在聚合物微球HEMA/NVP表面接枝聚合甲基丙烯酸的研究

采用悬浮聚合法制备了甲基丙烯酸羟乙酯与N-乙烯基吡咯烷酮的交联共聚微球;接着用甲基丙烯酰氯对交联微球进行了表面化学改性,将可聚合双键引入微球表面,制得了改性微球;然后,用"接出"法实施了甲基丙烯酸(MAA)在改性微球表面的接枝聚合,得到了接枝微球.用红外光谱法对几种微球的化学结构进行了表征,使用扫描电镜观察了形貌;考察了对MAA接枝聚合的主要影响因素.结果表明,交联微球在表面改性后,可顺利地实现MAA在微球表面的接枝聚合;在接枝聚合过程中,微球表面所产生的接枝聚合物层会形成动力学位垒,反应12h后接枝度不再变化,且在接枝度-温度与接枝度.引发剂用量曲线上出现最高点;接枝聚合适宜的反应温度为70℃,引发剂用量为单体质量的0.3%.对碱性蛋白的吸附性能的观察表明,在氢键与静电相互作用的协同作用下,接枝微球对溶菌酶具有很强的吸附能力.     

聚合物模板微球表面电性对中空二氧化硅微球形貌的影响

分别以过硫酸钾和偶氮二异丁基脒盐酸盐为引发剂,以聚乙烯吡咯烷酮(PVP)为分散剂,在水中引发苯乙烯聚合制备了2种表面分别带负电性和正电性基团的聚苯乙烯(PS)模板微球.在氨水催化下,利用正硅酸乙酯的水解缩合,形成PS/SiO_2复合微球,去除模板后得到中空SiO_2微球,并对其进行FTIR、电子显微镜、TGA以及氮气吸附等分析表征.结果表明,PS模板微球表面的电性决定了OH-的分布,从而导致PS模板微球表面SiO_2壳层不同的形成机制.当以表面带负电的PS微球为模板时,可得到树莓状的中空SiO_2微球;而以表面带正电的PS微球为模板时,得到是表面光滑的,具有介孔结构的中空SiO_2微球.     

两步后交联法制备氯甲基化聚苯乙烯交联微球

以平均粒径为40μm的非交联氯甲基化聚苯乙烯(CMPS)微球为出发物料,采用水解-轻度交联与重度交联两步骤的后交联方法,制备了氯甲基化聚苯乙烯交联微球.用红外光谱表征了交联前后微球化学结构的变化,使用扫描电镜观察了交联微球的形貌,重,点考察了各种交联条件对微球交联度的影响规律,分析了交联反应机理.结果表明:先将非交联氯甲基化聚苯乙烯微球部分水解并轻度交联,然后使CMPS微球在良溶剂中溶胀,使用Friedel-Crafts催化剂,再度进行交联反应,可顺利地制得氯甲基化聚苯乙烯(CCMPS)交联微球;控制交联反应的条件,如反应温度、反应时间、溶剂性质、催化剂种类与用量等,可获得交联度不同的微球,其球形度依然保持良好.     

DNA改性聚砜多孔微球选择性清除环境激素

将DNA视为生物大分子材料,制成DNA改性聚砜微球,在生物体外考察改性微球对环境激素,包括重金属离子的选择性清除.制备了2种改性聚砜微球:DNA共混微球(将DNA共混入聚砜溶液,当混合溶液滴入水中时,发生相分离而沉淀)和DNA表面改性聚砜微球(先制备聚砜多孔微球,再通过紫外线照射的方法将DNA接枝到聚砜微球表面).两种DNA改性聚砜微球在水中比较稳定,在酸或碱性条件下,由于DNA水解而不稳定.对环境激素的清除结果表明,DNA改性聚砜微球可以选择性清除包括联苯、苯酚和二恶荚类环境荷尔蒙物质;同时选择性吸附锌、铜、银、铅和铬等重金属离子.     

