) multimonomer melt-grafted polypropylene [PP-g-(GMA-co-St)] were investigated by DSC,crystals of the grafted PP were observed through polarized optical microscope．Avrami equation was used to analyze the kinetics of crystallization．The crystallization of the grafted PP was heterogeneous nucleated,and three dimensional growth of spherulites can be observed as in the case of neat PP．Compared to neat PP,the crystallization temperature(Tc) of the grafted PP increased 16～19℃ and the overall crystallization rate was accelerated dramatically．The grafts of GMA-co-St reduced the interfacial free energy of the surfaces of the crystal nuclei and promoted the heterogeneous nucleating．When the degree of grafting was not very high,Tc and overall crystallization rate of the grafted PP increased with increasing the degree of grafting．In the range of higher degree of grafting,with increasing the degree of grafting,Tc stopped rising and the overall crystallization rate was slowed down due to the severe obstruction of the grafts to the growth of the crystal．
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发布时间：2021-03-19 - 摘要：Butadiene(Bd) and isoprene(Ip) were copolymerized with TiCl4／MgCl2-Al(i-Bu)3 catalyst system．The effect of polymerizafion conditions such as feed ratio,temperature,Al／Ti mole ratio,Ti／M mole ratio and comonomer concentration on catalytic efficiency and intrinsic viscosity of the copolymers was investigated in details．The DSC results indicated that the products with low butadiene feed ratio(f01≤20％) were copolymers．IR and 1H-NMR spectra analysis of the copolymers showed that the copolymers were mainly trans-1,4-structure. Ip units of the copolymers had trans-1,4-contents above 98％ and Bd units had trans-1,4-cntents above 90％ and copolymerization conditions had little effects on micro-structure of the copolymers．It was found that the reaction activity of Bd was greater than that of Ip．
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发布时间：2021-03-19 - 摘要：The stimuli-response of hydrophilic-hydrophobic semi-IPN hydrogels consisted of polyacrylic acid (PAAc)／poly (N-dodecyl-4-vinyl pyridinium bromide) (QPVPD) under DC electric field was investigated．The QPVPD chains were entangled with the PAAc polymer network and were fixed in the semi-IPN hydrogels．Under the contact electric fields,the deswelling of the gel was observed in the anode side of the gel,which was attributed to the hydrophobic interaction．Under the non-contact electric field,the gel bars bend toward the cathode side in a weak alkaline solution (pH=9),but toward anode side in a weak acidic solution (pH=4)．These properties of the gel are related to both the change of hydrophilic interaction and hydrophobic interaction．
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发布时间：2021-03-19 - 摘要：The crystallite size,crystallinity(Xc) and chemical properties of the poly(cyanoarylether) (PCE) at various temperatures were studied by using wide angle X-ray diffraction(WAXD) and DSC．The results show that the crystallite size,crystallinity and Tm will rise with increasing the heat treatment temperature,the glass transition temperature(Tg) rises slightly first and approaches a constant value．We found the crystallinity of samples at various temperatures is lower than that of the original sample．The results show that the heat treated sample began to crosslink．If melting temperature rises,crosslinking will be more．
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发布时间：2021-03-19 - 摘要：Poly {6-[4-(4-cyanophenylazo)phenoxy]hexyl methacrylate} (PM6ABCN) was synthesized by the method reported before．After a simple casting film was made by removing the solvent on glass substrate,its photoinduced orientation behavior under temperature below Tg was studied．After studying the photoinduced orientation behavior of PM6ABCN film under irradiation of light at 366 nm,400 nm,and 436 nm,it is found that the ohotoinduced orientation process not only depends on the light intensity,but also on the temperature and the wavelength of polarized light used．The maximum degree of orientation below Tg can be obtained within 100 s under irradiation of polarized light of 20 mW／cm2 at 400 nm,and irradiation at 366 nm causes a lower degree of orientation than that by irradiation at 400 nm and 436 nm because relatively more cis isomer was produced in the steady state．
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发布时间：2021-03-19 - 摘要：In order to enhance the ionic conductivity of PEO based polymer electrolytes and improve the stability of the interface between the lithium electrode and the polymer electrolyte,PEO／LiClO4/nano-SiO2 composite polymer electrolytes were prepared by adding self-synthesized nanometric SiO2(NMSIO) or commercial nanometric SiO2 (MN1P and modified MN1P) powder into the PEO／LiClO4 complex．There was 1～2 orders of magnitude increase in the ionic conductivities for these composite PEO electrolytes．It could reach as high as 1.24×10-5S／cm at room temperature．There are two reasons of the increase in ionic conductivity．First,the addition of SiO2 powder can suppress the crystallization of PEO．