纳米二氧化硅的疏水改性及其对Pickering乳液的稳定作用

为了探究固体粒子对乳液的稳定作用,采用L-赖氨酸作为催化剂合成纳米SiO2粒子,并用六甲基二硅胺烷(HMDS)对纳米SiO2粒子进行表面疏水改性,将经过HMDS改性后的纳米SiO2粒子作为稳定剂制备出Pickering乳液。通过粒径分析仪、场发射透射电子显微镜、FTIR、TG-DSC、接触角测量仪、光学显微镜、电导率仪分别对纳米SiO2的制备、表面改性和Pickering乳液的性能进行了表征。结果表明,成功合成出粒径小且形貌均一的硅球,具有疏水性的三甲基硅基成功接枝到纳米SiO2的表面;不同纳米SiO2浓度制备的Pickering乳液,发现随着SiO2浓度的增大,乳液的稳定性逐渐增强,乳液液滴直径呈现减小的趋势;不同油水比制备的Pickering乳液,发现随着油相体积的增大,乳液的稳定性呈现增大的趋势。     

疏水改性籽粒苋淀粉颗粒稳定的Pickering乳液

利用碱提法从籽粒苋种子中提取了籽粒苋淀粉(St)颗粒,使用辛烯基琥珀酸酐(OSA)对提取的淀粉颗粒进行疏水改性,得到了两亲性的辛烯基琥珀酸淀粉酯(OSA starch)颗粒。通过红外光谱(FTIR)及X射线衍射仪(XRD)对其结构进行了表征。随着改性淀粉颗粒取代度的增加,其疏水性增强。以液体石蜡作为油相,将改性淀粉颗粒作为单一的乳化剂应用于Pickering乳液的制备。当油水体积比为1∶1时,取代度为0.089的改性淀粉颗粒的质量分数为0.5%以上,即可得到优异稳定性的乳液。随着改性淀粉颗粒用量的增加,乳液液滴粒径变小,乳液稳定性增强。     

Ugi反应海藻酸衍生物协同疏水改性高岭土稳定Pickering乳液的制备

通过Ugi反应疏水改性海藻酸钠(Alg),制备了两亲性的海藻酸衍生物(Ugi-Alg)。以聚甲基氢硅氧烷(PMHS)作为疏水改性剂,利用干法球磨对高岭土(KL)微粒表面疏水改性。并利用FTIR、1HNMR、接触角测量仪、激光粒度和Zeta电位分析仪对改性产物进行表征。用改性后的高岭土(MKL)协同Ugi-Alg制备稳定的Pickering乳液,并探究了水相p H对Pickering乳液形貌和液滴大小的影响。结果表明:Alg通过Ugi反应成功地疏水改性;PMHS在球磨的机械作用下吸附在KL微粒表面,使MKL成为具有高疏水性能的活性微粒;Ugi-Alg在超声作用下协同吸附在MKL微粒表面,改变了MKL微粒表面的润湿性,可提高Pickering乳液的稳定性;随着水相p H的升高,MKL/Ugi-Alg稳定的Pickering乳液液滴粒径逐渐减小,当p H=10.32时,其液滴粒径达到7.4μm。     

非共价改性纳米颗粒稳定Pickering乳液的制备及可逆调控

用具有氧化还原活性分子乙酰基二茂铁吖嗪(Fc⁺A)对磁性纳米颗粒Fe₃O₄@SiO₂进行非共价疏水改性,将改性颗粒作为乳化剂制备Pickering乳液。通过TEM、SEM、FTIR、XRD、接触角测量、光学显微镜等对纳米颗粒及Pickering乳液的结构、形貌和性能进行表征。结果表明：制备的核壳结构纳米颗粒粒径为150 nm左右,分散均匀;Fc⁺A成功修饰到纳米颗粒表面,且随Fc⁺A浓度的增加,改性颗粒的接触角明显增大;Fc⁺A浓度为12.5 mmol/L,乳化剂浓度为0.3%(质量),油水比为4∶6,搅拌速率为10000 r/min,得到的Pickering乳液具有良好的稳定性。而且,所得乳液具双重响应性,通过氧化还原和磁场可实现对乳液稳定性的可逆调控。     

