最新刊期
      卷 ， 期 11 ， 2007

        Research Article

      • TAO Rui,MA Huan,CHEN Xiaonong,XIA Yuzheng,SHI Shuxian,JIAO Shuke
        Issue 11, Pages: 1009-1016(2007)
        摘要：Thermo-sensitive poly(N-isopropylacrylamide)(PNIPAM)-poly(N-vinylpyrrolidone)(PVP)and PNIPAM-poly(ethylene oxide)(PEO)comb-block copolymers with PVP and PEO hydrophilic branches,respectively,were synthesized using RAFT polymerization of NIPAM and PVP or PEO macromonomers.Polystyrene(PS)microspheres were treated in aqueous suspension with different copolymers obtained to allow polymer adsorbing on PS microsphere surface.Protein adsorption resistance of the PS microsphere with pre-adsorbed copolymer was evaluated,using lysozyme as the model protein,by flocculating test,particle coagulation(by dynamic light scattering),electrophoretic mobility measurement and quantitative analysis of protein adsorption.It was found that pre-adsorption of the comb-block copolymer on PS microsphere surface could effectively inhibit protein adhesion to the surface.A larger number of hydrophilic branches in the copolymer resulted in a better protein resistance both at room temperature and at temperatures higher than the LCST of PNIPAM.Transmission electron microscopy and dynamic light scattering measurements of the copolymer colloids confirmed that the hydrophilic branches formed an outer adsorb-layer and provided resistance to protein when the copolymer adsorbed on PS microsphere surface.Moreover,flocculation tests on heating and cooling of PS microsphere suspension in the presence of protein provided a simple and effective method to qualitatively evaluate the protein resistance of the polymers used for pre-adsorption treatment.  
        关键词：Thermo-sensitive polymer;Comb-block copolymer;Polystyrene microsphere;Surface treatment;Protein adsorption resistance   
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        发布时间：2021-08-24
      • LIANG Yuan,ZHOU Qingmei,ZENG Youlin,XU Mancai,XIE Qingji
        Issue 11, Pages: 1017-1021(2007)
        摘要：An amperometric glucose enzymatic electrode was constructed by using dopamine polymer to immobilize glucose oxidase on the pencil lead.It was used to quantify cyclodextrin units in cyclodextrin polymer.The response to the concentrate of cyclodextrin and the stability of glucose enzymatic electrode were investigated.It was found that a good linear relationship exists between the quantity of cyclodextrin and the response current of the enzymatic electrode.It was also found that the enzyme electrode is very robust and can be used repeatedly.The response current only decreased by 7%,and no obvious deterioration in its response performance was found even if the glucose enzymatic electrode was keep using for one month.Compared with the conventional Sulfate-Phenol method,the relative deviation of the determination results from the two methods in within 8%.  
        关键词：Cyclodextrin;Cyclodextrin polymer;Glucose oxidase;Enzymatic electrode   
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      • ZHAI Linfeng,SHI Tiejun,WANG Hualin
        Issue 11, Pages: 1022-1027(2007)
        摘要：This reports on the preparation of polyvinylpyrrolidone(PVP)micro spheres in ethyl acetate by dispersion polymerization with N-vinylpyrrolidone(NVP)as initial monomer,P(NVP-co-VAc)as dispersant,and AIBN as initiator.The influences of monomer concentration,dispersant concentration and initiator concentration on the size of PVP micro spheres as well as the monomer conversion rate were studied.The structure and properties of PVP micro spheres were analyzed.The results show that the prepared PVP micro spheres have a mean diameter of 3～4 μm.As the concentration of NVP increased,the micro sphere size and the molecular weight of the PVP increased and the monomer conversion rate also increased.As the concentration of P(NVP-co-VAc)increased,the size of micro spheres decreased,and the molecular weight of the PVP and the monomer conversion rate increased.As the concentration of AIBN increased,the size of micro spheres and the monomer conversion increased,the molecular weight of the PVP is also increased.The PVP prepared by dispersion polymerization has crystal structure and its molecular weight is low as compared to those prepared by solution polymerization.  