Secondly,the interface between the SiO2 powder and polymer electrolyte also makes a contribution to the increase in ionic conductivity．PEO based composite gel electrolytes were prepared by the addition of plasticizer PC(propylene carbonate)／EC(ethylene carbonate) into the PEO based composite electrolytes．The ionic conductivity was increased by another two orders of magnitude．The highest one reached 2×10-3 S／cm at room temperature．A half-cell of Li | composite gel electrolyte | Li was assembled with the above mentioned composite gel PEO electrolyte．The variation of the AC impedance spectra with post-preparing time of the half-cell was measured．It was found that the AC impedance of the passivation layer increased quickly within l44 h,but stabilized gradually in the following time．It revealed that SiO2 powder could suppress the growth of the passivation layer between the composite gel PEO electrolyte and the lithium electrode．
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发布时间：2021-03-19 - 摘要：Polyaromatic ether sulfoxides were prepared by low temperature solution copolymerization of diphenyl ehter with thionyl chloride in the presence of aluminum chloride 1,2-dichloroethane and N-methylpyrrolidone．The effect of using N-methylpyrrol-idone with aluminum chloride and mole ratio of monomers upon polymerizaton reation was investigated．Properties of polymers were characterised by IR,DSC,TG,X-ray diffraction etc．The results showed that these polymers didn’t crystallize but had a high glass transition temperature (Tg)．The softening temperature was about 260℃ and there were two decomposition temperatures in the dynamic thermogravimetry．
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发布时间：2021-03-19 - 摘要：A well-defined graft copolymer of styrene(St) and n-butyl acrylate(BA) was synthesized by atom transfer radical polymerization(ATRP) with the copolymer of styrene and chloromethyl stryrene as macroinitiator,which was first synthesized by the nitroxide-mediated copolymerization of St and 4-chloromethyl styrene (CMS) at 130℃ with benzoyl peroxide／4-hydro TEMPO as initiator．The kinetics of the two kinds of “living”／controlled polymerization were also studied．These copolymers,i．e．P(St-co-CMS) and P(St-g-BA),were characterized by means of GPC,DSC and 1H-NMR,respectively．The average graft number and length of side chains for such a kind of graft copolymer were defermined．
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发布时间：2021-03-19 - 摘要：From a theoretical background similar to that of Ghedgaonkar’s,using a general description of breakup and the Smoluchowski theory of coalescence of droplets,a relation has been derived for estimating the dispersed phase droplet size during mixing of polymer blends in the steady state．The influences of dispersed phase concentration,shear rate and elasticity of polymers are studied．In a less concentrated system,the diameter of the droplets increases linearly with their concentration．In a more concentrated system,the coalescence effects become increasingly important,the simultaneous collisions of three and more droplets should be considered and the drop diameter versus concentration dependence becomes more complicated．In PS(dispersed)／PP(matrix) blend system,it was observed that the drop diameter continued to decrease up to a maximum shear rate of 128 S-1．In PS(matrix)／PP (dispersed) blend system,however,as the shear rate increased,the drop diameter initially decreased．At a critical shear rate,the diameter reached a minimum value,and beyond it,the diameter increased with shear．The elasticity ofpolymers plays a crucial role．
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发布时间：2021-03-19 - 摘要：The dynamic laser scattering (DLS) method was used to study the structure of polyacrylamide (PAAm) gel,whose crosslinker ratio ranged from 1.6％ to 4.8％ while the total monomer concentration kept constant at 2.66％. The data analysis method of DLS and the meaning of the analysis were studied intensively．The results of DLS experiments showed that there were two different phases with distinguishing dynamic correlation length (LC) in PAAm gels．Analysis based on the gelation mechanism revealed that the existence of the two kinds of phases in PAAm gels Was mainly due to the poor solubility of the crosslinker．The phase with LC about 85 nm was polymer rich phase formed by the microgel spheres in the pregel solution while the other with LC within 10～20 nm was polymer poor phase formed by the crosslinking area between those spheres．So the LC of polymer rich phase was its size and that of polymer poor phase was the mesh size of PAAm gels．The irregular distribution of the two kinds of phases would lead to the inhomogeneity,which increased significantly with crosslinker ratio because the increase of crosslinker ratio would increase the fraction of polymer rich phase and decrease the fraction of polymer poor phase．In addition．the points with same scattered intensity had same fraction of polymer poor phase and polymer rich phase with the same LC,which meant that the structure of the points with same scattered intensity were similar．