刺激响应型Pickering乳液的制备及应用研究进展

固体纳米颗粒代替传统表面活性剂作为乳化剂稳定的Pickering乳液具有高抗聚结性、环境友好性、成本较低等优点,在多种领域具有广阔应用前景。通过适当刺激精确调控乳液稳定性及构建响应型Pickering乳液的研究引起广泛关注。该文详细综述了多种刺激响应型Pickering乳液的构建、调控及其应用。首先阐述了Pickering乳液的稳定性影响因素和备固体颗粒乳化剂表面改性技术;继而介绍了多种刺激响应性Pickering乳液的响应机理和性能;最后综述了Pickering乳液的应用研究;分析展望了Pickering乳液研究应用中存在的问题和发展前景。     

刺激响应型Pickering乳液的制备及应用进展

固体纳米颗粒代替传统表面活性剂作为乳化剂稳定的Pickering乳液具有抗聚结性高、环境友好、成本较低等优点,在多个领域具有广阔应用前景.通过适当刺激精确调控乳液稳定性及构建响应型Pickering乳液的研究引起广泛关注.综述了多种刺激响应型Pickering乳液的构建、调控及应用.首先,阐述了Pickering乳液的...     

改性高岭石稳定W/O/W双重Pickering乳液的制备

双重乳液是一种能满足对亲水亲油特性不同的两种药物同时进行输送的载体系统,但传统乳液中表面活性剂的使用给环境造成的重危害问题使乳液的应用受到限制。以卵磷脂改性的高岭石为乳化剂制备W/O/W双重Pickering乳液,主要研究了改性剂用量、改性高岭石特征、乳液体系的油水比等对双重Pickering乳液稳定性的影响。以接触角为130°的改性高岭石稳定的内相(W1/O),以接触角为88°的改性高岭石稳定外相(O/W2),获得了可以对两种不同亲水性特征药物同时进行包封的W1/O/W2双重Pickering乳液。     

改性柑橘果胶-乳清蛋白稳定的精油Pickering乳液

以改性柑橘果胶和乳清蛋白为乳化剂,对月桂精油、百里香精油、牛至精油及佛手柑精油进行包埋,通过高压均质法制备了改性柑橘果胶-乳清蛋白复合纳米粒稳定的四种精油Pickering乳液。采用马尔文激光粒度仪、SEM、FTIR和哈克流变仪等对乳液进行了表征,并通过药敏实验评价了乳液的抑菌效果。结果表明,经过辐照处理后的改性果胶的乳化能力显著增强,提高至548.11 m2/g。红外光谱证明了聚合物的形成和精油的成功包封。乳液粒径大小在829~1147 nm之间,耐受离心且贮存77d后的稳定性均高于90%。流变学测试表明,四种乳液均属于假塑性流体。乳液对不同精油的包封率为5.81%~21.54%,负载率为0.81%~5.81%,且对包埋的精油具有控释效果。四种乳液对两种食品微生物（大肠杆菌和金黄色葡萄球菌）均具有显著抑制作用,抑菌圈范围为7.51~34.98 mm。     

高亲水性纳米二氧化硅颗粒稳定Pickering乳液

用未修饰的高亲水性纳米二氧化硅颗粒(SiO2 NPs)在其等电点附近制备Pickering乳液。结果表明,等电点(pH 2.7)条件下SiO2 NPs借助高能均质与油水界面剧烈混合,并在范德华引力的驱动下以弱吸附的状态在界面处负载,从而稳定得到O/W型Pickering乳液。增加SiO2 NPs的浓度或减小油相体积分数可提高单位油滴界面的颗粒负载率,增大连续相黏度并促进乳液液滴之间形成三维网络结构从而提高乳液稳定性。通过调节连续相的pH以促进SiO2 NPs表面的硅烷醇发生质子化与去质子化的转变,实现乳液多次pH响应循环。     

改性蜡质玉米淀粉稳定Pickering乳液的制备及应用

采用辛烯基琥珀酸酐(OSA)对蜡质玉米淀粉(WS)疏水改性制得辛烯基琥珀酸酐改性蜡质玉米淀粉(OSA-WS),以不同取代度OSA-WS制备了稳定的Pickering乳液。测定了OSA-WS取代度(DS)、反应效率(RE)及三相接触角,对其进行了FT-IR、XRD和SEM表征。结果表明,OSA通过与淀粉表面羟基反应对其进行改性并未改变淀粉颗粒结构;随着取代度的增大,淀粉颗粒乳化性增加,制得Pickering乳液稳定性增强;以OSA-WS为乳化剂制得包埋辅酶Q10的Pickering乳液,通过透皮运输实验可知,与辅酶Q10的油溶液相比,包埋辅酶Q10的Pickering乳液更有利于辅酶Q10的透皮运输。     

Characteristics of Stable Pickering Emulsions under Process Conditions

Emulsions stabilized by solid particles are so called Pickering emulsions which are characterized by their high stability against coalescence. This type of emulsion can be used for a lot of applications. Very little is known about how reaction conditions affect their properties. In this study the influence of important reaction conditions like shear stress, pressure, temperature, and the influence of synthesis gas on Pickering emulsions is investigated. It is shown that the emulsions remain stable in terms of coalescence in a broad range of the reaction conditions and are suitable as reaction media for industrial processes and for a reaction optimization with a subsequent separation step.     

