多孔Pd/α-Al2O3 活性膜上 1,5-环辛二烯选择加氢

利用微乳液及浸渍技术制备了多孔Pd/α-Al2O3催化活性膜.利用透射电镜、扫描电镜和X射线衍射对微乳液中及α-Al2O3陶瓷膜孔结构中纳米Pd颗粒的形貌和分布进行了表征.分析结果表明,通过浸渍技术,微乳液中的纳米Pd颗粒以几百纳米大小的晶体形态均匀负载于陶瓷膜孔中.在"催化接触器"型膜反应器中,以1,5-环辛二烯催化加氢为模型反应,考察了多孔Pd/α-Al2O3膜的活性与选择性,并与Pd-聚丙烯酸(PAA)有机催化膜反应器、悬浮床反应器和固定床反应器中的催化性能进行了比较.结果表明,Pd/α-Al2O3膜反应器的催化活性与目的产物1-环辛烯的选择性远高于Pd-PAA有机膜反应器和固定床反应器.Pd/α-Al2O3膜反应器在强化传质和消除孔内扩散方面效果显著,这与Pd在陶瓷膜孔中的分布及反应物在膜反应器中的高速流动有关.     

新型光驱动形状记忆有序多孔膜的设计及构筑

长期以来,设计和制备微纳米尺寸的有序多孔结构是材料科学领域的重要研究课题。聚合物有序多孔膜因兼具高度规则的孔结构和聚合物的多功能性,在工程技术和科学研究领域受到广泛关注。有序多孔膜的孔隙大小、形状及可重复使用等性质对其功能化和潜在应用具有重要影响。形状记忆特性是一种独特的环境响应特性。形状记忆材料能够记忆初始形状,并且在形变后能够在外界刺激下回复其初始形状。将形状记忆特性引入到有序多孔膜中,可实现多孔膜孔形状、尺寸的有效调控,并提高薄膜的可重复使用性,但由于多孔膜孔结构难以实现均匀形变,形状记忆有序多孔膜鲜有报道。华东理工大学林绍梁课题组在光驱动形状记忆多孔膜的设计和制备方面取得了一些新进展。     

聚合物纳米粒子乳液的制备及性能研究——添加组分对乳胶粒子形态及胶膜吸水率的影响

本文采用种子微乳液聚合方法,经后期氨化反应,合成了聚丙烯酸酯纳米粒子乳液,讨论了乳化剂、缓冲剂和水溶性丙烯酸单体等添加组分对乳粒子形态和胶膜吸水率的影响,并探讨了微乳液聚合的反应机理。     

微乳法制备的负载型铑催化剂粒子大小对CO加氢反应性能的影响

 利用微乳法,通过调节W0值(水与表面活性剂的摩尔比), 实现了负载型Rh/SiO2催化剂中金属铑粒子大小的可控合成. 该催化剂具有核壳结构,其中铑为核, SiO2为壳. TEM表征及反应评价结果显示金属铑的粒子大小(1.8～5.0 nm)对CO加氢反应性能具有显著的影响. 当粒子大小为3 nm时, CO加氢反应活性存在最小值; 随着粒子的进一步增大, CO加氢反应活性上升. 与浸渍法制备的催化剂相比,微乳法制备的催化剂粒子大小均一; 对负载量相同、平均粒子大小相同的两种催化剂,微乳法合成的Rh/SiO2催化剂对CO加氢反应具有较高的催化活性.     

二次阳极氧化方法制备有序多孔氧化铝膜

通过二次阳极氧化方法制备多孔氧化铝膜与一次阳极氧化方法制备多孔氧化铝膜孔排布规律性的对比,结果发现,二次阳极氧化方法制取的多孔氧化铝膜孔排布规律性明显好于一次阳极氧化法制取的多孔膜.在几个微米范围内,孔呈理想的六角排布.去除一次阳极氧化膜后,二次阳极氧化得以在更良好的表面进行,制取的氧化铝膜孔规律性和有序度更高.有序区域的尺寸与晶粒内的亚晶大小有一定关系.     

