硫酸铵水溶液中丙烯酰胺与正离子单体的分散共聚研究

以硫酸铵(AS)水溶液为介质,进行丙烯酰胺(AM)与正离子单体甲基丙烯酰氧乙基三甲基氯化铵(DMC)分散共聚合,制备出水溶性聚合物分散体.研究了盐浓度、分散稳定剂浓度及其分子量、单体浓度等对反应体系及分散体粒径的影响.结果表明,随着分散稳定剂的用量从6%增加到14%,分散体的平均粒径先下降,后又随之上升.分散稳定剂分子量越大,所得分散体的平均粒径越小.硫酸铵和单体的浓度对平均粒径和粒子形态等影响显著,只有在较小的范围内才能制备出粒径较均一的正离子型水溶性聚合物分散体;硫酸铵浓度越大,生成聚合物分子量越低.     

阿维菌素纳米水分散体的制备、表征及稳定性

利用阿维菌素具有2个活性羟基的特性,设计合成了一种具有阿维菌素结构单元的阴离子型聚氨酯分散剂,采用核磁共振和红外光谱表征了其结构.利用分散剂与阿维菌素结构的相似性,将溶有阿维菌素的分散剂溶液加入水中,制备了阿维菌素的纳米水分散体.研究分散剂中羧基含量及其分子量对分散体粒径的影响,结果表明,随着羧基含量的增加,分散体粒径逐渐降低,适当控制分子量有助于改善分散剂的分散能力.透射电镜显示分散粒子具有近似球形的形貌,粒径在20~40 nm之间.纳米分散体具有较高的离心稳定性和稀释稳定性.     

荧光素与电子给体/受体LB膜的制备、表征和光电性质

本论文涉及的问题是功能材料的分子设计、合成和按预定分子顺序取向排列的薄膜制备,是当前科学技术的前沿课题之一。合成了一系列荧光素衍生物包括由荧光素和电子给体(葱、吩唾嗓)及电子受体(紫精)组成的模型化合物和二元化合物,其中九种是具有亲水基团和疏水基团的长链烷烃衍生物。并在此基础上制备了LB膜,详细地研究了它们的成膜特性。运用荧光显微镜、透射电子显微镜、原子力显微镜、反射椭圆偏振法、X-射线衍射法、转移折叠法和偏振红外光谱法等多种现代仪器和分析方法,研究了膜的均匀度、平均折射率和厚度、功能团取向与LB膜的结构问题,并讨论了分子结构和取向与性能的关系。     

寡链聚苯乙烯纳米颗粒的制备及其凝聚态特征

用一种新的苯乙烯 乳化剂 引发剂体系 ,通过微乳液聚合得到了聚苯乙烯(PS)纳米粒子 (直径为 2 0～ 43nm) ,并用凝胶色谱、激光光散射、透射电子显微镜测量了PS的分子量、粒子的平均粒径和质量 ,由此计算每个PS粒子所包含的平均分子链数 (Np) .系统地考察了单体、乳化剂和引发剂浓度对分子量、粒径和Np 的影响 .以一种每个纳米粒子中平均含 4根分子链的寡链聚苯乙烯颗粒 ( 4CPS)为例 ,用调制型示差扫描量热计、Fourier红外光谱、荧光光谱、固体13 C 核磁共振分别研究了原始的 4CPS颗粒 ,以及经冷冻、玻璃化转变温度以上热处理及溶解浇铸成膜后样品的热行为、光谱和分子运动特征 .结果进一步表明 ,在原始的 4CPS中 ,链段间凝聚缠结较少 ,而经冷冻和热处理后 ,形成了更多的凝聚缠结 .     

组份可控的钌螯合物功能单分子膜

用作“表面离子”的钌螯合物Ru(dpphen)32+与脂肪酸类成膜分子以1:2混合时能够得到稳定的混合单分子膜.以十八烷基三氯硅烷（octadecayl trichloro silane, OTS）分子部分取代Ru(dpphen)32+,得到功能分子组份可控的混合单分子膜.研究表明,OTS分子在纯水表面上可以形成交联网状单分子膜结构,混入硬脂酸（SA）分子后,网状结构逐渐被破坏.SA含量增加,破坏的程度就增大,直至SA/OTS为3:1时,完全没有网状交联结构,形成可以用来沉积LB膜的均匀致密的单分子膜.表面离子Ru(dpphen)32+与OTS和SA一起构成三组份混合单分子膜,OTS和Ru(dpphen)32+为表面离子.单分子膜中混有Ru(dpphen)32+分子,可以有效地阻止OTS的交联发生,同时Ru(dpphen)32+/SA基团与OTS/SA基团是均匀共混的.改变Ru(dpphen)32+/SA基团与OTS/SA基团的混合比,即可以做到Ru(dpphen)32+的组份精确可控,得到可用来沉积LB膜的均一、稳定的单分子膜.     

