高压静电喷雾法制备天然纤维素微球及影响因素研究

以绿色环保的碱脲体系溶解天然纤维素,并采用高压静电喷雾法制备再生纤维素微球.主要探讨了表面张力、静电力、溶液黏度和推进速度对微球形态和粒径的影响,并用扫描电镜、红外光谱和X射线衍射图谱进行了表征.结果表明,溶液表面张力的降低会使得微球粒径减小,其中粒径减小的程度与溶剂体系的挥发程度和溶液的均一性相关;同时,微球粒径随着静电力的增大呈减小趋势,而随着推进速度增加粒径呈单调上升趋势;微球形态与溶液黏度密切相关,当溶液黏度下降时,微球球形度下降,由球形变为楔形甚至带状结构,并且平均粒径有所减小,粒径分布增大.此外,再生后的纤维素微球具有良好的多孔性结构,纤维素化学性质没有发生改变,但晶型从纤维素Ⅰ转变为纤维素Ⅱ.     

分散聚合法制备PVP微球的研究

以N-乙烯基吡咯烷酮(NVP)为初始单体,乙酸乙酯为分散介质,采用分散聚合法制备了分散性能良好、粒径为3～4μm的聚乙烯基吡咯烷酮(PVP)微球.考察了单体、分散剂及引发剂浓度对PVP微球的粒径、单体转化率及分子量的影响,并对PVP的结构和性能进行研究.结果表明,单体浓度增加,PVP微球粒径和分子量增大,单体转化率升高;分散剂浓度增加,PVP微球粒径变小,分子量增大,单体转化率升高;引发剂浓度增加,PVP微球粒径变大,分子量减小,单体转化率升高.与溶液聚合法相比,分散聚合法制备的PVP分子量较小且具有一定的结晶性.     

静电喷雾法制备聚膦腈微球

用静电喷雾法制备了粒径窄分布的甘氨酸乙酯-苯丙氨酸乙酯取代聚膦腈的微球.主要探讨了溶剂、溶液浓度、流速、喷射电压及接收距离对微球形貌和粒径的影响.微球的表面形貌与溶剂性质和聚合物溶液浓度密切相关,微球粒径受聚合物溶液流速的影响比较显著,随流速增大粒径呈单调上升趋势.结果显示对于[η]=0.1 dL/g的(甘氨酸乙酯)0.3(苯丙氨酸乙酯)0.7取代聚膦腈,以0.25 g/mL的四氢呋喃溶液进行静电喷雾,可获得粒径分布窄(1~2μm)且近球形的微粒,其工艺条件可进一步用于载药聚膦腈微球的制备和控制释放研究.     

pH值、盐浓度敏感性两性聚电解质微球的合成及性质

以丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)和甲基丙烯酸(MAA)为单体,在乙醇介质中制备出对pH值、盐浓度双敏感的两性聚电解质微球。 采用透射电子显微镜(TEM)和红外光谱(IR)方法对其形貌和结构进行了表征。 研究了聚电解质微球在不同pH值溶液及NaCl、CaCl2盐溶液中粒径的变化情况。研究结果表明,第二步中反应制备的微球粒径为1 177 nm,多分散指数(PDI)为0.181;相比第一步反应制备的微球(d=764 nm;PDI=0.069)其粒径明显增大,PDI数值略有增加。当溶液pH＜4.3时,微球的粒径随溶液pH值的减小而逐渐增加;当pH＞4.3时,微球的粒径随溶液pH值的变大逐渐增加;pH=4.3时,微球的粒径具有最小值。盐溶液的pH值接近等电点时,在单价态NaCl溶液中,两性聚电解质微球表现出典型反聚电解质效应;而在多价态CaCl2溶液中,其粒径先增长再逐渐下降。     

Mn0.6 Zn0.4 Fe2 O4 磁性亚微球的可控合成及磁性能

采用溶剂热法制备了单分散Mn0.6Zn0.4Fe2O4磁性亚微米球, 研究了反应工艺参数对磁性亚微米球结构形貌、 直径和静磁性能的影响规律. 研究发现, 随着反应时间的延长, 体系中的金属离子首先水解沉淀, 形成羟基氧化铁及Mn, Zn氢氧化物, 然后脱水转化为Mn0.6Zn0.4Fe2O4球形纳米粒子, 这些纳米粒子发生团聚, 形成结构疏松、 大小不均匀的亚微米粒子, 最后通过Ostwald熟化过程, 形成致密的单分散亚微米球. 降低反应溶液的pH值、 增加乙二醇或聚乙二醇的用量, 均会使亚微球的直径增大, 并可在150~500 nm范围内调控微球的粒径; 但组成磁性亚微球的纳米粒子的粒径逐渐减小, 产物的饱和磁化强度增大, 矫顽力和剩磁减小.     

