乳化剂分子亲水组分含量对相反转乳化过程的影响

高分子树脂水基分散体系 ,因其结构的可灵活调节性 ,在许多方面得到应用 ,又因其不含有机溶剂 ,能完全满足环境保护和生态的要求而备受关注 [1～ 3] .相反转乳化技术是制备高分子水基体系的新方法 ,它适用于制备包括加聚物和缩聚物的大多数高分子水基体系 ,大大拓宽了水基体系的范围 [4 ] .杨振忠等[5] 利用自己合成的高分子非离子型乳化剂将环氧树脂乳化成微粒尺寸小且分布窄的水基分散体系 ,对相反转机理和相反转技术进行了深入研究 .研究表明 ,乳化剂浓度和乳化温度对相反转后水基微粒尺寸和形态有重要影响 ,高乳化剂浓度和较低的乳化温…     

无皂相反转乳化法制备高分子水基分散体系

高分子树脂水基分散体系是指高分子树脂以微粒形式分散于水中 ,包括高分子乳液、高分子悬浮液等体系 .由于高分子树脂水基分散体系具有低成本 ,高性能 ,无污染等优点 ,一直受到普遍关注 .高分子树脂乳液一般通过乳液聚合制备 .该方法只适用于由含双键的单体制备的加聚产物 .而在制备缩聚产物的乳液时 ,乳液聚合方法局限性很大 ,而最近发展起来的相反转乳化技术 ,适用于制备包括加聚产物和缩聚产物在内的大多数高分子水基分散体系 ,拓宽了高聚物水基分散体系的范围 [1] .杨振忠等 [2～ 5] 利用相反转乳化技术制备了未固化和可固化的环氧树脂…     

双酚A型环氧树脂水基化微粒分析

高分子树脂水基化微粒化就是使高分子树脂以微粒形式分散于水中,高分子乳液、悬浮液都属于此范畴．因其不含有机溶剂,且具有无环境污染及不易失火等优点,放这方面的研究正成为高分子技术的一个研究热点．通常的乳液聚合或悬浮聚合方法是从小分子单体到聚合物水基化体系的化学反应过程,一般只适于制备加聚物的水基化体系,而不适用于制备维聚物的水基化体系．本文提出的相反转技术是一种有效的制备高分子水基化体系的方法,它能将几乎所有的高分子树脂通过物理的乳化方法制成相应的水基化体系[1,2],大大拓宽了其制备范围．相反转[3。4]…     

环氧树脂相反转乳化过程相态发展研究

以扫描电镜为主要手段,观察了环氧树脂相反转乳化过程中的相态演化过程.结果表明:在较高乳化剂浓度下,当水含量达到某一临界值时,原W/O体系中水滴间的相互吸引大于水滴间的排斥作用,导致相邻水滴同时快速地融合为连续相并得到水基微粒,水基微粒的尺寸较小,约为亚微米级,尺寸分布窄,微粒为单个粒子.在乳化剂浓度较低情况下,非相邻较大水滴在剪切场作用下随机地融合为连续相,发生不完全相反转,并得到W/O/W结构,水基微粒尺寸较大,约10微米数量级,尺寸分布宽且为一种复合多孔结构.此外,分析了相反转发展演变过程.     

环氧树脂相反转乳化过程相态发展研究＊

以扫描电镜为主要手段,观察了环氧树脂相反转乳化过程中的相态演化过程.结果表明 在较高乳化剂浓度下, 当水含量达到某一临界值时, 原W/O体系中水滴间的相互吸引大于水滴间的排斥作用, 导致相邻水滴同时快速地融合为连续相并得到水基微粒, 水基微粒的尺寸较小, 约为亚微米级, 尺寸分布窄,微粒为单个粒子.在乳化剂浓度较低情况下,非相邻较大水滴在剪切场作用下随机地融合为连续相,发生不完全相反转, 并得到W/O/W 结构, 水基微粒尺寸较大,约10微米数量级,尺寸分布宽且为一种复合多孔结构.此外,分析了相反转发展演变过程.     