壳聚糖交联膜结构及性能的研究

壳聚糖是一种天然生物高分子聚合物，是甲壳素脱乙酰化产物，具有很好的成膜特性．用一种金属离子把壳聚糖分子中的螫合基团络合保护后，用戊二醛交联，并在酸性条件下将该金属离子洗脱，得到了螯合基团依然保留的壳聚糖交联膜．对壳聚糖交联膜的结构及性能进行了研究．结果表明：金属离子有效地保护了壳聚糖分子上的络合基因，该膜的性能较好，对阴离子的选择透过性比较好，并将其应用于元素的分离．     

半连续乳液聚合

从聚合速率，粒径及粒径分布，粒子数，分子量及分子量分布，共聚物组成；胶乳稳定性及有面基团浓度，膜性能等方面介绍了半连续乳液聚合的特点，并阐述水溶性大单体对半连续乳液聚合及其产物性能的影响。     

可在90℃工作的自交联碱性聚合物电解质膜的制备及表征

报道了一种具有短程自交联结构的碱性聚合物电解质.由于聚合物的交联仅发生在成膜过程且不需要外加交联剂,因此既可获得稳定的聚合物溶液供电化学器件制作使用,又可获得具有优异耐高温抗溶胀性能的交联型聚合物膜.此碱性聚合物电解质膜在室温纯水中电导率超过20mScm^-1,在90℃热水中电导率达到63mScm^-1且经过1000h后仅下降4%.在90℃水中膜溶胀率仅3%且具有良好的机械性能.     

一种新型的氢键自组装液晶光控取向膜

报道了一种新型的以氢键为驱动力的液晶自组装光控取向膜, 研究了薄膜的制备方法与光敏特性. 通过聚(4-乙烯基吡啶)中的吡啶基团与光敏聚丙烯酰氧基肉桂酸间的氢键作用制备了LBL(layer-by-layer)型的自组装多层膜, 制备过程的紫外-可见光谱表明, 该组装过程为逐层、均匀沉积过程. 傅里叶变换红外光谱表明, 多层膜的成膜驱动力为氢键. 用线性偏振紫外光辐照该薄膜, 多层膜中与光矢量方向匹配的光敏基团发生[2+2]环加成反应, 形成表面张力各向异性的薄膜. 用该薄膜作为向列相液晶的取向膜制成平行液晶器件, 在偏光显微镜下观察, 发现获得了均一、稳定的取向效果.     

侧链为光敏感基团的可生物降解聚氨酯的合成及表征

设计合成2-甲基-2-肉桂酰氧甲基-1,3-丙二醇(MCO)作为扩链剂,并以聚乳酸二醇(PLA diol)为软段,异佛尔酮二异氰酸酯(IPDI)和MCO为硬段制备了一系列侧链含有肉桂基团的可生物降解聚氨酯.结果表明MCO具有较高的反应活性,可满足制备高分子量聚氨酯的要求.聚氨酯结构中的肉桂双键可在紫外光和光引发剂的共同作用下,发生快速的交联反应,短时间内形成交联结构.软段结构相同时,凝胶含量随MCO含量的增加而增加.硬段结构相同时,凝胶含量随软段分子量的增加而减少.适度的交联可提高拉伸强度和形变回复率.     

Physical and Chemical Properties of Magnetite and Magnetite-Polymer Nanoparticles and Their Colloidal Dispersions

The properties of polymer-coated magnetite nanoparticles, which have the potential to be used as effective magnetic resonance contrast agents, have been studied. The magnetite particles were synthesized by using continuous synthesis in an aqueous solution. The polymer-coated magnetite nanoparticles were synthesized by seed precipitation polymerization of methacrylic acid and hydroxyethyl methacrylate in the presence of the magnetite nanoparticles. The particle size was measured by laser light scattering. It was shown that the particle size, variance, magnetic properties, and stability of aqueous magnetite colloidal dispersion strictly depend on the nature of the stabilizing agent. The average hydrodynamic radius of the magnetite particles was found to be 5.7 nm in the stable aqueous colloidal dispersion. An inclusion of the magnetite particle into a hydrophilic polymeric shell increases the stability of the dispersion and decreases the influence of the stabilizing agent on the magnetic and structural properties of the magnetite particles as was shown by X-ray diffraction and M?ssbauer and IR spectroscopy, as well as by vibrating sample magnetometry. The variation in the polymeric shell size and the polymer net density can be useful tools for evaluation of the polymer-coated magnetite particles as effective contrast agents. Copyright 1999 Academic Press.     