呼吸图案法制备蜂窝状有序多孔薄膜及其功能化应用

呼吸图案(BF)法是一种制备微纳米级规整多孔结构的简单、廉价和高效的方法, 它以水滴为模板, 通过水滴有序排列得到蜂窝状有序多孔结构, 其孔的形貌可以通过选择不同的成膜材料和成膜环境等条件得到控制, 所以在分离膜、模板、响应性表面、催化剂、光电材料等研究领域有广阔的发展前景. 但是, 到目前为止, 人们发现由于成膜条件的不同, 多孔膜的孔形貌受多种因素影响, 规整多孔膜形貌的控制机理还不是很明确, 没有一个统一的结论. 本文结合本课题组所做工作及近五年来国内外呼吸图案法制备蜂窝状有序多孔薄膜的研究成果, 对多孔薄膜的形成过程及其影响因素、多孔膜的功能化及应用等方面进行了归纳总结, 试图揭示孔的形成及孔形貌的调控等相关规律, 希望对后续的进一步研究与应用奠定基础.     

二氧化钛接枝聚(苯乙烯-二乙烯苯)/马来酸酐多孔纳米复合微球的制备及表征

中孔聚合物微球,由于具有大的比表面积、小的孔径和孔容,并有与外界环境介质相通的多孔孔道等特点而被应用于化妆品活性物和药物的缓释载体,以提高药物及化妆品活性物的安全性和使用效率.在早期的工作中,我们报道了聚苯乙烯-二乙烯苯[P(St-DVB)]多孔聚合物微球的制备及其在化妆品活性物缓释中的应用[4].[P(St-DVB)]多孔聚合物微球用于化妆品活性物的负载取得了较好的缓释效果,但是此种多孔聚合物微球在负载如Pasorl-1789类易光解的活性组分时,由于聚合物本身的透明性,当在紫外线等强光照射下,易光解的活性物就会发生分解,最终导致失去活性作用,因此纯的聚合物微球对易光解的活性物起不到良好的保护和缓释.纳米二氧化钛由于具有良好的紫外吸收和折射能力及无毒等优点而广泛地应用于化妆品的物理防晒剂.因此,将纳米二氧化钛均匀地覆盖在多孔聚合物微球的表面可以在聚合物微球表面形成一道阻挡紫外线的屏障,有效防止负载于多孔聚合微球内部的活性物的分解.本文通过开环反应方法制备了二氧化钛接枝聚(苯乙烯-二乙烯苯)/马来酸酐中孔复合微球.首先用氨基基团对纳米二氧化钛粒子表面进行修饰,一方面防止其团聚,另一方面使纳米粒子具有与聚合物微球产生共价键合的基团.然后对多孔聚合物粒子表面进行马来酸酐修饰,使其在保持原有的多孔形貌的基础上产生可与纳米粒子表面氨基开环反应的马来酸酐基团.制得的多孔纳米复合微球经红外光谱、扫描电镜、透射电镜、X光衍射能谱及紫外分光光度计等表征,结果表明,纳米复合微球表面均匀地覆盖了纳米二氧化钛粒子,复合粒子比纯聚合物粒子和未经修饰的二氧化钛粒子具有更好的紫外吸收效果.将制得的复合微球用于对活性物Parsol1789(一种化妆品活性组分,见光易氧化)的负载和缓释结果表明,纳米复合多孔微球对负载于多孔网络中的活性物具有屏蔽紫外防止氧化和缓释作用.     