种子表面改性法制备核壳结构PSt/SiO_2复合微球

首先采用无皂乳液聚合法合成了表面带负电荷、粒径为360nm的单分散聚苯乙烯(PSt)种子乳液,并以EtOH/H2O混合物为分散介质,利用γ-氨丙基三乙氧基硅烷(KH-550)在25℃下对PSt微球表面进行改性,得到了表面硅烷化并带有正电荷的改性PSt种子乳液,然后在碱性条件下加入原硅酸乙酯(TEOS)使其和微球进行共水解与共缩聚,制备出了核壳结构PSt/SiO2复合微球,并利用电镜对复合微球的结构形态进行了表征.研究表明,PSt种子乳液改性时体系的zeta电位随着KH-550用量的增加而升高,当KH-550用量为PSt种子重量的1/3时,体系的zeta电位从原来的-34.5mV升高到了38mV,达到对PSt微球表面改性的最佳值;在制备PSt/SiO2复合微球时,TEOS水解缩聚形成的SiO2包覆到改性微球上的量随着反应时间的延长而增加,反应24h时达到97.9%的最大值;随介质中水含量的增加,吸附到复合微球表面上的SiO2纳米颗粒逐渐减少,复合微球表面逐渐变得光滑,当EtOH/H2O质量比降低到60/28.5时,得到结构均一、壳层厚度为35nm的核壳结构PSt/SiO2复合微球。     

碱式碳酸铜微球的表面改性和组装

报道了通过分散聚合反应在碱式碳酸铜微球表面锚接聚苯乙烯纳米粒子, 以调节其亲水/亲油性的方法. 结果表明, 锚接的聚苯乙烯纳米粒子尺寸愈大, 所得的改性碱式碳酸铜微球疏水性愈强. 用对油和水润湿性适中的改性碱式碳酸铜微球为乳化剂, 能够制备出稳定的油包水型Pickering乳液. 改性碱式碳酸铜微球组装在Pickering乳液的分散相液滴表面, 形成一个固体壳层. 将Pickering 乳液的分散相水核凝胶化, 合成出分级结构琼脂糖凝胶微球.     

PNVA-g-PSt微球的功能化与离子吸附研究

由大分子单体法合成了表面聚N-乙烯基乙酰胺接枝聚苯乙烯(PNVA-g-PSt)微球,通过对该接枝链进行化学改性得到了新型功能化高分子微球.用透射电子显微镜、激光光散射和X射线光电子能谱对高分子微球的形态、表面组成和直径大小进行了表征,发现微球经水解后形态更加规整,在分散状态下直径有所增加且保持核-壳型结构.实验比较了几种高分子微球对Cu2 ,Pb2 离子的吸附效果.定量测定结果表明:高分子微球经功能化处理后,其吸附效果有了很大的改进,在较低浓度范围,Pb2 离子的脱除率可达100%.     

表面含羧基的交联磁性高分子复合微球的合成

首先用化学共沉淀法制备了Fe3O4纳米微粒,并对其表面进行改性。然后在分散介质水中,以二乙烯基苯(DVB)为交联剂,采用改进的乳液聚合法,制备了磁性Fe3O4为核、苯乙烯和丙烯酸的共聚物为壳的交联复合微球,并利用FT-IR、TEM、XRD和XPS等对其进行表征。结果表明:该复合微球的粒度分布均匀、表面含有一定羧基,为单分散性、表面功能化的交联磁性高分子纳米复合微球。     