乙酸乙酯/乙醇混合溶液中分散聚合制备单分散亚微米级聚丙烯酰胺微球

以乙酸乙酯/乙醇混合溶液为分散介质, PVP为分散剂, 通过分散聚合法合成了单分散亚微米级PAM微球. 在反应初期, 自动加速现象明显. 由于凝胶效应的影响, 分子量随着单体转化率的提高而逐渐增大. 考察了分散剂浓度对最终产物增率的影响, 并用IR光谱对产物的结构进行了表征, 证明分散聚合体系中吸附稳定机理和接枝稳定机理同时存在, 且以后者为主. 同时还研究了混合溶剂比例、分散剂浓度、初始单体浓度和引发剂浓度对微球粒径及粒径分布的影响. 结果表明, 乙酸乙酯/乙醇体积比在5∶5-7∶3范围内, 可得到粒径在200 nm左右, 且分布较窄的PAM微球; 分散剂浓度增大, 粒径减小; 引发剂浓度增加, 粒径增大; 初始单体浓度较高或较低时, 都得不到单分散性微球.     

沉淀聚合制备聚(季戊四醇三丙烯酸酯-苯乙烯)单分散微球及其形成机理

以季戊四醇三丙烯酸酯(PETA)作交联剂,苯乙烯作共聚单体,偶氮二异丁腈作引发剂,在乙醇或其与水的混合溶剂中沉淀聚合制备了交联聚合物微球.研究了反应时间、交联剂用量以及溶剂中水含量对聚合过程及微球的影响.结果表明当PETA用量在单体质量的5%-35%之间且反应时间不低于6h时可制得单分散聚合物微球.当PETA用量低于20%时,所得微球的粒径随PETA用量的增加逐渐减小,粒径分布逐渐变窄;此后继续提高PETA用量,微球粒径又逐渐增大,粒径分布逐渐变宽.向反应介质中加入水,可明显提高微球产率及单体转化率,但其体积分数达30%时,所得微球分散性变宽.在此基础上对微球的形成机理也进行了讨论.     

阿司匹林-蒙脱土-壳聚糖缓释微球的制备及其体外释放性能

利用溶液法预先制备壳聚糖(Cs)-蒙脱土(MMT)复合材料(Cs-MMT),以Cs-MMT、Cs为原料,采用反相悬浮聚合法制得一种新型药物缓释体系阿司匹林-蒙脱土-壳聚糖载药微球(Asp-MMT-Cs)。采用FT-IR、SEM表征了Cs-MMT和Asp-MMT-Cs载药微球的结构及形态;设计正交实验优化了Asp-MMT-Cs载药微球的制备工艺;通过体外释放实验探讨了载药微球在不同模拟释放液中的释药规律。结果表明:所得微球球形度好,粒径分布较均匀;最优工艺制得的载药微球平均粒径为81.20μm,载药量为9.61%,包封率为76.78%。该缓释体系具有pH敏感性,更倾向于在pH较高的磷酸盐缓冲溶液中释放。     

结构与制备条件对两亲性偶氮聚合物胶体球尺寸和光响应性的影响

合成了3种具有不同官能团或官能化度的双亲性多分散偶氮聚合物.系统研究了它们在选择性溶剂中形成聚合物胶体球时,各种因素对胶体球尺寸和光响应性能的影响规律.结果表明,不仅官能团和官能化度对胶体球的尺寸与光响应性有明显影响,具体的制备条件(如初始浓度、沉淀剂加入速率等)对胶体球尺寸和光响应性能也有重要影响.聚合物胶体球的粒径随官能化度的增加而增大;随初始浓度的增加和沉淀剂加入速率的减小而增大.聚合物PEAPE胶体球的光致异构化速率快于PCNPE胶体球的光致异构化速率.聚合物胶体球的光致异构化速率随官能化度的增加而减小;随初始浓度的增加和沉淀剂加入速率的减小而减小.这些影响表现出了明显的规律性.从双亲性聚合物在选择性溶剂中自组装形成胶体球的热力学与动力学因素出发,讨论了上述现象产生的原因.     

