SYNTHESIS OF POLY(DIVINYLBENZENE-co-ACRYLIC ACID) HOLLOW MICROSPHERES WITH GOLD NANOPARTICLES ON THE INTERIOR SURFACE

Poly(divinylbenzene-co-acrylic acid) (poly(DVB-co-AA)) hollow microspheres with gold nanoparticles on the interior surfaces were prepared from the gold nanoparticles-coated poly(methacrylic acid) (PMAA@Au@poly(DVB-co-AA)) core-shell microspheres by removal of the PMAA core in water.Au nanoparticles-coated PMAA microspheres were afforded by the in-situ reduction of gold trichloride with PMAA microsphere as stabilizer via the interaction between carboxylic acid groups and Au nanoparticles.Gold nanoparticle...     

亲/疏水不对称空心聚合物微球制备及磁性粒子装载研究

首先将(马来酸酐-醋酸乙烯酯共聚物)核/(马来酸酐-二乙烯基苯共聚物)壳微球的壳层外表面酐基烷基溴化,然后将核溶蚀、壳层内表面酐基水解,制得内表面含亲水羧基、外表面含烷基溴、具有微孔(Barrett-Joyner-Halenda平均孔径14.9nm)的空心聚合物微球.以此空心微球为微反应器,使Fe2+和Fe3+通过球壁...     

聚L-乳酸/聚(天冬氨酸-co-乳酸)共混物的制备及其相容性研究

采用氯仿/乙醇共沸溶液浇铸法制备了混合均匀的聚L-乳酸/聚(天冬氨酸-co-乳酸)共混物(PLLA/PAL)体系.研究了PLLA/PAL共混体系的热性能、结晶行为、形态结构和力学性能,评价了PLLA和PAL之间的相容性.结果表明,PAL对PLLA的结晶行为和热性能产生了较大的影响,共混物的结晶度较低,共混体系中部分PAL会进入PLLA球晶的片晶而导致PLLA球晶结构不完善,熔点降低.PAL的含量小于20%的PLLA/PAL共混物的拉伸强度和断裂延伸率均高于纯PLLA.PLLA和PAL分子链相互缠结,产生的氢键使分子链间存在较强的相互作用,具有较好的相容性.     

PREPARATION OF POLY（ETHYLENEGLYCOL-co-ACRYLIC ACID） MICROSPHERES WITH DIVINYLBENZNE AS CROSSLINKER BY DISTILLATION-PRECIPITATION POLYMERIZATION

Monodisperse poly（poly（ethyleneglycol） methyl ether acrylate-co-acrylic acid） （poly（PEGMA-co-AA）） microspheres were prepared by distillation-precipitation polymerization with divinylbenzene （DVB） as crosslinker with 2,2＇- azobisisobutyronitrile （AIBN） as initiator in neat acetonitrile without stirring. Under various reaction conditions, four distinct morphologies including the sol, microemulsion, microgels and microspheres were formed during the distillation of the solvent from the reaction system. A 2D morphological map was established as a function of crosslinker concentration and the polar monomer AA concentration, in comonomer feed in the transition between the morphology domains. The effect of the covalent crosslinker DVB on the morphology of the polymer network was investigated in detail at AA fraction of 40 vol%. The ratios of acid to ethylene oxide units presenting in the comonomers dramatically affected the polymer-polymer interaction and hence the morphology of the resultant polymer network. The covalent crosslinking by DVB and the hydrogen bonding crosslinking between two acid units as well as between the acid and ethylene oxide unit played key roles in the formation of monodisperse polymer microspheres.     

CONFORMATIONAL CHARACTERISTICS OF POLY(ACRYLIC ACID) AND POLY(METHACRYLIC ACID)

A full-relaxation optimization of molecule and the Dreiding force field are employed toobtain the geometry parameters and the conformational energy surfaces of meso or racemicdyad of poly(acrylic acid) (PAA) and poly(methacrylic acid) (PMAA). Three differentcarbonyl-bond orientations of side-groups resulted in the differences in depth of potentialwells in their energetic contours for a meso or a racemic dyad. These discrepancies areinterpreted as a result of various fine structures corresponding to grid search conformationsas well as thereby different interactions. The analysis on the most stable conformationsof PMAA confirmed that the ester groups are nearly perpendicular to the plane definedby the two adjacent skeletal bonds but may possibly change their relative orientations tomeet the requirement of lower energy during the conformational state transition. For eachpolyme, two global energy maps of a meso and a racemic dyad were finally constructedfrom the superposition of energy data for the three kinds of side-group orientations by theBoltzmann factors. From an ensemble average, the proposed scheme with three rotationalisomeric states (RIS) allowed us to access the experimentally unperturbed dimensions ofPAA chain via the configurational statistical mechanics. Although the calculation wasbased on the short-range, local interactions, it was interested to note that the experimentalcharacteristic ratios just fell within the range calculated for atactic chains.     