种子乳胶粒表面修饰法制备核壳结构PSt/TiO_2复合微球

首先采用无皂乳液聚合法合成了表面带负电荷、粒径为360 nm的单分散聚苯乙烯(PSt)乳液,并利用聚乙烯亚胺(PEI)在25℃下对PSt乳胶粒表面进行修饰,得到了表面带有正电荷的PSt种子乳液;然后以乙醇和水的混合物为反应介质,采用种子乳液加入法,使钛酸正丁酯(TBT)在修饰后的乳胶粒表面进行水解与缩合,制备出了核壳结构PSt/TiO2复合微球,利用电镜对复合微球的结构形态进行了表征.结果表明,PSt乳液改性时体系的zeta电位随着PEI用量的增加而升高,当PEI用量为PSt聚合物重量的15%时,体系的zeta电位从原来的-40.3 mV升高到了38.3 mV,达到对PSt乳胶粒表面改性的最佳值;在制备PSt/TiO2复合微球时,TiO2包覆量随着反应时间的延长而增加,反应7 h时达到90.2%的最大值;随介质中水含量的增加,吸附到复合微球表面上的TiO2纳米颗粒逐渐减少,复合微球表面逐渐变得光滑,当EtOH/H2O质量比为100/6.0时,得到结构均一、壳层厚度为29 nm的核壳结构PSt/TiO2复合微球.     

交联微球GMA/MMA的表面化学改性及卟啉在其上的固载化

采用悬浮聚合法,制备了甲基丙烯酸缩水甘油酯(GMA)与甲基丙烯酸甲酯(MMA)的交联共聚微球GMA/MMA。在此基础上,使用Brnsted酸对羟基苯甲醛(HBA)对交联微球进行了化学改性,通过环氧基团的开环反应,将HBA键合在交联微球表面,制得了化学改性微球HBA-GMA/MMA;重点考察了主要反应条件对改性反应的影响,表明采用极性较强的溶剂并升高温度有利于改性反应的进行。随后以微球HBA-GMA/MMA、溶液中的苯甲醛衍生物及吡咯为共反应物,使Adler反应在固-液界面上进行,实现了卟啉在交联微球GMA/MMA表面的同步合成与固载。     

A New Monodisperse Reactive Resin with Active Groups on the Particle Surface

The cross-linked polymer beads with reactive groups as active supports have been widely used in many fields such as chromatographic separation, solid phase synthesis, catalytic reaction, ion exchange and adsorption etc. In resent years, the synthesis and application of monodisperse polymer beads with different structures have been rapidly developed1~4. It is obvious that this type of monosized resin as matrix of active supports will be even more advantageous in some applications. This paper pr…     

SYNTHESIS AND PROPERTIES OF ACRYLIC-BASED SUPERABSORBENTS WITH ENHANCED CROSSLINKING ON PARTICLE SURFACE

A series of acrylic-based superabsorbent resins were synthesized by inverse suspension polymerization, using potassium persulfate as the initiator, N, N＇-methylene bisacrylamide （BIS） and divinylbenzene （DVB） as the multiple crosslinking agents. The morphology of the resulting superabsorbent resins revealed by SEM demonstrated that a hard shell layer was indeed formed due to surface crosslinking. The swelling and deswelling properties, and the mechanical strength of superabsorbents were investigated. The results indicated that the adding time of DVB and the amount of DVB participated in the crosslinking show a significant influence on the properties of superabsorbents. When DVB was added in polymerization later, the amount of DVB participated in reaction decreases and the surface crosslinked shell becomes thinner. It is suitable for DVB to be introduced in the later stage of the polymerization process, because the absorption rate of resin is efficiently improved in conjunction with higher water absorption. Furthermore, it was found that the mechanical strength of swollen superabsorbent with surface crosslinking was indeed enhanced in comparison with that of the conventional one.     

Synthesis of crosslinked resin based on methacrylamide, styrene and divinylbenzene obtained from polymerization in aqueous suspension

A series of porous copolymer beads based on methacrylamide (MA), styrene and divinylbenzene (DVB) was prepared by aqueous suspension polymerization in the presence of diluents to act as precipitants. As MA is totally soluble into aqueous phase, the use of two types of phase transfer agent was investigated, namely: TritonX-100^TM [polyoxyethylene-(10)-isooctylphenyl-ether] and tetrabutylammonium perchlorate. The effect of the diluents on the surface appearance and the porous structure of copolymer beads was studied. Suitable particle stabilisation was achieved by using a combination of two suspension agents, namely: gelatin and 2-hydroxy-ethyl-cellulose. The network resins were characterized by optical and scanning electron microscopy, IR spectroscopy, elemental analysis (CHN), apparent density, swelling in different solvents and specific area by BET method. It was observed that the MA incorporation was more effective when Triton^TM was employed as phase transfer agent.     