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发布时间：2021-03-19 - 摘要：Pressed films of blends nf polypropylene (PP) with ethylene-propylene rubber(EPR) were examined by small-angle X-ray scattering(SAXS),and scanning electron microscope(SEM)．The correlation distance ac,average chord length l and radius of gyration Rg were calculated using Debye-Buech statistical theory,both ac and Rg had a maximum values at 50／50 (PP-EPR) in blends,l1 EPR (EPR phase) increased with EPR content,whereas l2 IPP (IPP Dhase) decreased．Using X-ray scattering,Pored’s index a was further calculated,and the fractal behavior and shapes of scattering units were analyzed,the results showed that the shapes of the scattering particles were intermediate between sheets and spheres and were self-similar．The structure and morphology of blends were also studied by SEM,the average diameter D of dispersed phase was also calculated,and the change of D with EPR content was in accord with that of ac,Rg and l．
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发布时间：2021-03-19 - 摘要：The overall isothermal crystallization kinetics and melting behavior of poly(β-hydroxybutyrate) (PHB) and maleated PHB with different graft degree were studied by using differential scanning calorimetry (DSC)．The Avrami analysis indicates that the introduction of maleic anhydride results in the decrease in the overall crystallization rate of PHB,but does not affect its nucleation mechanism and geometry of crystal growth．The activation energy of the overall crystallization process increases with the increase in graft degree．The phenomenon of multiple melting endotherms is observed,which results from melting and recrystallization during the DSC heatingrun.
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发布时间：2021-03-19 - 摘要：High performance plastic resins PEK-C,PES,PEI and PSU were mixed with organoclay CH3(CH2)17 (CH3)3N3+-Montmorillonite in solution．The XRD results revealed that the PEK-C and PES were very easy to intercalate into the clay and drove the clay to exfoliate,as a result,exfoliated polymer／clay nanocomposites were obtained．On the contray,PEI and PSU could not intercalate into the clay．The possible reasons caused these different results might be that the interaction between the former two polymers and clay were strong while the interaction between the latter two polymers and clay were weak．The Tgs of PEK-C／clay and PES／clay nanocomposites were 210℃ and 229℃,much lower than that of pure PEK-C and PES,which were 227℃ and 237℃,respectively．But the decomposing temperatures Td of PEK-C and PES rose from 469℃ to 507℃ and from 514℃ to 579℃ after mixed with clay,increased 38℃ and 65℃,respectively．For the polymer PEI and PSU,which could not intercalate into the clay,both their Tg and Td changed little after mixed with the clay．The positron annihilation life time spectroscopy results indicated that larger free volumes formed as PEK-C combined with clay,which was supposed to be responsible for the decreases of its Tg．
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发布时间：2021-03-19 - 摘要：Vinyl chloride／N-phenylmaleimide copolymer (VC/PMI) and vinyl chloride／N-phenylmaleimide／acrylonitrile terpolymer (VC／PMI／AN) were synthesized in the suspension copolymerization process for improving the heat resistance of poly(vinyl chloride) (PVC)．This paper emphasized on the studies on the characterization of the heat resistant properties of these three (CO)polymers mainly by means of dynamic mechanical experiment with the change of storage modulus(E′),change rate of E′with temperature and mechanical loss factor (tanδ) near the glass transition．The Vicat softening point (VSP) was also tested supplementaLly for comparison．The lower the change rate of E′with temperature is,the higher the heat resistance of VC／PMI and VC／PMI／AN will be．The effects of the amount of PMI and AN in the recipes of copolymerization on the change rate of E′with temperature,tanδ and VSP were also investigated．The results show that the increase of the amount of PMI will increase the rigidity of the backbone of the copolymer chain so as to improve the heat resistance．On the other hand,the introduction of AN into the copolymer will give more uniform distribution of PMI unit or segment in the backbone,and thus improves the heat resistance of the copolymer further．It is discovered that there are two peaks of mechanical loss or two glass transition temperatures of VC／PMI／AN copolymerization product．It may be interpreted from the higher reactivities of PMI and AN than VC．During the copolymerization process of VC,PMI and AN,the more active PMI and AN will copolymerize more rapidly and will consume entirely at conversion of about 45％～50％．Thereafter,VC continues to homopolymerize to form PVC homopolymer until a final conversion of 85％．Actually,the final product is a mixture of VC/PMI/AN terpolymer and homo-PVC,showing two TgS．