导电聚间甲基苯胺空心微球的制备及表征

在无任何掺杂酸的条件下,以过硫酸铵(APS)既为氧化剂、又为掺杂剂,采用无模板(template-free)自组装的方法制备了导电聚间甲基苯胺(PMT)空心微球.该空心微球的平均直径约为2μm,壳的厚度约为140nm.研究表明PMT空心微球是以球状的间甲苯胺胶束为软模板(soft-template)经过自组装过程而形成的.借助FTIR、UV-Vis和XRD等结构表征证实自组装的空心微球为导电态的聚间甲基苯胺.     

嵌段液晶高聚物对聚醚砜 - 聚对苯二甲酸乙二醇酯/聚对羟基苯甲酸共混物的增容作用

嵌段液晶高聚物对聚醚砜 聚对苯二甲酸乙二醇酯／聚对羟基苯甲酸共混物的增容作用张海良张雪飞王霞瑜（湘潭大学化学化工学院湘潭４１１１０５）关键词增容作用，嵌段共聚物，原位复合材料基于热致性液晶高分子（ＴＬＣＰ）的原位复合材料以其高性能及易加工等特点而得...     

P(St-AM)核壳聚合物微球的制备及其光子晶体膜

采用一步乳液聚合法,调节引发剂用量,制备了不同粒径的具有核壳结构的功能性聚(苯乙烯-丙烯酰胺)乳胶微球.用透射电子显微镜表征了乳胶微球的核壳结构和粒径,所制微球的粒径分别为195,217,234和255 nm.用红外光谱对微球的化学成分进行了表征,证实聚丙烯酰胺已包覆在聚苯乙烯外层.通过竖直沉积自组装法制备了聚合物微球的光子晶体薄膜.扫描电子显微镜表征了所制光子晶体膜的表面形貌,反射和透射光谱表征了光子禁带.结果表明,聚合物微球以面心立方紧密堆积,其(111)面与基底平行;微球粒径不同,光子晶体的光子禁带不同.制备了不同光子禁带的光子晶体,禁带分别位于473,515,574和630 nm,相应的薄膜分别呈蓝色、绿色、黄色和红色,对于光子晶体的拓展和应用具有重要的意义.     

苯胺与吡咯共聚物空心球的自组装制备及性能

以碱性溶液为反应介质,苯胺和吡咯为单体,采用稀释聚合法制备苯胺-吡咯共聚物自组装空心微球.研究了搅拌条件、共聚单体摩尔比、聚合反应介质和聚合时间对共聚物形貌的影响.采用扫描电子显微镜、透射电子显微镜、红外光谱、广角X射线衍射、热重分析仪和四探针技术表征了共聚物的形貌、结构和性能.研究结果表明,聚合反应条件对共聚物的形貌有重大影响,通过调整聚合反应条件,可以实现共聚物形貌的有效调控.共聚单体总摩尔浓度为0.05 mol/L,氨水溶液作为反应介质,在静态条件下反应24 h可以得到尺寸均一、平均外直径为610～863 nm,壳厚144～162 nm的自组装共聚物空心微球.同时,研究了共聚物对银离子的吸附性能,结果表明共聚物对银离子有还原作用,吸附后共聚物表面有纳米银的生成.     

聚丙烯酸/聚氧化乙烯高分子复合溶液的结构与粘度

通过溶液折光指数和粘度测定,研究了聚丙烯酸（ＰＡＡ）与聚氧化乙烯（ＰＥＯ）高分子链间在复合溶液中的相互作用和ＰＡＡ／ＰＥＯ高分子氢键复合溶液的结构与粘度,研究了复合溶液粘度随溶液ｐＨ值的变化规律及不同浓度时剪切速率对复合溶液粘度和复合增粘效果的影响。结果表明：ＰＡＡ／ＰＥＯ复合溶液结构不同于ＰＡＡ和ＰＥＯ两组分聚合物溶液结构,ＰＡＡ与ＰＥＯ高分子链间的氢键相互作用形成构象更为伸展、流体力学体积列大     