二氧化钛接枝聚(苯乙烯-二乙烯苯)/马来酸酐多孔纳米复合微球的制备及表征 二氧化钛接枝聚(苯乙烯-二乙烯苯)/马来酸酐 多孔纳米复合微球的制备及表征

中孔聚合物微球, 由于具有大的比表面积、小的孔径和孔容, 并有与外界环境介质相通的多孔孔道等特点而被应用于化妆品活性物和药物的缓释载体, 以提高药物及化妆品活性物的安全性和使用效率. 在早期的工作中, 我们报道了聚苯乙烯-二乙烯苯[P(St- DVB)]多孔聚合物微球的制备及其在化妆品活性物缓释中的应用[4]. [P(St-DVB)]多孔聚合物微球用于化妆品活性物的负载取得了较好的缓释效果, 但是此种多孔聚合物微球在负载如Pasorl-1789类易光解的活性组分时, 由于聚合物本身的透明性, 当在紫外线等强光照射下, 易光解的活性物就会发生分解, 最终导致失去活性作用, 因此纯的聚合物微球对易光解的活性物起不到良好的保护和缓释. 纳米二氧化钛由于具有良好的紫外吸收和折射能力及无毒等优点而广泛地应用于化妆品的物理防晒剂. 因此, 将纳米二氧化钛均匀地覆盖在多孔聚合物微球的表面可以在聚合物微球表面形成一道阻挡紫外线的屏障, 有效防止负载于多孔聚合微球内部的活性物的分解. 本文通过开环反应方法制备了二氧化钛接枝聚(苯乙烯-二乙烯苯)/马来酸酐中孔复合微球. 首先用氨基基团对纳米二氧化钛粒子表面进行修饰, 一方面防止其团聚, 另一方面使纳米粒子具有与聚合物微球产生共价键合的基团. 然后对多孔聚合物粒子表面进行马来酸酐修饰, 使其在保持原有的多孔形貌的基础上产生可与纳米粒子表面氨基开环反应的马来酸酐基团. 制得的多孔纳米复合微球经红外光谱、扫描电镜、透射电镜、X光衍射能谱及紫外分光光度计等表征, 结果表明, 纳米复合微球表面均匀地覆盖了纳米二氧化钛粒子, 复合粒子比纯聚合物粒子和未经修饰的二氧化钛粒子具有更好的紫外吸收效果. 将制得的复合微球用于对活性物Parsol 1789 (一种化妆品活性组分, 见光易氧化)的负载和缓释结果表明, 纳米复合多孔微球对负载于多孔网络中的活性物具有屏蔽紫外防止氧化和缓释作用.     

应用微乳法制备二氧化硅包裹钯纳米粒子

以氯钯酸为钯源,正硅酸乙酯(TEOS)为硅源,利用十六烷基三甲基溴化铵(CTAB)/正己醇/水构成的微乳体系制备了二氧化硅包裹纳米金属Pd粒子.其中Pd的粒径可在5～30 nm调变,外部SiO₂层的厚度可在5～35 nm调变.详细考察了氯钯酸和正硅酸乙酯的浓度、微乳体系中水和正己醇的量等参数对制备的Pd/SiO₂粒子的大小及形态的影响.     

单分散聚苯乙烯微球的制备及表征

应用膜乳化-液中干燥法成功制备出粒径为2～20μm的单分散聚苯乙烯(PS)微球.PS微球的粒径主要由膜孔径决定,其值约为膜孔径的2倍;PS溶液的浓度对其也有一定的影响.膜乳化过程中的压力对微球粒径的分散性有很大的影响,在一定压力范围内,粒径呈单分散.在分散相中加入致孔剂,制备出表面多孔的PS微球.采用复乳-液中干燥法制备出中空PS微球.     