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发布时间：2021-03-19 - 摘要：A novel diamine 2-(4-aminophenyl)-4-(3-pheny-4-phenoxy)-2,3-phthalazinone-1 (1,BAPPP) containing aza hetero cyclic was synthesized from 4-(3-phenyl-4-hydroxyphenyl)-2,3-phthalazinone-1 (OP-HPPZ) conveniently．Diamine 1 was utilized to prepare a class of new aromatic polyamides with various aryl dicarboxylic acids using Yamazaki method with high molecular weight．The synthesized polyamides had the inherent viscosity in the range of 0.63～0.75 g dL-1．They exhibited high glass transition temperature of 320.9～329.9℃ and good thermooxidative properties．The polymers were readily soluble in polar solvents such as NMP,DMF and cresol etc and their structure was confirmed by MS,FT-IR and 1H-NMR studies．
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发布时间：2021-03-19 - 摘要：The cyclic voltammograms and AC impedance spectra of poly(methylene green) were investigated in the temperrature range of 10℃ to 60℃．The effect of temperature on the conductivity of the solution was determined. There are an anodic peak and a cathodic peak in the cyclic voltammogram of poly(methylene green) at various temperatures．Their peak currents increase with increasing temperature,which means that the reaction rate of the electrode increases with increasing temperature．The result from AC impedance plots shows that the charge transfer resistance／Rct increases with increasing temperature．The TG curve shows that the polymer was decomposed by three steps．The step at 263.1℃ corresponds to the polymer’s decomposition．The scanning electron micrograph of the surface of poly(methylene green) polymerized on platinum foil shows that the surface of poly(methylene green) is consisted of some particles．
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发布时间：2021-03-19 - 摘要：The increasing use of commercial,military,and scientific electrical products and electronic devices has raised the problem of electromagnetic interference(EMI),also called electromagnetic environmental pollution,so there is an increased interest in EMI shielding．By use of mechanical mixing doping method,highly conducting polyaniline films were prepared by the variation of dopant loading and solvent types．When dopant camphor sulphonic acid／emeradine base repeat unit molar ratio is 0.5／1,the conductivity of doped PANI is maximum．The conductivity results show that using m-cresol as solvent is better than N-methyl-2-pyrrolidinone (NMP)．The mechanical mixing doping method is better than other doping methods．It employs less solvent and less dopant．The maximum conductivity of the prepared films is up to 370 S／cm．The total shielding efficiency(SET) of highly conducting polyaniline films was measured at 10 GHz of microwave frequency．The dependence of SET on thickness of polyaniline films was studied．When the thickness of the film is l8 μm,the calculated SET is up to 40 dB．The SET result shows that the electromagnetic shielding property of highly conducting PANl film can meet the desire of commercial standard．Electromagnetic shielding efficiencies of films with different thickness are calculated by the far-field shielding theory．The practical measured SET values are compared with the calculated values．It is found that the measured SET values are very consistent with the theoretically calculated ones．
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发布时间：2021-03-19 - 摘要：A side-chain azo polyelectrolyte,poly(2-[4一(4′-carboxyphenylazo)phenoxy]ethyl acrylate) (PCAPEA) was synthesized through free radical polymerization．Influences of solution pH values on the UV-Vis absorption spectra and photo-responsive behaviors of PCAPEA in aqueous solution were studied．The results showed that the UV-Vis absorption spectra of PCAPEA in aqueous solutions change with the solution pH value,and its photo-responsive behaviors also significantly depend on the solution pH value. This observation indicated that ionization degree changing with pH variation controls the existing conformation or aggregation of PCAPEA in the solution．PCAPEA not only in aqueous solution but also in water-tetrahydrofuran mixture was successfully fabricated into self-assembled multilayers with poly(diallydimethylammonium chloride)by an electrostatic layer-by-layer process．This new self-assembly technology supplied a feasible way for the electrostatic self-assembly of the polyelectrolytes with poor aqueous solubility．
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发布时间：2021-03-19 - 摘要：A polymerizable photoiniferter,β-methacrylyoxylethyl 2-N,N-diethyldithiocarbamylacetate (MAE-DCA),was used for preparation of graft copolymers containing poly(methyl methacrylate) (PMMA) and polystyrene (PSt) segments via two pathways．One is called the grafting-through method,which involves the synthesis of PMMA-macromonomers by using MAEDCA as a photoiniferter,and the copolymerization of the macromonomers with St initiated by conventional initiator．The effects of the molecular weight and the concentration of the macromonomers on the copolymerization behavior were studied．It shows that the lower molecular weight and the lower concentration of macromonomers were used,the higher monomer conversion and the higher molecular weight of graft copolymers were obtained．The other is called the grafting-from method,which involves the synthesis of copolymers containing pendant DC groups by copolymerization of MMA and MAEDCA initiated by AIBN,and graft copolymerization of St initiated by this copolymer under UV light irradiation．The results show that the graft copolymerization has the characteristics of living radical polymerization,and the grafted chain length can be controlled by the monomer conversion．