表面亲水性粒度单分散交联PMMA树脂的合成及表征

用种子溶胀聚合方法 ,合成出了粒度单分散的交联聚甲基丙烯酸甲酯微球 .将微球通过水解 ,使其转化为表面带羧基的树脂 .分别用多糖化合物Dextran和DEAE Dextran对水解树脂表面进行包覆涂层 ,然后用n 丁二醇双环氧丙醚分别进行交联 ,制备出两种表面带高交联多糖覆盖层的树脂 .以两种改性树脂为填料 ,以人血清蛋白为试样 ,用HPLC方法对树脂的亲水性能进行了表征 .研究表明 ,两种改性树脂均有很好的亲水性 ,蛋白质的回收率分别在 97%和 99%以上 ,并有良好的机械强度和化学稳定性     

Modification of aqueous polyurethanes by forming latex interpenetrating polymer networks with polystyrene

A series of latex particles with interpenetrating polymer network structure have been synthesized from waterborne polyurethane (PU) and polystyrene (PS). The effect of PU/PS composition, cross-linking density in the PS domain as well as in PU have been studied in terms of dispersion size, transmission electron microscopy morphology, mechanical and dynamic mechanical properties in addition to swellability in water and toluene of the dispersion cast film. It was found that inverted core (PS)–shell (PU) morphology was well defined and that the domain size as well as the film properties were well controlled by the latex composition and cross-linking density of both phases. Received: 15 March 2000 Accepted: 21 February 2001     

表面富集季胺盐的交联聚苯乙烯微球合成与表征及其溶胀行为研究

在聚合物微球表面引入不同的基团 (如亲水性的羟基或羧基 ) ,可以改善聚合物微球的稳定性甚至生物相容性[1～ 4] ;利用表面基团可以把无机半导体微粒和功能有机分子以及生物分子引入聚合物微球[5～ 8] ,赋予聚合物微球特殊的性能 ,使其广泛应用于涂料、光电功能材料和生物医用材料等领域[9～ 15] .其中 ,表面带有阳离子的聚合物微球在絮凝剂、胶粘剂、水性涂料等方面已经得到广泛研究[16～ 2 0 ] .通常阳离子聚合物微球可以根据不同的需要利用常规乳液聚合、核壳乳液聚合等方法来合成 .亲水性和疏水性单体进行的无皂乳液聚合[2 1] ,因其能在…     

Dispersion copolymerization of styrene and other vinyl monomers in polar solvents

Dispersion polymerization is a very attractive method for preparing micrometer‐size monodisperse polymer particles. The applications of microspheres have been greatly expanded by the use of copolymers. Here, the dispersion copolymerization of styrene and seven other vinyl monomers was carried out in polar solvents. The effect of the different comonomers on the particle size was systematically investigated. The particle size first decreased and then increased with an increasing fraction of acrylamide in the monomer feed, and at a higher fraction of such a comonomer, only a gel‐like polymer was obtained. The particle size also increased with the increase in the contents of the hydrophilic comonomers in the monomer mixtures, and the copolymer molecular weight decreased meanwhile. Although the amount of the hydrophobic comonomer in the monomer mixture changed, the particle size was hardly affected. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 555–561, 2001     

Size-dependent self-organization of colloidal particles on chemically patterned surfaces

A study of the self-organization of colloidal particles during the evaporation of particle solutions on chemically patterned surfaces is presented. On a surface with hydrophilic and hydrophobic regions, colloidal particles form compact structures on the hydrophilic sites. When a colloidal solution containing a mixture of particles with a variation in size is used, the number density of each type of particle deposited on the hydrophilic islands after evaporation decreases with increasing particle size. This makes it possible to produce a concentration gradient of the particles on islands of different sizes. It is shown that this technique could allow for particle separation.     

Effect of the content of urea groups on the particle size in water-borne polyurethane or polyurethane/polyacrylate dispersions

A series of anionic water-borne polyurethane and polyurethane/polyacrylate dispersions and their paint films was prepared. It was found by using TEM that there were three phases in the polyurethane/polyacrylate film, i.e. the hard segment-rich phase and the soft segment-rich phase of polyurethane, and the polyacrylate phase. By increasing the content of urea groups, the glass transition temperature of the soft segments and the dissociation temperature of the long-distance ordering of the hard segments were raised. This should mean that the motion of macromolecular chains was hindered by increasing the content of urea groups, and the hydrophilic carboxyl groups embedded initially in macromolecular coils could thus not transfer easily to the particle surface, which resulted in a greater average particle size in the dispersion.     