Synthesis of Poly(Vinyl Alcohol) and/or Poly(Vinyl Acetate) Particles with Spherical Morphology and Core-Shell Structure and its Use in Vascular Embolization

Poly(vinyl alcohol), PVA, is the most frequently used material in embolization of tumors, aneurisms and arteriovenous malformations due to its low toxicity, good biocompatibility and desirable physical properties. It is well known that PVA particles cannot be prepared by direct polymerization of vinyl alcohol. Its synthesis is typically performed by the suspension polymerization of vinyl acetate to produce poly(vinyl acetate), PVAc, followed by the saponification of the PVAc particles. This work shows that, using the suspension polymerization technique, it is possible to obtain spherical particles with a core-shell structure of PVA/PVAc with regular morphology, instead of particles with irregular shapes and sizes, as usually found in many commercial embolization products. Therefore, this work presents the production of PVA/PVAc spherical particles that can be used to occlude blood vessels, eliminating the disadvantages of commercial PVA. In vivo clinical tests with white “New Zealand” rabbits undergoing kidney inflammation reaction have shown that these spherical particles are much more efficient for vascular embolization.     

Characterization of poly(vinyl alcohol) during the emulsion polymerization of vinyl acetate using poly(vinyl alcohol) as emulsifier

During the emulsion polymerization of vinyl acetate (VAc) using poly(vinyl alcohol) (PVA) as stabilizer and potassium persulfate as initiator, the VAc reacts with PVA forming PVA-graft-PVAc. When the grafted polymer reaches a critical size it becomes water-insoluble and precipitates from the aqueous phase contributing to the formation of polymer particles. Since particle formation and therefore the properties of the final latex will depend on the degree of grafting, it is important to quantify and to characterize the grafted PVA. In this work, the quantitative separation and characterization of the grafted water-insoluble PVA was carried out by a two-step selective solubilization of the PVAc latex, first with acetonitrile to separate PVAc homopolymer, followed by water to separate the water-soluble PVA from the remaining acetonitrile-insoluble material. After the separation, the water-soluble and water-insoluble PVA were characterized by Fourier Transform Infrared (FTIR) spectroscopy and ¹H and ¹³C nuclear magnetic resonance (NMR) analyses, from which the details of the PVA-graft-PVAc structure were obtained. © 1996 John Wiley & Sons, Inc.     

Nanogels based on poly(vinyl acetate) for the preparation of patterned porous films

The use of poly(vinyl acetate) (PVAc) nanogels for the fabrication of patterned porous surfaces is described. These nanogels were synthesized by controlled radical cross-linking copolymerization (CRCC) involving a xanthate-mediated reversible addition-fragmentation chain transfer (RAFT) mechanism. This synthesis methodology allowed for the preparation of nanogels based on PVAc with a controlled constitutive chain length and average numbers of chains and cross-links. Solutions of these branched polymers were prepared in THF with a fixed amount of water and spin coated onto a surface of graphite. The surface porosity of corresponding films was observed by atomic force microscopy (AFM). Compared with linear PVAc homologues with a degree of polymerization (DP) sufficiently high to favor the formation of porous structures (DP = 50), a sharper and better defined porosity was observed with nanogels, the constitutive chains of which had the same DP. For nanogels differing only in their cross-link density, the pores were smaller and better defined in the case of the higher cross-link density, suggesting an enhanced stabilization of the water droplets during film formation. To explain these observations, it is postulated that PVAc nanogels can behave as compact particles providing steric stabilization of water droplets, which is referred to as a Pickering effect. The coalescence of water droplets would be better prevented as the cross-link density of the nanogels increases, resulting in a smaller size pore.     

室温交联型硅丙微胶乳的合成研究II.改性微胶乳的粒径控制及其微观形态表征

采用种子微乳液聚合法和单体预乳化法分别合成了室温交联型有机硅改性聚丙烯酸酯微胶乳,研究了硅烷单体的添加和氨化反应对改性微胶乳粒子大小及分布的影响。结果表明:采用种子微乳液聚合法得到的硅丙微胶乳粒子大小与硅烷单体的种类、用量和添加顺序无关,平均粒径约为40~60nm。TEM照片显示出,采用种子微乳液聚合法合成的硅丙微胶乳粒子由于内部存在交联结构而导致表面形状不规则,有“乳突”现象;而采用预乳化法合成的硅丙微胶乳粒径粗大,呈规则的球形,氨化后粒径从100nm以上减小到80nm左右,粒子表面出现“绒毛”现象,这是由于硅烷组分的水解反应受到抑制而使粒子内部的交联密度降低的缘故。     