        关键词：Polyvinylpyrrolidone;Microsphere;Dispersion polymerization;Preparation   
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        发布时间：2021-08-24
      • GAO Nan1,HU Chunpu2,YING Shengkang2
        Issue 11, Pages: 1028-1034(2007)
        摘要：The partitions coefficients of Cu（Ⅰ）/phen,Cu（Ⅱ）/phen、SLS and phen between the styrene（St）phase and water phase were measured respectively in the reverse atom transfer radical polymerization reaction system of styrene initiated by benzoyl peroxide（BPO）with phenanthroline（phen）as ligand and sodium lauryl sulfate as surfactant.The results indicated that the partition behavior of Cu（Ⅰ）/phen and Cu（Ⅱ）/phen could be affected by the temperature.Based on the partition coefficients measured,the number of controlled active species in the CuBr/CuBr2/phen/BPO reverse ATRP emulsion polymerization system was theoretically calculated,and the reaction mechanism of reverse ATRP was discussed in detail.Though the bulk polymerization after the catalyst partitioning between the St phase and the water phase,we proved that the calculated results was reasonable.  
        关键词：Reverse atom transfer radical polymerization;Styrene;Partition coefficient   
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        发布时间：2021-08-24
      • WU Zhiqiang1,LI Baohui1,JIN Qinghua1,DING Datong1,SHI Anchang2
        Issue 11, Pages: 1035-1039(2007)
        摘要：The phase behavior of binary blends of symmetric long diblock copolymers and nearly short symmetric diblock copolymers with different ratio of chain lengths is studied using the self-consistent field theory.The occurrence of order-order transition,disorder-order transition and regions of order-disorder coexistence has been examined.Comparisons are also made with the theoretical study of the binary blend of symmetric long and short diblock copolymers and experiments on the similar systems.The effects of the short nearly symmetric diblock copolymer on the symmetric long diblock copolymer in their blends were analyzed.  
        关键词：Diblock copolymer;Blend;Self-assemble;Micro-separation;Phase behavior   
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        发布时间：2021-08-24
      • ZHANG Bei,WU Yixian,LI Yan,LIU Xun,XU Xu,WU Guanying
        Issue 11, Pages: 1040-1046(2007)
        摘要：The cationic polymerization of isobutylene（IB）by utilizing difunctional initiator p-dicumyl chloride（DCC）in conjunction with coinitiator AlCl3 was carried out in CH2Cl2/Hex（40/60,V/V）solvent mixtures.The effects of concentrations of 2,6-di-tert-butylpyridine（DtBP）,triphenylamine（TPA）and AlCl3 on monomer conversion,molecular weight and molecular weight distribution（MWD）of polyisobutylene（PIB）were investigated.The small amount of water in the polymerization system in conjunction with AlCl3 could induce a conventional uncontrolled rapid polymerization of IB and lead to polyisobutylene with broad molecular weight distribution（Mw/Mn =4.55）.It was found that the GPC trace of resultant polymers obtained by DCC/H2O/AlCl3 systems exhibited a bimodal distribution,which was attributed to the competition of initiation from two different active centers,i.e.,H+AlCl<sub>3OH-（a）and AlCl-+4C（CH3）2C6H4（CH3）2C +-AlCl4（b）even at high DCC concentrations.The initiation by active center（b）was increased whereas the molecular weight of the polymer decreased with a decrease in AlCl3 concentration.The addition of proton trap DtBP in the monomer solution could obviously decrease or even suppress the initiation from active center（a）and the chain transfer reaction to monomer,leading to the polymers with unimodal molecular weight distribution.The initiation from active center（a）could be suppressed by introduction of TPA and DtBP even at low DCC concentrations.A desirable cationic polymerization of IB would be achieved with the DCC/AlCl3 initiation system in the presence of TPA and DtBP,and the telechelic tert-Cl-polyisobutylene with relatively high molecular weight（Mw=103200）and unimodal molecular weight distribution（Mw/Mn=2.09）could be obtained.  
