基于Ugi多组分反应的海藻酸酰胺衍生物改性二氧化硅纳米粒子的制备

采用海藻酸酰胺衍生物通过Ugi多组分反应制备了新颖的聚合物-二氧化硅(Oct-Alg-Si O_2)纳米粒子.通过氢核磁共振波谱(~1H NMR)和X射线光电子能谱(XPS)对Oct-Alg-Si O_2的结构和表面元素组分进行了表征.采用透射电子显微镜(TEM)、Zeta电位和激光粒度分析仪对Oct-Alg-Si O_2的形貌、粒径和胶体性能进行了探索.结果表明,海藻酸酰胺衍生物共价接枝到氨基二氧化硅(Si O_2-NH_2)纳米粒子的表面,提高了其平均直径,调控了其Zeta电位,在水介质中能够表现出良好的分散稳定性.以10%的液体石蜡为油相,采用Oct-Alg-Si O_2制备了Pickering乳液.在油水界面能够形成液滴粒径为5.7μm的稳定Pickering乳液.随着水相p H值的增大,乳液体积分数增大,稳定性增强.细胞相容性实验结果表明,Oct-Alg-Si O_2纳米粒子具有极好的生物相容性.     

NiFe2O4与TiO2稳定的多重Pickering乳液的制备

由沉淀法和溶胶-凝胶法分别制备了Ni Fe_2O_4和Ti O_2,并用XRD和SEM对两种粒子进行了表征,结果表明成功制备了粒径大小较为均匀的目标产物。用CTAB对Ni Fe_2O_4进行了改性,并由IR和Zeta电位测试予以确认。以改性Ni Fe_2O_4和Ti O_2作为稳定粒子,由两步法制备了W/O/W型多重Pickering乳液,采用数码照片和光学显微照片观察所制备的乳液的宏观与微观形貌。研究表明,制备的单重Pickering乳液粒径较为均匀,多重Pickering乳液粒径范围稍宽,但两者稳定性能都非常良好。     

纳米玉米醇溶蛋白微球稳定的O/W型Pickering乳液

利用相分离工艺制备玉米醇溶蛋白(zein)纳米微球,微球粒径可控制在40 nm左右;经旋转蒸发制得zein溶胶体系,zein溶胶具有明显的丁达尔现象,静置数月不聚沉,Zeta电位法测得zein微球在pH值为4.0时分散性能最佳。 以纳米zein微球为固相稳定剂制备O/W型Pickering乳液,考察了zein胶体加入量、油水体积比等因素对乳液稳定性的影响。 实验结果表明,zein胶体加入量的质量分数控制为0.4%,高油水体积比将有利于Pickering乳液的长时间稳定。 基于zein分子的两亲结构和界面组装特点,提出了zein微球稳定Pickering乳液的作用机制。     

苯丙乳液合成反应条件优化

以苯乙烯、丙烯酸、丙烯酸丁酯、甲基丙烯酸甲酯等为单体,采用乳液聚合制备了苯丙乳液,研究了合成温度、引发剂用量、乳化剂用量、功能性单体丙烯酸用量等反应条件对苯丙乳液性能的影响,并探讨了丙烯酸单体对乳液耐酸碱稳定性的影响,确定了合成反应条件.结果表明,随着合成温度的提高,混合单体的转化率迅速增加,78℃时转化率最大(达到97.1%),而后随温度继续提高基本保持不变.混合单体转化率随过硫酸钾引发剂用量的增加呈现先增加后逐渐降低的趋势,当过硫酸钾与混合单体质量比为0.010时转化率最大,此时单体转化完全.此外,随着乳化剂用量增加,乳液的外观、钙离子稳定性、凝胶等性能都有所提高,但吸水率也相应增加.最佳合成反应条件为:合成温度为78℃,混合单体组成为15g苯乙烯、2g丙烯酸、18g丙烯酸丁酯、8g甲基丙烯酸甲酯,引发剂和乳化剂与单体质量比分别为0.010和0.035.得到的苯丙乳液在酸性条件下具有良好的稳定性.     

超浓反相聚合物乳液的粒径双峰分布特征及其与稳定性的关系

以丙烯酸、丙烯酰胺、2-丙烯酰胺基-2-甲基丙磺酸作为混合单体,Span-80和Tween-60作为复合乳化剂、采用氧化还原引发体系在常温下引发聚合,制备了稳定的超浓反相聚合物乳液,同时制备了低分散相体积分数的普通乳液及由普通乳液离心得到的超浓反相聚合物乳液作为对比研究.用显微镜观察了乳胶粒的形态,统计计算了乳胶粒粒径...     