有机硅改性丙烯酸酯核-壳乳液的研制

采用种子乳液聚合法，以丙烯酸异辛酯为壳，MMA为核，MAA、K-12和有机硅偶联剂为官能性单体，合成了内硬外软的核-壳型有机硅改性丙烯酸酯乳液。讨论了官能性单体、核-壳单体结构、引发剂等对乳液性能的影响，以及影响乳液聚合的因素。     

Influence of Nanoparticles and Drop Size Distributions on the Rheology of w/o Pickering Emulsions

The rheological behavior of particle/oil suspensions and w/o Pickering emulsions consisting of water, 1‐dodecene and different fumed silica nanoparticles was investigated. The particles varied in hydrophobicity and specific surface area. The influence of particle concentration and water content on rheology was determined and the emulsion drop size distributions were examined. Emulsions with different drop sizes were created by either varying the particle concentration or the water content. It was found that the particles in the continuous oil phase and not the drop size distribution seem to be the major influencing factor on the Pickering emulsion rheology.     

Evaluation of Pickering emulsions stabilized with nano-cellulose and nano-chitin treated with deep eutectic solvent

Developing bio-friendly and degradable Pickering emulsifiers as surfactants to replace traditional surfactants with bio-toxicity is imperative in the food, coating, cosmetics, and pharmaceutical industries. Nanocellulose and chitin can be used directly as an emulsifier to prepare Pickering o/w emulsions. As the concentration of nanoparticles increases, the stability of the emulsion also increases, and an overly large nanoparticle aspect ratio is not conducive to the stabilization of the emulsion. In comparison, nanocellulose-prepared Pickering emulsion has improved stability. Of these, nanocellulose prepared by DES with a molar ratio of 3:1 to LA:CC has been shown to have the best stability when used to equilibrate the oil/water mass ratio of 2/8. The Zeta potential is −38.4 mV, and the size of the droplets is the most uniform. With a mean droplet diameter of 770 nm. This study had certain research significance and reference value for the development of bio-friendly surfactants.     

Hydrophobic Modification and Regeneration of Shirasu Porous Glass Membranes on Membrane Emulsification Performance

The effect of hydrophobic modification and regeneration of Shirasu porous glass (SPG) membranes was systematically investigated on the monodispersity of emulsions. The results showed that the hydrophobic modification and regeneration of SPG membranes had little influence on the monodispersity of emulsions, no matter how many modification and regeneration runs were operated. The emulsification runs affected the emulsification performance to a certain extent when hydrophobically‐modified SPG membranes were used for preparing water‐in‐oil (W/O) emulsions repeatedly. However, they almost did not affect the emulsification performance when regenerated hydrophilic SPG membranes were used for preparing oil‐in‐water (O/W) emulsions. The SPG membranes could be used repeatedly after hydrophobic modification or regeneration with almost the same emulsification performance as fresh or freshly‐modified ones. The results provided some valuable guidance for the repetitive use of SPG membranes to prepare monodisperse O/W and W/O emulsions.     

Effect of Hydrophobic Modification on the Properties of Polymer‐Blended Microemulsion Gels

Phase behavior of sodium oleate (NaOl)/isoamyl alcohol‐based lamellar gel phase in cedar oil/water medium in the presence of the nonionic polymer hydroxyethyl cellulose (HEC) and its hydrophobic modified product (HMHEC) is investigated for the development of polymer‐embedded surfactant gels. HMHEC is more soluble in oil‐in‐water (o/w) microemulsions, but nonionic HEC shows limited solubility in the lamellar microemulsion (o/w type). Quantitative estimation of rate of adsorption of the polymer on lamellae bilayers can be easily done by Sudan solubilization and methylene blue complexation methods. Addition of HMHEC to the lamellar gel phase increases the polymer solubilization limit of lamellar gels as well as the viscoelasticity and thermal stability. The polymer‐embedded microemulsion gel acts as a “clean gel” since it exhibits good solubilization in different hydrocarbon media at ambient conditions. Elastic modulus of the polymer‐embedded gel influences directly the suspension performance of gels at high temperature and yields a reasonable sand‐settling velocity acceptable according to fracturing standards. The thermal characteristics and viscoelastic properties of polymer‐embedded gel were found to be suitable for moderate‐temperature reservoir stimulation where the bottom hole temperature is in the range 70–75 °C. Already a large amount of experimental data on pure microemulsions (without polymer) exists. Our studies indicate that the developed polymer‐embedded microemulsion gel has great potential as a model system for the study of polymer–microemulsion interactions.     