苯乙烯和N-乙烯基吡咯烷酮共聚物/Ag复合微球的制备及性能研究

首先用无皂乳液聚合法制备了单分散聚苯乙烯(PSt)乳液,以此为种子乳液,使用N,N-亚甲基双丙烯酰胺(MBA)为交联剂,过硫酸钾(KPS)为引发剂,进行苯乙烯和N-乙烯基吡咯烷酮(NVP)共聚合制备了以PSt为核、St和NVP共聚物为壳的具有核-壳结构的聚合物微球(P(St-NVP)).以此微球为模板通过化学沉积法得到了粒径分布均匀、单分散的P(St-NVP)/Ag复合微球.傅里叶红外光谱、X-射线衍射、扫描电镜、透射电镜、激光粒度仪和紫外-可见光谱对复合微球的结构、形貌、物相及催化性能进行了表征.结果表明,P(St-NVP)/Ag复合微球具有规则的球形结构,粒径在400～700 nm之间,随交联剂浓度或种子乳液浓度的增加,复合微球粒径减小.粒径在十几个纳米左右的银粒子均匀分布在微球表面和内部.载银复合微球在NaBH4还原4-硝基苯酚为4-氨基苯酚的模型反应中表现出较高的催化活性.     

Preparation of polyvinylpyrrodione microspheres by dispersion polymerization

The preparation of polyvinylpyrrolidone (PVP) microspheres in ethyl acetate by dispersion polymerization with N-vinylpyrrolidone (NVP) as initial monomer, poly(N-vinylpyrrolidone-co-vinyl acetate) (P (NVP-co-VAc)) as dispersant, and 2, 2′-azobisisobutyronitrile(AIBN) as initiator is reported. The influences of monomer concentration, dispersant concentration and initiator concentration on the size of PVP microspheres as well as the monomer conversion were studied. The structure and properties of PVP microspheres were analyzed. The results show that the prepared PVP microspheres have a mean diameter of 3-4 μm. With an increase in NVP concentration, the size and the molecular weight of the PVP microspheres as well as the monomer conversion all increase. With increasing P(NVP-co-VAc) concentrations, the PVP molecular weight and monomer conversion both increase while the size of the microspheres becomes smaller. As the concentration of AIBN increases, the microsphere size and monomer conversion increase whereas the PVP molecular weight decreases. The PVP prepared by dispersion polymerization has a crystal structure, and its molecular weight is lower compared to that prepared by solution polymerization. __________ Translated from Acta Polymerica Sinica, 2007, 11 (in Chinese)     

Poly(N,N‐diethylacrylamide) microspheres by dispersion polymerization

Poly(N,N‐diethylacrylamide)‐based microspheres were prepared by ammonium persulfate (APS)‐initiated and poly(vinylpyrrolidone) (PVP)‐stabilized dispersion polymerization. The effects of various polymerization parameters, including concentration of N,N′‐methylenebisacrylamide (MBAAm) crosslinker, monomer, initiator, stabilizer and polymerization temperature on their properties were elucidated. The hydrogel microspheres were described in terms of their size and size distribution and morphological and temperature‐induced swelling properties. While scanning electron microscopy was used to characterize the morphology of the microspheres, the temperature sensitivity of the microspheres was demonstrated by dynamic light scattering. The hydrodynamic particle diameter decreased sharply as the temperature reached a critical temperature ～ 30 °C. A decrease in the particle size was observed with increasing concentration of both the APS initiator and the PVP stabilizer. The microspheres crosslinked with 2–15 wt % of MBAAm had a fairly narrow size distribution. It was found that the higher the content of the crosslinking agent, the lower the swelling ratio. High concentration of the crosslinker gave unstable dispersions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6263–6271, 2008     

Effect of Polyvinylpyrrolidone on Separation Performance of Cellulose Acetate-Polysulfone Blend Membranes

Blend membranes comprising cellulose acetate and polysulfone (CA/PSf) were prepared through a solution casting method using a different concentration of polyvinylpyrrolidone (PVP) as the pore former. Fourier transform infrared spectroscopy (ATR-FTIR) was used to investigate structural properties of membranes. Membranes morphology and its thermal properties were characterized by scanning electron microscope (SEM) and thermogravimetric analysis (TGA). The strength of membranes was studied by mechanical stability. The effect of PVP concentration on separation performance of the prepared membranes was studied. The separation performance of prepared membranes was tested by using an aqueous solution of cadmium metal complexed with humic acid. The results showed that an increase in the PVP concentration in the cast film from 0 to 3 wt% increased the thermal stability, water content (%), pure water flux, and solute rejection. SEM results showed that the pore size decreased but the number of pores increased on an increase in the PVP concentration.     