        关键词：Cationic polymerization;Isobutylene;Polyisobutylene;Nucleophile   
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        发布时间：2021-08-24
      • LUO Ning,WU Zhanpeng,MOU Nanxiang,JIANG Lizhong,WU Dezhen
        Issue 11, Pages: 1047-1051(2007)
        摘要：Polyimide/silica/silver hybrid films were prepared via the combination of sol-gel method and in situ single-stage self-metallization technique.The structure of polyimide films in the thermal curing process and the influence of silica content on the transfer and aggregation of silver particles to the surface of hybrid films were investigated.Films were characterized by transmission electron microscopy,dynamic mechanical thermal analysis,Fourier transform infrared spectroscopy,ultraviolet visible spectroscopy and mechanical measurements.The results indicated that there was no degradation of polyimide matrix after the formation of silica and silver particles.Silica acted as the nucleus for the silver particles.With increasing the content of silica,more and more silver particles keep in the hybrid films instead of transferring onto the surface of the hybrid films,and the reflections of hybrid films decreased gradually.  
        关键词：Polyimide;Silica;Silver;Self-metallization;Hybrid films   
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        发布时间：2021-08-24
      • FAN Pengwei,LI Xinyang,TUO Xinlin,WANG Xiaogong
        Issue 11, Pages: 1052-1056(2007)
        摘要：Acid treated single-wall carbon nanotubes(SWNTs)were fabricated into multilayers with a hyperbranched polymer of diazonium salt(DAS)using the layer-by-layer electrostatic adsorption technique.The fabrication process,multilayer thickness variation,multilayer surface morphology and the interaction between SWNTs and DAS were detected by UV-Vis absorption spectroscopy,ellipsometry,atomic force microscopy,scanning electron microscopy and Raman spectroscopy,respectively.Moreover,the nanomechanical properties of the multilayer film was measured by nanoindentation.All results show that SWNTs and DAS can be fabricated into multilayers based on the cooperation of electrostatic attraction and chemical cross-linkage between SWNTs and DAS.Further,this cooperation endows the SWNTs/DAS multilayer films with outstanding nanomechanical properties.Their hardness and modulus may be as high as 2.0 GPa and 10.0 GPa,respectively.Finally,the SWNTs/DAS multilayer film can be peeled off from the substrate as a free-standing membrane.  
        关键词：SWNTs;Hyperbranched diazonium salt;Cross-linkage;Self-assembled multilayers   
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        发布时间：2021-08-24
      • LIU Xiaoxuan 1,BAI Yingkun2,JING Yanni2,WANG Hongbo2,CHEN Bing2,WU Guangguo2
        Issue 11, Pages: 1057-1063(2007)
        摘要：The anchoring of the photoinitiator and the photo-grafting polymerization of methyl methacrylate(MMA)on the surface of nanometer silica particles have been performed.The anchoring of the initiator on the silica was achieved by treating silica with thionyl chloride and reacting with Irgacure2959.Poly(methyl methacrylate)(PMMA)has effectively grafting on the surface of the nanometer silica particles during the photo-grafting polymerization initiated by Irgacure2959.The change of particle surface and the grafting of PMMA polymers were confirmed by IR,TGA and TEM technique.Monomer conversion,grafting ratio and grafting efficiency under various conditions were investigated.It is shown that grafting reaction with stirring has a prominent effect on the grafting ratio and the grafting efficiency during the photo-grafting polymerization.The grafting ratio of MMA could be up to 110% initiated by Silica-2959 with stirring in the presence of nitrogen,and the thermostability of the products measured by TGA would be remarkably improved.However the grafting ratio can only reach a less degree in a static state(no stirring)during the process.  
          
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        发布时间：2021-08-24
      • CHEN Xiaoli,ZHU Fangming,LIN Shang’an
        Issue 11, Pages: 1064-1068(2007)
        摘要：Two novel nickel complexes of bis[N-(4-nitrophenyl)salicylaldiminate]nickel(Ⅱ)A and bis[N-(4-methoxyphenyl)salicylaldiminate]nickel(Ⅱ)B weresynthesized.These new type bis(N,O)chelated nickel complexes/MAO catalysts are effective to catalyze polymerization of polar monomer methyl methacrylate(MMA).The A system which contains p-nitro substitution groups on the ligand having electron attractive effect exhibits better activity than B at higher polymerization temperature(50℃).At the polymerization conditions,T_p=30℃;Al/Ni=600,the B system shows the best activity.The chain sequence distribution of PMMA obtained with B systems is 73.2% rr triads as determined by 13C-NMR,and the glass-transition temperature(T_g)is up to 106.4℃ by DSC measurements.  