大分子单体聚N-乙烯甲酰胺与苯乙烯共聚合成热敏性功能高分子微球

用自由基聚合法合成了大分子单体聚N 乙烯甲酰胺和功能高分子微球 .用GPC、分光光度仪和扫描电子显微镜等对合成的聚合物进行了表征 .研究结果表明 ,大分子单体聚N 乙烯甲酰胺和功能高分子微球具有明显的热敏性特性 ,且合成的功能高分子微球具有单分散性 ,粒径在 1～ 5 μm之间     

PREPARATION OF POLYMER MICROSPHERES WITH PYRIDYL GROUP AND THEIR STABILIZED GOLD METALLIC COLLOIDS

Narrow disperse poly(ethyleneglycol dimethacrylate-co-4-vinylpyridine)(poly(EGDMA-co-4-VPy))microspheres were prepared by distillation-precipitation copolymerization of ethyleneglycol dimethacrylate(EGDMA)and 4-vinylpyridine (4-VPy)with 2,2'-azobisisobutyronitrile(AIBN)as initiator in neat acetonitrile.The polymer microspheres containing pyridyl group were then utilized as stabilizer for gold metallic colloids with the diameter around 7 nm,which were prepared by the in situ reduction of gold chloride trihydrate with sodium borohydride through the coordination of the pyridyl group on the gel layer and surface of the microsphere with the gold metallic nano-particles.The catalytic properties of the pyridyl- functionalized microsphere-stabilized gold metallic colloids and the behavior of the stabilized-catalyst for the recycling were investigated with reduction of 4-nitrophenol to 4-aminophenol as a model reaction.     

在非水溶剂中聚甲基丙烯酸甲酯及其甲基丙烯酸共聚物与Rh6G的相互作用

本文用乙酸乙酯与不同比例乙醇配成混合溶剂, 考察在不同极性的介质中, Rh_6G对聚甲基丙烯酸甲酯及其与甲基丙烯酸共聚物分子形态的影响, 以及聚合物对Rh_6G荧光强度的影响, 发现Rh_6G与聚甲基丙烯酸甲酯没有特殊相互作用, 而与共聚物的相互作用受溶剂的极性影响很大, 随着极性增加, 从氢键作用过渡到静电作用。     

STUDIES OF THE CRYSTALLIZATION BEHAVIOR IN THE CRYSTALLINE/AMORPHOUS POLYMER BLENDS: POLY(ETHYLENE OXIDE)/POLY(METHYL METHACRYLATE) AND POLY(ETHYLENE OXIDE)/POLY(VINYL ACETATE)

The crystallization process of poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA)and PEO/poly(vinyl acetate) (PVAc) blends has been characterized by Fourier Transform Infrared(FTIR) spectra in conjunction with Differential Scanning Calorimeter (DSC) measurements. Thecrystallinity of PEO varies consistently with PEO content in PEO/PVAc blends and the PEO/PMMAblends containing 50 wt% or less PMMA. For the PEO/PMMA blends containing 60 wt% ormore PMMA, the crystallinity of PEO decreases more than PEO content but develops with crystal-lization time. These results can be explained in terms of difference between the crystallization tem-perature (T_c) and glass transition temperature (T_g) of the blends as a function of content of amorphouscomponent.     

改性聚偏氟乙烯接枝磺化聚(苯乙烯-co-丙烯酸)膜的研制

以过氧化苯甲酰(BPO)作引发剂,通过溶液接枝聚合法把苯乙烯/丙烯酸同时接枝到原硅酸钠改性的聚偏氟乙烯(PVDF)膜上,磺化后得到聚偏氟乙烯接枝磺化聚(苯乙烯-co-丙烯酸)膜(PVDF-g-P(SSA-co-AA)).研究了苯乙烯和丙烯酸的不同比例对膜的接枝反应及其相对湿度对膜电导率和含水量的影响.用傅立叶变换红外光谱(FTIR)检测原硅酸钠改性的PVDF膜经过接枝和磺化后所发生的结构变化,并用扫描电镜(SEM)观察PVDF膜接枝前后的形貌以及接枝磺化后产物PVDF-g-P(SSA-co-AA)膜的形貌及硫和硅分布.结果表明,原硅酸钠改性的PVDF膜与苯乙烯/丙烯酸同时发生接枝聚合反应,环境的相对湿度在20%～80%范围,对添加10wt%Na4SiO4的PVDF-g-P(SSA-co-AA)膜的电导率的影响基本不变,并达到0.0198S·cm-1.原硅酸钠改性的PVDF膜结构在接枝前后和磺化前后发生变化,确认磺化反应不只是在膜表面,同时渗入膜中进行.     