Structural conformation in a poly(ethylene oxide) film determined by X-ray emission spectroscopy

The electronic structure of pol(ethylene oxide) (PEO) in a thin (<1 mu) film sample was experimentally probed by X-ray emission spectroscopy. Both nonresonant and resonant X-ray emission spectra were simulated by using density functional theory (DFT) applied to four different models representing different conformations in the polymer. Calculated spectra were compared with experimental results for the PEO film. It was found that the best fit was obtained with the polymer conformation in PEO electrolytes from which the salt (LiMF6, M = P, As, or Sb) had been removed. This conformation is different from the crystalline bulk polymer and implies that film casting, commonly used to form electrolytes for Li polymer batteries, induces the same conformation in the polymer not depending upon the presence of salt.     

Surface active properties of polyoxyethylene macromonomers and their role in radical polymerization in disperse systems

Conventional dispersion polymerization and copolymerization of low-molecular weight (conventional) unsaturated monomers allows preparation of monodisperse and micronsize polymer particles. A similar behavior can be found in the surfactant-free dispersion polymerization of non-traditional vinyl monomers, unsaturated macromonomers. The latter systems allow preparation of random, comb-like, star-like and graft copolymers as well. An interesting alternative arises with the use of amphiphilic reactive macromonomers that contain a polymerizable group and aggregate into an organized structure -- a micelle. Under such conditions the high rate of polymerization and ultrafine (microparticles) polymer dispersions are generated. Thus, the surface-active macromonomers promote the formation of micelles and polymer growth within the main reaction loci -- polymer particles. Furthermore, the surface-active compounds can be formed during the copolymerization of hydrophilic macromonomer and hydrophobic low-molecular weight comonomer. The reactive surface-active oligomeric radicals are incorporated into the polymer matrix or the particle surface layer, which prevents them from subsequent migration. Besides, the covalently bound surface-active groups at the particle surface strongly increase the colloidal stability of final polymer dispersion. This article presents a review of the current literature in the field of the surfactant-free dispersion polymerization of the polyoxyethylene unsaturated macromonomers. Besides a short introduction into some kinetic aspects of radical polymerization of traditional monomers in homogeneous and disperse systems, we mainly focus on the organized aggregation of amphiphilic polyoxyethylene macromonomers, the characterization of amphiphilic graft copolymers and their aggregation properties, and radical copolymerization of polyoxyethylene macromonomers. We discuss the birth and growth of chains, the transfer of reaction loci from the continuous phase to polymer particles, the diffusion-controlled termination, association of amphiphilic reaction by-products, the particle growth by agglomeration, the particle nucleation, the deactivation of polymer chain growth and the colloidal stability. Effects of initiator type and concentration, the surface activity of macromonomer, the macromonomer type and concentration, temperature, additives and the type of continuous phase on the kinetics of polymerization, and colloidal parameters of the reaction system are also evaluated. Variation of the polymer coil density, the polymer-polymer interaction, and polymer-solvent interaction with the molecular weight, diluent and method (light scattering, the size exclusion, etc.) are discussed. Polymerization of macromonomers provides regularly branched polymers with varied branching density. Since both the degree of polymerization and the length of branches may be varied, polymeric materials with specific properties can be prepared.     

Synthesis and characterization of carboxylate waterborne cellulose emulsion based on cellulose acetate

With cellulose acetate (CA) as a base material, a novel environmentally friendly carboxylate waterborne cellulose acetate (CWCA) emulsion was synthesized via the method of self-emulsification. Taking advantage of acrylic acid, hydroxyethyl acrylate as a modifier, and isophorone diisocyanate as a bridging agent, the molecular structural design of CWCA dispersion was completed successfully, and the structure was confirmed by Fourier transform infrared spectroscopy (FTIR). In this work, the particle size and distribution of the stable CWCA dispersion with solid content of 22.6% are 115.6 and 0.158 nm, respectively. It was found that the microstructure of emulsion particles is a core-shell structure containing a hydrophilic carboxylate group as the shell and hydrophobic cellulose acetate molecular as the core. In addition, the hydrophobic behavior of CWCA film is presented as a contact angle of 109.9°. Furthermore, CWCA film provided a higher thermal decomposition temperature of 345.42 °C than that of CA film at the largest mass loss rate.