Synthesis and characterization of monodisperse porous polymer particles

Monodisperse porous polymer particles in the size range of 10 μm in diameter were prepared via seeded emulsion polymerization. Linear polymer (polystyrene seed) or a mixture of linear polymer and solvent or nonsolvent were used as inert diluents. The pore diameters of these porous polymer particles were on the order of 1000 Å with pore volumes up to 0.9 mL/g and specific surface areas up to 200 m²/g. The physical features of the porous polymer particles depended on the diluent type and the crosslinker content, as well as the molecular weight of polymer seed particles. By varying the molecular weight of the linear polymer, monodisperse porous polymer particles with different pore size distribution could be synthesized. Polymer seed with a low degree of crosslinking instead of linear polymer could also be used to prepare monodisperse porous polymer particles with smaller pore volume and pore size.     

A Comparison of Membrane Emulsification Obtained Using SPG (Shirasu Porous Glass) and PTFE [Poly(Tetrafluoroethylene)] Membranes

SPG (Shirasu porous glass) membrane emulsification used to prepare uniform polymeric microspheres is briefly reviewed, and the performance of a hydrophilically treated PTFE [poly(tetrafluoroethylerie)] membrane is described and compared with that of the SPG membrane. A mixture of styrene. divinyl benzene and hexadecane (HD) was extruded through the membranes and dispersed in an aqueous phase containing polyvinylalcohol (PVA) and sodium lauryl sulfate (SLS) as mixed stabilizers. A hvdrophilically treated PTFE membrane was used with a stainless steel mesh support so that the membrane would not expand to affect the pore size during the emulsification. The nominal pore size of the PTFE membrane was replaced with the calculated one using a theoretical expression derived from the force balance between the external pressure and the interfacial tension between oil and water phases. The emulsion droplets prepared with the PTFE membrane revealed a broader size distribution than those obtained with the SPG membrane, and the rate of emulsificaton was nearly same for both membranes. Droplet size control was readily possible. The performance was significantly affected by the adsorption behavior of the stabilizers on the membrane surfaces. The contact angle profile of oil droplets on the PTFE membrane implied that the hydrophilically treated PTFE membrane is still hydrophobic compared to the SPG membrane. This tendency was reflected by the dependence of the average droplet diameter (and coefficient of variation, CV) on the concentration and composition of mixed stabilizers.     

致孔剂对HP（MA—VAc—MMA）载体孔结构的影响

以二乙烯苯和双丙烯酸多缩乙二醇酯为交联剂、聚醋酸乙烯酯（ＰＶＡｃ）或它与醋酸丁酯（ＢＡＣ）的混合物为致孔剂、ＢＰＯ为引发剂，用悬浮聚合随后水解的方法制得了部分水解聚（丙烯酸甲酯－醋酸乙烯酯－甲基丙烯酸甲酯）［ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）］多孔载体，研究了ＰＶＡｃ及（ＰＶＡｃ＋ＢＡＣ）用量、分子量及混合比对ＨＰ（ＭＡ－ＶＡｃ－ＭＭＡ）孔结构的影响。结果表明，当ＰＶＡｃ的Ｍ＞２．５×１０５，ＰＶＡｃ／ＢＡＣ为２．３，用量为１０～２０％时，可制得孔隙率较高，孔径分布较窄，孔表面积较大的多孔载体。这种载体适用于微生物固定化。     

Preparation of porous polylactide microspheres by emulsion‐solvent evaporation based on solution induced phase separation