PAm-g-PMAA亲水性聚合物微球的合成

利用链转移自由基聚合和端基置换反应法 ,合成了苯乙烯基单封端的聚甲基丙烯酸叔丁酯 (PBMA)大分子单体 .在N ,N′ 亚甲基二丙烯酰胺 (Bis A)存在的条件下 ,使PBMA大分子单体与亲水性单体丙烯酰胺(Am)在乙醇 水的混合介质中进行分散共聚反应 ,得到了表面为PBMA接枝的聚丙烯酰胺 (PAm g PBMA)聚合物微球 .将所得PAm g PBMA微球在酸性条件下水解 ,得到了整体亲水的聚甲基丙烯酸接枝的聚丙烯酰胺(PAm g PMAA)聚合物微球 .用激光光散射、透射电子显微镜和X射线光电子能谱仪等对聚合物微球的直径、形态及表面组成进行了表征 .研究结果表明 ,在共聚反应中PBMA大分子单体的分子量与浓度、Bis A浓度和介质的组成对微球的形成与颗粒直径的大小有明显影响 ;所形成的聚合物颗粒是以PBMA为壳、以交联PAm为核的核壳结构微球 .     

PREPARATION AND PROPERTIES OF POLY(LACTIC ACID-CO-GLYCOL TEREPHTHALIC ACID)COPOLYESTER

1. INTRODUCTIONThe amount of industrial and municipal waste has been increasing all over the world. Therefore, the design and development of materials capable of being degraded into safe components under specific environmental conditions have become incre…     

无机聚合物正极材料聚三硫代磷氮烯的制备与表征

合成了无机化合物聚三硫代磷氮烯[NPS3]n,借助红外光谱与元素分析测试确定了聚合物的重复单元结构;并通过比表面积分析、粒度测试和扫描电子显微镜观察了无机聚合物材料的微观形貌;热重分析测试表明材料在300℃以下能够稳定使用;循环伏安实验发现,作为锂二次电池正极材料使用,聚三硫代磷氮烯的电化学还原反应在2.25 V(versus Li/Li+)发生,其可逆的电化学氧化反应在2.51 V(versus Li/Li+)进行;充放电测试显示这种无机材料具有745.2 mAh.g-1的首次放电容量,与理论值(759.0 mAh.g-1)十分接近,经过60次充放电循环后放电容量保持在708.8 mAh.g-1,容量保持率95.1%,循环性能优秀.     

温度及pH敏感聚（丙烯酸）／聚（N—异丙基丙烯酰胺）互穿聚合物网络水凝胶的...

合成聚（丙烯酸）／聚（Ｎ－异丙基丙烯酰胺）互穿聚合物网络（ＰＡＡｃ／ＰＮＩＰＡ ＩＰＮ）水凝胶，具有温度及ｐＨ双重敏感特性。这种水凝胶在弱碱性条件下的溶胀率远大于酸性条件下的溶胀率。在酸性条件下，随着温度上升，凝胶的溶胀率也随之逐渐上升；而在弱碱性条件下，温度低于聚（Ｎ－异丙基丙烯酰胺）（ＰＮＩＰＡ）的较低临界溶解温度（ＬＣＳＴ）时，溶胀率也随着温度的上升而上升，而温度达到ＬＣＳＴ时，凝胶的溶胀率     

PREPARATION AND PROPERTIES OF POLY （LACTIC ACID-CO-GLYCOL TEREPHTHALIC ACID） COPOLYESTER

To obtain a kind of biodegradable polymer material with satisfactory properties, a new biodegradable copolyester poly(lactic acid-co-glycol terephthalate) (PETA), was synthesized from three monomers of lactic acid, glycol and terephthalic acid. The resulting copolyesters, PETA, were characterized by FT-IR, 1H-NMR, DSC, TGA and by the ways of weight loss rate to characterize their biodegradability. The findings in this work indicated that, the TmS and TdS of copolyesters PETA increased with increasing contents of the terephthalic acid units. From the biodegradation tests in natural soil, boiling water, acid buffer solution and alkali buffer solution, it was shown that the biodegradability of copolyesters PETA decreased with increasing contents of the terephthalic acid units.