Formulation characterization and in vitro evaluation of acacia gum–calcium alginate beads for oral drug delivery systems

In the present work, new matrix bead formulations based on linear and branched polysaccharides have been developed using an ionic gelation technique, and their potential use as oral drug carriers has been evaluated. Using calcium chloride as a cross‐linking agent and sodium diclofenac (SD), as a model drug, acacia gum–calcium alginate matrix beads were formulated. The response surface methodology based on 3² factorial design was used as a statistical method to evaluate and optimize the effects of the biopolymers‐blend ratio and the concentration of calcium chloride on the particle size (mm), density (g/cm³), drug encapsulation efficiency (%), and the cumulative drug release after 8 hours (R_8h,%). The optimized beads with the highest drug encapsulation efficiency were examined for a drug‐excipients compatibility by powder X‐ray diffraction, differential scanning calorimetry, thermo‐gravimetric analysis, and Fourier transform‐infrared spectroscopy analyses. The swelling and degradation of the matrix beads were found to be influenced by the pH of medium. Higher degrees of swelling were observed in intestinal pH than in stomach pH. Accordingly, the drug release study showed that the amount of SD released from the acacia gum–calcium alginate beads was higher in intestinal pH than in stomach pH. Therefore, the in vitro drug release from the SD‐loaded beads appears to follow the controlled‐release (Hixson‐Crowell) pattern involving a case‐2 transport mechanism operated by swelling and relaxation of the polymeric blend matrix.     

Narrow‐disperse,cross‐linked polymer microspheres by one‐step dispersion polymerization with a chain transfer agent

The increasing demand for monodispersed cross‐linked polymers in high‐quality applications requires continuous improvement in their preparation process. In this study, an appropriate amount of a chain transfer agent was added to a traditional cross‐linking system, resulting in the preparation by one‐step dispersion polymerization of cross‐linked polystyrene (PS) microspheres with a particle size of 3.867 μm and a diameter coefficient of variation of 0.011. The particles were characterized using scanning electron microscopy (SEM) and an Ubbelohde viscometer. The results show that the tertiary dodecyl mercaptan (TDDM) chain transfer during nucleation increases the oligomer concentration, promotes the aggregation of the oligomers, increases the primary particle size, and reduces the cross‐linking effect. This controls the volume of cross‐linked chains in the primary particles, thus avoiding the problem of poor dispersion of the polymer microspheres due to the introduction of divinylbenzene (DVB). This study produces a preparation method for cross‐linked microspheres.     

聚苯乙烯基偶氮聚合物的合成研究

改进了聚苯乙烯的硝化、还原、重氮化和偶合反应路线 (NRDC) ,使每步反应都得到很高的产率 ,并利用大分子重氮盐 (MDS)分别与苯胺、N 烃基苯胺和酚等三类化合物偶合 ,得到相应的聚苯乙烯基偶氮聚合物 .核磁共振分析结果证明了产物的高偶联率 .通过对大分子重氮盐热稳定性的研究 ,发现偶合反应之后需要一步加热反应以消除残余重氮基团 .还研究了这些聚合物的紫外 可见吸收光谱性质 ,氨 (胺 )基偶氮产物的水溶液表现出了明显的pH敏感性     

Suspension polymerization of poly(ethylene glycol) methacrylate: a route for swellable spherical gel beads with controlled hydrophilicity and functionality