          
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        发布时间：2021-08-24
      • ZHANG Wenxiong,LI Mingmin,JING Qi,LIU Jingbing
        Issue 11, Pages: 1069-1073(2007)
        摘要：A specific polyamide-amide block copolymer with monomers of triethyleneglycol bis(4-carboxypheny)ether(PEG3),4,4’-diamino-3,3’-dimethylbiphenyl and ε-caprolactam was synthesized via condensation copolymerization.FT-IR,1H-NMR,POM,DSC and WAXD analyses of samples elicit that this new type of block copolymer can demonstrate liquid crystalline characteristics.By contrast to thermotropic homopolyamide liquid crystalline(TLCP),the thermal dynamic properties of the thermotropic liquid crystalline copolyamide containing N6(TLCP-N6)were modified.This block copolymer can show nematic phase in a wide temperature range,and is able to form morphologic textures of solidification-induced band and shear stripes under certain conditions.  
        关键词：Thermotropic polyamide liquid crystalline;Nematic phase;Solidification-induced band texture   
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        发布时间：2021-08-24
      • LI Xin 1,ZHAO Xin2,CHEN Cuixian2,LI Jiding2
        Issue 11, Pages: 1074-1079(2007)
        摘要：Polyethersulfone with cardo(PES-C)was a developed engineering thermoplastic and membrane material with high glass transition temperature,PES-C ultrafiltration membranes were prepared by phase inversion method using dimethylacetamide(DMAC)as solvent and oxalic acid(OA)and polyethylene glycol as additives.The membrane morphology forming and evolution could be observed by the experimental system and method.The effect of additive and polymer concentration on cast solution and the gelation kinetics of polyethersulfone with cardo asymmetric membrane were studied.The result showed that the gelation kinetics and membrane morphology were coincident.It was found that the relation between the square of gelation front motion and time was nonlinear,the gelation kinetics process did not follow the Fick diffusion behavior,which was different from the result of Strathman et al.  
        关键词：Gelation kinetics;Asymmetric membrane;Phase inversion;Polyethersulfone with cardo   
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        发布时间：2021-08-24
      • TIAN Wei,FAN Xiaodong,JIANG Min,WANG Shengjie,LIU Yuyang,YU Yu
        Issue 11, Pages: 1080-1087(2007)
        摘要：Hyperbranched polycarbosilane-g-β-cyclodextrin（β-CD）polymer brushes based on carbosilane core were synthesized.At first,hyperbranched polycarbosilanes（HBP）with carbosilane cores of 3 to 5 generations were prepared via hydrosilylation addition and pseudo-one-step using methyldiallylsilane as monomer（AB2）and 1,2-bis（diallyl（methyl）silyl）ethane as core（B4）,respectively.Then,HBP was modified by 1,1,3,3-tetrmethyldisiloxane,allyl alcohol and chloroacetyl chloride for obtaining hyperbranched polycarbosilanes carrying chloride atoms（HBP-Cl）.It may which act as a macroinitiator for further polymerization of a hyperbranched polymer with functional arms.For this purpose,HBP-g-poly（N,N-dimethylaminoethyl methacrylate）（PDMA）with different arm length was synthesized by atom transfer radical polymerization（ATRP）.Finally,HBP-g-PDMA-β-CD with functional polymer brushes was obtianed by immobilization of Mono-6-I-β-CD onto PDMA chains.Their macromolecular structures were characterized by FTIR,1H-NMR,13C-NMR and 29Si-NMR.In addtion,the macromolecular architecture of HBP-g-PDMA-β-CD,including the inner HBP structure with carbosilane core and the exterior PDMAEMA layer,was confirmed by SEC/MALLS and particle size analyses.Besides,it was found that the amount of β-CD content incorporating onto PDMA segments can also be regulated by changing reaction time.  