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发布时间：2021-03-19 - 摘要：Radical polymerization of styrene and methyl methacrylate was investigated using a nickel-based initiating system,i．e．DCDPS／NiCl2／PPh3,in which diethyl 2,3-dicyano-2,3-diphenyl-succinate (DCDPS) is a hexa-substituted ethane thermal iniferter and the nickel based catalyst reacted from Ni2+ to Ni1+．The polymerization of styrene (St) was successfully controlled in bulk at 120℃．The kinetics studies showed that the kinetics is first order in monomer．The number average molecular weight Mn increased linearly with conversion from 57100 to 126000,and the molecular weight distributions(Mw／Mn) were around l.5 as the monomer conversion was increased from 38％ to 86％．Well defined polystyrene with α-(carbethoxycyanophenyl)methyl-ω-chlorine end groups was obtained from the polymerization of St with DCDPS／NiCl2／PPh3 initiating system,and the polymerization proceeded via reverse ATRP．While the polymerization behavior of methyl methacrylate (MMA) initiated with the same system was absolutely different．The molecular weights of so-obtained PMMA did not increase with the monomer conversions and at the same time the molecular weight distributions kept narrow (Mw／Mn=1.19) during the polymerization．
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发布时间：2021-03-19
Research Article
- 摘要：Atactic-polystyrene (a-PS) films cast from solutions of different concentrations in dichloromethane under vacuum conditions were prepared．Their tensile mechanical behavior has been studied．It was found that the tensile strength of films cast in vacuum increases significantly with the solution concentration when the solution concentration is above 0.02 g／mL．The existence of a critical concentration value in the region of 0.01～O.02 g/mL is in agreement with the results of previous experiments．The critical concentration has been identified as ce for coil entanglement．
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发布时间：2021-03-19 - 摘要：Chitosan/bovine serum albumin (BSA) ultrathin films were fabricated on modified quartz wafer through layer-by-layer deposition．The effects of experimental conditions,such as pH value,molecular weight of CS,ionic strength and polyanions coexisting in BSA solution,on the fabrication and the stability of films were investigated with a radio-labeled method．The results show that the absorbed BSA is almost proportional to the number of assembly cycle except the first 2 cycles,and chitosan／BSA films are favorable to be fabricated in chitosan aq AcOH at pH=5.2 as compared with at pH=1.0．When two different molecular weight (MW) chitosans were used (Mη≈1.2×105,Mη≈1.0×106),the lower MW chitosan adsorbs more BSA,but less stable ultrathin films are fabricated．Similar results were obtained that the amount of adsorbed BSA is higher hut the films formed are less stable in water than in phosphate-buffered saline (PBS)．The adsorption of BSA is restricted greatly in the presence of poly(sodium styrene-sulfonate) (PSS) mainly because of the competitive adsorption．
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发布时间：2021-03-19 - 摘要：Atom transfer radical polymerization of protected 2-hydroxyethyl acrylate (HEA-TMS) was conducted to prepare well-defined bromo-terminated macroinitiators,which were further allowed to react with large excess amount of C60 under ATRP condition．A well-defined hammer-shaped C60-PHEA was then obtained by hydrolysis of C60-PHEA-TMS under mild conditions．A TEM observation of the association behavior of these well-defined hammer-like C60-PHEA macromolecules showed that they assemble into spherical vesicles in water．Their characteristic inner water phase was further confirmed by fluorescence probe method．Also,it was found that the size of vesiclesdecreased as the increase of molecular weight of PHEA．
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发布时间：2021-03-19 - 摘要：To avoid the damage to catalytic system in ATRP by the carboxyl groups in vinyl benzoic acid,a welldefined poly(p-vinyl benzoic acid) was synthesized via ATRP in the tertiary butyl ester form．The ATRP of t-butylp-vinyl benzoate (t-BVB) was studied kinetically．The results showed that t-BVB can be polymerized in a controlled way by ATRP．It was found that the polymerization late of t-BVB is much faster than that of St,meaning that the electron-withdrawing ester group affects the polymerization obviously．Well-defined diblock copolymers of St and t-BVB were prepared by using bromo-terminated PBVBs as macroinitiators via ATRP．After removal of the t-butyl group by hydrolysis,well-defined amphiphilic diblock copolymers of styrene and p-vinyl benzoic acid(PSt-b-PBVA) were obtained．
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发布时间：2021-03-19
Research Bulletin
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