乙醇对HIPEs法制备吸油憎水树脂及其性能的影响

以苯乙烯、二乙烯基苯为共聚单体,过硫酸铵为引发剂,十六烷基三甲基溴化铵为乳化剂,采用油包水型高内相比乳液模板法合成了聚苯乙烯/二乙烯基苯(PSD)多孔树脂。考察了相对于分散相不同体积分数的乙醇对乳液稳定性及PSD的密度、吸(释)液性、溶胀率等性能的影响。发现随着乙醇用量的增加,反应体系难以形成稳定的乳液,其密度、吸液性、溶胀性下降,而对甲苯的释放速率增加;PSD多孔材料经水-乙醇抽提后吸水率降低至0.26 cm3/g,而吸甲苯率仍达15.60~18.42 cm3/g,表现出明显的吸油憎水性能。     

疏水壳聚糖的制备及其凝血效果研究

为增强壳聚糖的止血效果,采用酰基化方法在壳聚糖氨基上连接长链烷基以形成疏水性壳聚糖。该制备工艺中采用单因素设计对反应过程中的温度、浓度进行筛选,以疏水壳聚糖的黏度、取代度以及凝血效果作为评价指标,通过梯度设计筛选得到最优工艺条件：温度55℃,壳聚糖浓度1%（g/ml）,月桂酸酐浓度0.3%（g/ml）。采用红外、核磁等方法对其进行表征,表明合成了疏水壳聚糖。由体外凝血实验发现,疏水壳聚糖的止血效果与其取代度在一定范围内呈正相关性,当其取代度小于9%时,1%（g/ml）的疏水壳聚糖乙酸溶液止血效果不理想;当超过15%时,相同质量浓度的疏水壳聚糖乙酸溶液呈凝胶状态,无法与血液充分混合,严重影响其止血效果。通过该实验发现取代度为9%-15%的疏水壳聚糖与血液混合后,且疏水壳聚糖的浓度不小于0.75%（g/ml）时,具有良好的凝血效果。又通过小鼠在体肝脏止血实验发现疏水壳聚糖粉末能够迅速止血,且效果显著优于壳聚糖。因此,由该方法合成的疏水壳聚糖作为止血材料时,能够显著改善壳聚糖的止血效果,达到快速止血,有望开发为新型止血材料。     

pH-triggered phase inversion and separation of hydrophobised bacterial cellulose stabilised Pickering emulsions

The pH-triggered transitional phase behaviour of Pickering emulsions stabilised by hydrophobised bacterial cellulose (BC) is reported in this work. Neat BC was esterified with acetic (C₂–), hexanoic (C₆–) and dodecanoic (C₁₂–) acids, respectively. We observed that C₆– and C₁₂–BC stabilised emulsions exhibited a pH-triggered reversible transitional phase separation. Water-in-toluene emulsions containing of 60 vol.% dispersed phase stabilised by C₆– and C₁₂–BC were produced at pH 5. Lowering the pH of the aqueous phase to 1 did not affect the emulsion type. Increasing the pH to 14, however, caused the emulsions to phase separate. This phase separation was caused by electrostatic repulsion between modified BC due to dissociable acidic surface groups at high pH, which lowered the surface coverage of the water droplets by modified BC. When the pH was re-adjusted to 1 again, w/o emulsions re-formed for C₆– and C₁₂–BC stabilised emulsions. C₂–BC stabilised emulsions, on the other hand, underwent an irreversible pH-triggered transitional phase separation and inversion. This difference in phase behaviour between C₂–BC and C₆–/C₁₂–BC was attributed to the hydrolysis of the ester bonds of C₂–BC at high pH. This hypothesis is in good agreement with the measured degree of surface substitution (DSS) of modified BC after the pH-triggered experiments. The DSS of C₂–BC decreased by 20% whilst the DSS remained constant for C₆– and C₁₂–BC.