        关键词：Functional polymer brushes;Hyperbranched polycarbosilane;Linear cyclodextrin polymer;Carbosilane core molecular   
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        发布时间：2021-08-24
      • XIAO Miaomiao1,TONG Bin1,ZHAO Wei1,SHI Jianbing1,PAN Yuexiu1,ZHI Junge2,DONG Yuping1,LAM Jacky Wing Yip3,TANG Benzhong3
        Issue 11, Pages: 1088-1091(2007)
        摘要：Full conjugated self-assembled multilayer films from the two polymers,partially doped polyaniline(PANI)as polycation and poly(o-aminobenzoic acid)(PCAN)or poly(aniline-2-sulfonic acid)(PSAN)as polyanion,were fabricated with the layer-by-layer(LBL)technique.The experiments revealed that the UV-Vis absorbance of LBL films increased linearly with the increase of dipping cycle number,which indicated that the amount of polyelectrolyte deposition on the surface of the films in every cycle was uniform.Because sulfonic groups in PSAN had higher electro-negativity than carboxylic groups in PCAN,the molecular chain’s stretch and distance among chains were greater than that of PCAN.So the deposition amount of PANI-PSAN in every dipping cycle was less than that of PANI-PCAN in the same condition,which the absorbance of PANI-PSAN film was smaller than that of PANI-PCAN film in the same bilayer number.In conventional three-electrode CV test,the electrochemical properties of the two LBL films mainly depended on pure PANI because the conductibilities of both PCAN and PSAN were weaker than PANI.Compared with PANI-PSAN films,the electrochemical properties of PANI-PCAN films were better due to the effect of deposition.  
        关键词：Polyaniline;Poly(o-aminobenzoic acid);Poly(aniline-2-sulfonic acid);Self-assembly;Electrochemistry   
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        发布时间：2021-08-24

        Research Bulletin

      • QIU Yipeng,TANG Liming,WANG Yu
        Issue 11, Pages: 1092-1096(2007)
        摘要：A hyperbranched polymer(HPE-1)with quadruple hydrogen bonding units was prepared through reacting Boltorn H20(HPE)with ureidopyrimidinone(Upy)at hydroxyl and isocyanate group ratio of 4∶1.The structure of HPE-1 was characterized by 1H-NMR and IR.The melting HPE-1 can form long fibers under pulling due to the strong interaction of the molecules,but HPE can’t.With both hydrophilic hydroxyl groups and hydrophobic Upy units,HPE-1 self-assembled into spherical aggregates in water.The aggregate become larger in acidic solutions,but dissociate under basic conditions,which provides a way for preparing sensitive material.  
        关键词：Quadrupolar hydrogen bond;Hyperbranched polymer;Supramolecular fiber;Solution aggregation   
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      • CHEN Hao,JIA Zhifeng,YAN Deyue
        Issue 11, Pages: 1097-1101(2007)
        摘要：The hyperbranched polyethers with hydroxyl end groups were prepared by one-step proton transfer polymerization of commercially available monomer poly(propylene glycol)diglycidyl ether and glycerol.The molecular structure of the hyperbranched polyethers was analyzed by 1H-NMR and 13C-NMR spectroscopy.The molecular weight of the obtained polymers ranges from 17600 to 24300,and the glass temperature ranges from-31.5℃ to-26.7℃,while the T_d ranges from 367℃ to 376℃.The obtained hyperbranched polyethers exhibited a LCST-type phase separation in water.The lower critical solution temperature(LCST)values can be tuned by controlling the feed molar ratio of poly(propylene glycol)diglycidyl ether to glycerol and the concentration of the polymer aqueous solutions.  
        关键词：Hyperbranched polymer;Temperature-sensitive polymer;Proton transfer polymerization   
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        发布时间：2021-08-24
      • YAN Qing,BAI Yaowen,MENG Zhe,YANG Wantai
        Issue 11, Pages: 1102-1104(2007)
        摘要：Acetonitrile,a substance harmful to human health,is the most commonly used solvent for the synthesis of cross-linked polymeric microspheres by precipitation polymerization.Here,the innoxious acetic acid has for the first time replaced acetonitrile as a solvent in the precipitation polymerization of narrow disperse crosslinked poly(divinylbenzene)(PDVB-55)microspheres.Scanning electron microscopy(SEM)results showed that the PDVB-55 particles were uniform and well separated,and the diameter was measured to be 2.69 μm.X-ray photoelectron spectroscopy(XPS)shows that there are significant amount of double bonds on the surface of the microspheres.  
        关键词：Precipitation polymerization;Acetic acid;Divinylbenzene;Microspheres;Narrow disperse   
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