Porous polylactide (PLA) microspheres were fabricated by an emulsion‐solvent evaporation method based on solution induced phase separation. Scanning electron microscopy (SEM) observations confirmed the porous structure of the microspheres with good connectivity. The pore size was in the range of decade micrometers. Besides large cavities as similarly existed on non‐porous microspheres, small pores were found on surfaces of the porous microspheres. The apparent density of the porous microspheres was much smaller than that of non‐porous microspheres. Fabrication conditions such as stirring rate, good solvent/non‐solvent ratio, PLA concentration and dispersant (polyvinyl alcohol, PVA) concentration had an important influence on both the particle size and size distribution and the pore size within the microspheres. A larger pore size was achieved at a slower stirring rate, lower good solvent/non‐solvent ratio or lower PLA concentration due to longer coalescence time. Copyright © 2005 John Wiley & Sons, Ltd.     

Pore structural studies of monodisperse porous polymer particles

Monodisperse polystyrene latex particles with molecular weight on the order of 10⁶ were used as inert diluents for the preparation of monodisperse porous styrene-divinylbenzene copolymer particles via seeded emulsion polymerization techniques. Mercury porosimetry and nitrogen adsorption-desorption isotherms were used to assess pore structure and pore size distribution. Pore size distribution was very sensitive to the molecular weight of the polystyrene latex particles used as inert diluent. Qualitative evidence from the techniques used indicated that the monodisperse porous polymer particles were macroporous (average pore diameter > 500 Å) in nature. As the molecular weight of the linear polymer decreased, the porous structure of the polymer particles ranged in complexity across the spectrum of macro/mesopore structures. Scanning electron microscope results indicated the existence of voids between the microspheres and their agglomerates within the porous polymer particle, and nitrogen adsorption isotherms confirmed that the pores were due to interstices between these crosslinked microspheres and agglomerates.     

Role of grafting in the emulsion polymerization of vinyl acetate with poly(vinyl alcohol) as an emulsifier. I. Effect of the degree of blockiness on the kinetics and mechanism of grafting

The role of grafting in particle nucleation during the emulsion polymerization of vinyl acetate with partially hydrolyzed poly(vinyl alcohol) (PVA) as an emulsifier and potassium persulfate as an initiator was investigated. The polymerizations were carried out in batch with a low solids (10%) recipe. An automated reaction calorimeter (Mettler RC1) was used for the direct monitoring of the kinetics of emulsion polymerizations with three medium molecular weight PVAs differing in their degrees of blockiness (Poval 217EE > 217E > 217). Smith–Ewart case 1 kinetics (average number of free radicals per particle < 0.5) were followed in all cases, and no constant rate in interval II was observed. Contrary to what was expected, a nonlinear relationship was observed between the rate of polymerization (R_p) and the number of particles (N_p). At R_{p max,} N_p (217E) > N_p (217EE) > N_p (217), and the final N_p was independent of the degree of blockiness of PVA. The particle size distributions were broad (particle diameter = 20–100 nm) and bimodal. On the basis of these data, we concluded that particle nucleation was continuous and was accompanied by extensive limited aggregation during the particle growth stages. The evolution of the amounts of grafted PVA and poly(vinyl acetate) (PVAc) were determined in polymerizations employing the two PVAs differing the most in blockiness (Poval 217EE and 217). The grafted PVAc followed similar profiles, increasing with conversion, particularly near the end of the two reactions. The amounts of grafted PVAc were about the same in the final latexes (37–39%). In contrast, the grafting of PVA was nearly complete by the time monomer droplets had disappeared in each reaction (25% conversion). However, the extent of grafting differed significantly, with the blockier PVA having about one‐third the grafting of the more random PVA (～10% vs ～30%). In these low solids recipes, grafting appeared to be primarily a solution event, occurring predominantly in the aqueous phase and not at the particle/water interface, as was previously speculated. The PVAc grafts grew until the molecules became water‐insoluble and precipitated, forming polymer particles. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3633–3654, 2001