 Spherical and swellable gel beads were obtained by the suspension polymerization of poly(ethylene glycol) methacrylate macromonomer (PEG-MA). The average size and size distribution properties, the equilibrium swelling behaviour and the protein adsorption characteristics of PEG-MA-based gel beads were determined. In the suspension polymerization system, the organic phase including monomer, cross-linker and diluent solution was dispersed in an aqueous medium by using poly(vinylpyrrolidone) as the stabilizer. The diluent solution was prepared by mixing cyclohexanol and octanol at different volume ratios. The suspension polymerization experiments were designed in two separate parts. In the first part, ethylene glycol dimethacrylate was selected as the cross-linker and swellable PEG-MA-based gel beads were obtained by changing the cross-linker concentration, the monomer/diluent ratio and the stirring rate. In the second part, a more hydrophobic structure, divinylbenzene (DVB) was tried as a cross-linker. In this part, PEG-MA-DVB copolymer beads were obtained by changing the DVB/PEG-MA feed ratio. Then, the hydrophicility of the resulting gel beads could be controlled by changing the feed ratio of hydrophilic macromonomer to hydrophobic cross-linker. This property was also used to control the extent of nonspecific protein adsorption onto the surface of the gel beads. The non specific albumin adsorption onto the gel beads decreased with increasing PEG-MA content. No significant nonspecific adsorption at the isoelectric point of albumin was detected onto the gel beads produced with the higher PEG-MA/DVB feed ratios. For specific albumin adsorption, a triazinyl dye (i.e., cibacron blue, CB F3G-A) was covalently attached onto the surface of the copolymer beads via terminal hydroxyl groups of PEG-MA. The results of albumin adsorption experiments with the CB F3G-A carrying beads indicated that an appreciable specific albumin adsorption capacity could be obtained with the gel beads produced with a PEG-MA/DVB feed ratio of 1.5/4.0. Received: 16 August 1999/Revised: 27 December 1999     

亚微米级聚苯乙烯/聚硅氧烷核壳粒子的制备及其应用

以乳液聚合制备的聚苯乙烯乳液为种子,加入甲基三甲氧基硅烷(MTMS)水解溶液进行缩聚反应,合成亚微米级聚苯乙烯/聚硅氧烷核壳粒子,并以此作为光散射剂添加至聚甲基丙烯酸甲酯(PMMA)树脂中,制备了光散射材料;考察了亚微米级核壳粒子添加在PMMA树脂中的分散性。结果表明:经过双螺杆剪切作用的挤出加工后,可以实现核壳粒子在PMMA树脂中的良好分散。核壳粒子可以大幅度提高PMMA的雾度,当聚苯乙烯/聚硅氧烷核壳粒子(NS82)的含量为1%时,制得的PMMA样片(厚度为2 mm)的雾度为89%,透光率为69%,有效光散射系数为61%。     

硫代-Iniferters法活性自由基嵌段共聚合

自由基活性聚合近来发展很快,本文在概述了自由基活性聚合及其最新进展的基础上,对硫代－Ｉｎｉｆｅｒｔｅｒｓ法自由基活性聚合的机理,硫代－Ｉｎｉｆｅｒｔｅｒｓ法大分子引发剂的合成以及这些大分子引发剂在嵌段共聚物的制备等方面进行了综述。     

Delivery systems for some biologically active 1,2,4‐triazine derivatives: synthesis and release

Triazine‐loaded polymer microparticles composed of cross‐linked polymethylmethacrylate (PMMA) have been prepared. A series of PMMA cross‐linked polymers were prepared from methylmethacrylate (MMA) and divinylbenzene (DVB) by suspension polymerization using different percentages of solvents and cross‐linkers. Biologically active compounds including 4‐amino‐6‐substituted‐3‐thioxo‐3,4‐dihydro‐2H‐5‐oxo (or thioxo)‐1,2,4‐triazines (I–IV) were prepared and reacted with PMMA. Since optimization of the polymer delivery system is required to improve clinical applications, the effect of surface area, cross‐linker percentage on the loading, and release of triazines were studied. Alkaline conditions seem to favorably affect triazine release. Triazine hydrochlorides were ion exchanged with sodium montmorillonite (Na‐MMT). X‐ray diffraction (XRD) analysis confirms the intercalation of triazines between the layers of MMT. The presence of mineral domains with an average size of 33 nm was observed by transmission electron microscopy (TEM). The release of triazine compounds is more controllable in intercalated layered silicates. Copyright © 2008 John Wiley & Sons, Ltd.