含三苯基乙基苯氧基聚氧乙烯醚甲基丙烯酸酯功能单体的缔合型乳液增稠剂的制备及增稠机理

采用半连续法乳液聚合以甲基丙烯酸、丙烯酸乙酯、邻苯二甲酸二烯丙酯和不同量的功能单体三苯基乙基苯氧基聚氧乙烯醚甲基丙烯酸酯(SEM-25)为原料合成了疏水改性碱溶性增稠剂乳液. 测定了增稠剂乳液的粘度、透光率、pH、粒径及其分布, 结果表明随着pH值的增加, 乳液的粘度和透光率首先迅速升高, 然后缓慢下降. 随着SEM-25用量的增加, 乳胶粒的粒径先增大后减小. 与不含SEM-25的乳液增稠剂相比较, SEM-25低含量增稠剂的增稠效果和抗剪切性没有提高, 只有当SEM-25用量提高至单体质量的12%, 且乳液固含量大于0.65%时, 所制备缔合型增稠剂乳液的粘度和流变性比不含SEM-25的增稠剂才有明显提高. 在此基础上研究了增稠剂对苯丙乳液的增稠性. 含有增稠剂的苯丙乳液的粘度和透光率随pH值的变化与纯增稠剂乳液的变化类似. 只有当加入0.34 wt%苯丙乳液固体质量的增稠剂, 并且增稠剂中SEM-25含量达到5 wt%时苯丙乳液的粘度与使用不含SEM-25的增稠剂增稠的粘度相比才有明显增高. 在此基础上对增稠剂的增稠机理进行了探讨.     

高固含量低粘度P(MMA/BA/AA)乳液的制备及性能研究

先利用半连续种子乳液聚合法制备固含量为50%,粒径480nm的单分散甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)与丙烯酸(AA)的共聚物种子乳液;然后以上述种子乳液为介质,十二烷基硫酸钠为乳化剂,碳酸氢钠为缓冲剂,过硫酸铵为引发剂制备固含量72%,乳胶粒具有二元分布特征的高固含量、低粘度稳定乳液:其中大乳胶粒径500～600nm,小乳胶粒径约80nm.所得乳液中乳化剂总含量为聚合物质量的2.1%;粘度在剪切速率为21s-1时为400mPa·s.另外,相对于常规乳液,所制备高固含量乳液胶膜具有更好的光泽度.     

喹乙醇分子印迹聚合物的制备及其应用

采用Pickering乳液聚合法,以纳米SiO_2作为稳定剂,制备喹乙醇分子印迹聚合物。通过扫描电镜对聚合物进行表征,对其吸附性能进行研究。结果表明,与传统的乳液聚合法相比,采用Pickering法制备的聚合物粒径更为均一,分散性更好。聚合物具有较高的吸附量以及良好的选择性,将其作为固相萃取填料,结合高效液相色谱法对饲料中的喹乙醇进行分离及检测,效果良好。方法回收率为85.71%～95.23%,相对偏差小于2.9%,检出限为0.96 mg/L。     

有机硅-丙烯酸酯聚合物乳液合成及粒径分析

通过种子乳液半连续法合成了有机硅改性丙烯酸酯聚合物乳液,并对其粒子形态及分布进行分析。结果表明:通过种子乳液半连续聚合工艺可制备出固含量42wt%,乳化剂含量4wt%(基于单体量)、窄分布纳米粒子的有机硅改性丙烯酸酯聚合物乳液。随反应进行,粒径分布变窄,平均粒径逐渐增大。随乳化剂中SDS与OP-10的摩尔比减少,粒径增大。     

粒子与聚合物协同稳定高内相Pickering乳液

选用二氧化硅纳米粒子(H30)和聚(乳酸-羟基乙酸)共聚物(PLGA)为复合稳定剂, 成功制备出内相体积分数高达90%的高内相Pickering 乳液. 对照实验表明: 单独用H30粒子作稳定剂, 内相体积分数上限为75%; 单独用PLGA 作稳定剂, 发生严重相分离, 不能形成乳液. 无机纳米粒子与聚合物之间的协同作用在制备高内相乳液的过程中起到了关键作用. 因此, 使用无机粒子和聚合物作为混合稳定剂制备高内相乳液是一种新型而有效的方法.     

Preparation of PEG-modified urethane acrylate emulsion and its emulsion polymerization

In order to improve stability and reduce droplet size, the PEG-modified urethane acrylates were synthesized by the reaction of polyethylene glycol (PEG) with residual isocyanate groups of urethane acrylate to incorporate hydrophilic groups into the molecular ends. The droplet sizes of the PEG-modified urethane acrylate emulsions were much smaller than those of unmodified urethane acrylate emulsions at the same surfactant composition, and the droplet sizes of these emulsions were significantly effected not by surfactant compositions and types, but by the reaction molar ratio of PEG, because the urethane acrylate containing polyoxyethylene groups as terminal groups aided the interfacial activity of surfactant molecules and acted as a polymeric surfactant. The actions of PEG-modified urethane acrylate were confirmed by the investigation of adsorption of urethane acrylate in a water/benzene interface.For polymerization of emulsions, the stability of emulsion in the process of emulsion polymerization was changed by the type of surfactant or initiator. In the case of emulsion polymerization with a water soluble initiator (K₂S₂O₈), the emulsions prepared using TWEEN 60 were broken in the process of polymerization. However, polymerization of these emulsions could be carried out using an oil soluble initiator (AIBN). The conversion of emulsion polymerization changed with the type of urethane acrylates, that is, the reaction molar ratio of PEG to 2-HEMA.     