Effect of solution extrusion rate on morphology and performance of polyvinylidene fluoride hollow fiber membranes using polyvinyl pyrrolidone as an additive

<正>Polyvinylidene fluoride(PVDF) hollow fiber membranes prepared from spinning solutions with different polyvinyl pyrrolidone(PVP) contents(1%and 5%) at different extrusion rates were obtained by wet/dry phase process keeping all other spinning parameters constant.In spinning these PVDF hollow fibers,dimethylacetamide(DMAc) and PVP were used as a solvent and an additive,respectively.Water was used as the inner coagulant.Dimethylformamide(DMF) and water(30/70) were used as the external coagulant.The performances of membranes were characterized in terms of water flux,solute rejection for the wet membranes.The structure and morphology of PVDF hollow fiber were examined by BET adsorption,dry/wet weight method and scanning electron microscopy(SEM).It is found that the increase in PVP content and extrusion rate of spinning solution can result in the increase of water flux and decrease of solute rejection.The improvements of interconnected porous structure and pore size are induced by shear-thinning behavior of spinning solution at high extrusion rates,which could result in the increase of water flux of hollow fiber membranes.The increase of extrusion rate also leads to the increase of membrane thickness due to the recovery effect of elastic property of polymer chains.     

Photoinitiated dispersion polymerization of methyl methacrylate: A quick approach to prepare polymer microspheres with narrow size distribution

Photoinitiated dispersion polymerization of methyl methacrylate was carried out in a mixture of ethanol and water as dispersion medium in the presence of poly(N‐vinylpyrrolidone) (PVP) as the steric stabilizer and Darocur 1173 as photoinitiator. 93.7% of conversion was achieved within 30 min of UV irradiation at room temperature, and microspheres with 0.94 μm number–average diameter and 1.04 polydispersity index (PDI) were obtained. X‐ray photoelectron spectroscope (XPS) analysis revealed that only parts of surface of the microspheres were covered by PVP. The particle size decreased from 2.34 to 0.98 μm as the concentration of PVP stabilizer increased from 2 to 15%. Extra stabilizer (higher than 15%) has no effect on the particle size and distribution. Increasing medium polarity or decreasing monomer and photoinitiator concentration resulted in a decrease in the particle size. Solvency of reaction medium toward stabilizer, which affects the adsorption of stabilizer on the particle surface, was shown to be crucial for controlling particle size and uniformity because of the high reaction rate in photoinitiated dispersion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1329–1338, 2008     

微米级单分散共聚物微球的制备

用分散聚合法制备了苯乙烯 甲基丙烯酸甲酯微米级单分散共聚物微球 ,粒径为 5 4 μm .将分散聚合体系与乳液聚合体系进行了比较 ,并对共聚物微球的形貌、粒径分布及共聚情况进行了表征研究 .     

聚二乙烯基苯微球的合成及其表征研究

采用分散聚合方法制备了聚二乙烯基苯微球 ,研究了引发剂、稳定剂、单体 溶剂比例和溶剂种类对微球粒径及其分布的影响 ,在适当的条件下可以得到平均粒径较大、粒径分布较窄的微球 .用红外光谱法研究了聚合物微球内稳定剂、悬挂双键以及对位和间位二乙烯基苯含量随聚合过程的进行发生的变化 .测得的微球TG曲线表明 ,聚合物微球具有良好的热稳定性 .     

分散聚合与水热处理相结合制备单分散聚苯乙烯微球的研究

将分散聚合与水热处理相结合,以聚乙烯醇为稳定剂,以乙醇和水为分散介质,三羟甲基丙烷三丙烯酸酯为交联剂,一步法成功制备得到不同粒径的单分散交联聚苯乙烯微球.以乙醇/水的比例为50/50的反应体系为基础,研究了聚乙烯醇类型和含量,有机相含量,引发剂浓度,以及水热釜填充量等对所制备的微球形貌的影响,发现聚乙烯醇类稳定剂的分子量的降低和含量的增多倾向于生成黏连的微球;在有交联剂的条件下,不含稳定剂的体系仍能够得到单分散的交联PS微球;有机相含量的增加会导致微球呈现多分散性;而体系中引发剂的含量和反应液在水热釜中的填充量对微球的形貌影响不大.进一步针对水热法的特点分析探讨了一步法成功制备单分散的交联聚苯乙烯微球的原因及其机理.     

Controllable Preparation of Monodisperse Polystyrene Microspheres with Different Sizes by Dispersion Polymerization

Summary: Monodisperse polystyrene (PS) microspheres with different sizes were prepared by dispersion polymerization in dispersion media of ethanol/water and isopropayl alcohol/water, respectively. The effect of polarity of the dispersion medium, stabilizer and initiator concentration on the average sizes and size range were evaluated. The results show that monodisperse PS microspheres with different sizes could be prepared in dispersion media of ethanol and isopropyl alcohol/water when appropriate initiator and stabilizer concentrations were employed, and the latter is a more appropriate medium to prepare uniform PS microspheres. It was found that the microsphere sizes reduced with increasing water content in the dispersion medium. Furthermore, in isopropyl alcohol/water dispersions, the average sizes decreased with increasing stabilizer concentration.