Destabilization of a dual emulsion to form a Janus emulsion

A vegetable oil (VO) was added to an emulsion of silicone oil in water (SO/W) with mixing limited to once turning the test tube upside down. Initially, the VO was dispersed into virtually centimeter-sized drops and the emulsion contained effectively no Janus drops, while after 1 h of agitation at a low level to prevent creaming, drops of 50–100-μm size of the two oils were observed: in addition to an insignificant number of Janus drops. The topology of the latter showed them to emanate from flocculated individual drops of the two oils, but with no discernible effect by the interfacial tension equilibrium on the drop topology. Continued gentle mixing gave increasing fraction of Janus drops of increased size with a topology gradually approaching the one expected from the interfacial equilibrium at the contact line. The spontaneous formation of Janus drops indicated a reduction of the interfacial free energy in the process and the interfacial energy difference between separate and Janus drops was calculated for an appropriate range of interfacial tensions and for all oil fractions. The calculations enabled a distinction of the decrease due to interfacial area changes from the reduction of interfacial tensions per se, with the latter only a minor fraction. Figure

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Asphalt-polyolefin emulsion breakdown

An analysis of factors controlling the stability of asphalt-polyolefin emulsions is given. From flocculation kinetics and changes in particle size distributions, it is concluded that the major cause of instability is due to Brownian coalescence followed by gravitational flocculation and creaming. A cyclical change in the particle size distribution, indicative of simultaneous flocculation and creaming, is observed only in the final stages of the emulsion breakdown.     

Non-ionic emulsion polymerisation

A process, similar to conventional emulsion polymerisation, is described by which sterically stabilised polymer dispersions are made in water alone. Ionic initiators and surfactants are replaced by non-ionic species, and a copolymerisable stabilising macromonomer is also used. The dispersions have good stability to solvent addition, high shear rates and freeze-thaw cycling; however, the effectiveness of stabilisation depends on the nature of both the monomers and the macromonomers.     

Kinetics of emulsion polymerization

The quantitative theory of the free-radical mechanism in emulsion polymerization is reexamined. A mechanism involving desorption and reabsorption of radicals is discussed. The average number of radicals per particle has been calculated as a function of three parameters. A simplified, approximate solution for the average number of radicals per particle is given for cases where this number is low.     

Doubly pH-responsive pickering emulsion

A pH-responsive Pickering emulsion has been designed on the basis of commercially available alumina-coated silica nanoparticles (Ludox CL silica particles) and potassium hydrogen phthalate (KHP). KHP was found to bind to cationic particle surfaces at pH values between 3.5 and 5.5, enabling the resulting surface-active particles to stabilize emulsions of xylenes in water. Above and below this pH range, the system demulsifies, resulting in a reversible Pickering emulsifier having two pH-controlled, reversible transitions.     

原位聚合法制备聚醋酸乙烯酯/纳米SiO2复合乳液

采用原位乳液聚合法制备了聚醋酸乙烯酯／纳米二氧化硅复合浮液。用红外光谱、原子力显微镜以及透射电镜等现代测试手段对复合材料进行了表征．考察了纳米二氧化硅在聚醋酸乙烯酯乳液中的分散状况及纳米二氧化硅用量对复合浮液性能的影响。结果表明：随纳米二氧化硅用量增加,复合乳液的干态,湿态粘接强度均而明显提高;乳液的粘度减小;复合乳液的胶膜耐热性提高。     

Asymmetric porous emulsion film

The formation mechanism of an “asymmetric” porous structure for the film cast from ethyl acrylate-methyl methacrylate copolymer emulsion prepared by emulsifire-free emulsion polymerization was investigated. The formation of this structure was affected by the emulsion stability which was varied by the postaddition of sodium sulfate or sodium dodecyl benzene sulfonate. It is concluded that it is derived from the production of porous skin film at the emulsion-air interface and the precipitation of flocculated particles at the bottom of emulsion during drying process.     

Atom transfer radical emulsion polymerization (emulsion ATRP) of styrene with water-soluble initiator

This study presents styrene emulsion polymerization initiated in aqueous media through an atom transfer radical polymerization (ATRP) mechanism. The water-soluble initiator employed in this process has been synthesized by our team by reacting diethanolamine with α-bromoisobutyryl bromide. The complexation of CuBr was realized by using a bicomponent complexation system comprised of 2,2′-bipyridine and N,N,N′,N′,N″-pentamethyldiethylenetriamine. The initiator ratio influence on the obtained emulsion was studied. The obtained latexes and polymer particles have been characterized by dynamic light scattering, scanning electron microscopy, and gel permeation chromatography.