制备高分子水基微粒体系的相反转技术

高分子树脂的微粒化水基化体系具有广阔的应用前途，正引起人们极大关上方面技术能把几乎所有的高分子树脂乳化为微粒化水基化体系，具有很宽的应用范围，本文简要地从相反转技术的发展，相反转模式，相反转类型，相反转的理论处理等４方面作以介绍。     

环氧树脂水基分散体系的相反转乳化

以聚乙二醇－邻苯二甲酸酐－环氧树脂Ｅ－４４多元嵌段共聚体为乳化剂,将环氧树脂Ｅ－４乳化成水包油的稳定水基乳液。用乳液体系电导率和粘度的变化表征了相反转乳化过程。研究了乳化剂浓度、三元多嵌段共聚体中亲水嵌段分子量和乳化温度对相反转乳化过程的影响。实验结果表明,体系在较高乳化剂浓度（９．１％）下为完全相反转,在低乳化剂浓度（４．１％）下为不完全相反转。相反转时水与环氧树脂Ｅ－４４的重量比值随乳化剂浓度     

高分子水基微粒形态与界面膜性质的关系

高分子水基微粒形态与界面膜性质的关系杨振忠赵得禄许元泽徐懋（中国科学院化学研究所高分子物理开放实验室北京１０００８０）关键词高分子树脂，相反转，水基微粒，界面膜相反转技术是制备高分子树脂微粒化水基化体系的新方法［１］，正成为高分子技术的一个热门方向...     

微乳液聚合制备多孔高吸油甲基丙烯酸酯类树脂的研究

研究了双连续相微乳液聚合制备多孔高吸油树脂,以甲基丙烯酸甲酯(MMA)、丙烯酸丁酯(BA)为共聚单体(油相),水(H2O)/乙醇(EtOH)为混合水相,2,2′-偶氮二异丁腈(AIBN)为引发剂,采用十二烷基硫酸钠(SDS)和复配十二烷基硫酸钠/吐温80(SDS/T80)两种乳化体系,调节油相和水相比例,配制出双连续相微乳液.聚合在无搅拌下进行.研究了乳化体系、混合水相含量、单体配比、交联剂和引发剂用量等因素对树脂吸油性能的影响.结果表明,多孔高吸油树脂比同系无孔树脂的吸油速率大大提高,最快可以在2min内达到吸油饱和.树脂对苯,四氢呋喃,四氯化碳的吸油倍率分别达到15.5g/g,15.5g/g,31.7g/g.     

磺化聚苯醚离聚体微乳化过程相反转的研究

以乙酰磺酸为磺化剂制备了磺化度为 3%～ 1 7%mol的磺化聚苯醚 (SPPO)并中和成盐 ,在一定的温度和搅拌速度下 ,加水将SPPO乳化成水包油的稳定水基微乳液。用乳化过程中的体系的电导率、粘度和表面张力的变化表征了乳化相反转过程。另外还研究了溶剂的极性和离子含量对SPPO溶液可乳化性和乳化过程的影响     

Mechanistic investigation on the formation of epoxy resin multi‐hollow spheres prepared by a phase inversion emulsification technique

Micrometer sized multi‐hollow spheres of epoxy resin were prepared by a physical method so‐called phase inversion emulsification technique. The formation mechanism of the titled spheres was studied by incomplete phase inversion. The requisite for the formation of multi‐hollow spheres was that irreversible coalescence among the water droplets under shear action before the phase inversion point existed. This process could be facilitated by a lower emulsifier concentration and a higher emulsification temperature. Moreover, a theoretical explanation of the formation of the titled spheres was presented.     

Preparation of waterborne dispersions of epoxy resin by the phase-inversion emulsification technique. 1. Experimental study on the phase-inversion process

 Waterborne dispersions of bisphenol A epoxy resin were prepared by the so-called phase-inversion emulsification technique. The electrical properties, rheological behavior and morphological evolution during the phase inversion process were characterized systematically. It was shown that both emulsifier concentration and emulsification temperature play great roles in controlling the phase inversion process as well as the structural features of the waterborne particles. A high emulsifier concentration, i.e. 10.90 wt% and a low emulsification temperature, i.e. 73 °C, facilitate complete phase inversion, in which all water droplets in the system are simultaneously transformed into the continuous phase at the phase-inversion point (PIP). In this case, sub-micron-sized, discrete waterborne particles were formed. In contrast, a complex water-in-oil-in-water structure was achieved by incomplete phase inversion at a low emulsifier concentration, i.e. 2.33 wt%, and a high temperature of 80 °C. The morphological evolution observed by scanning electron microscopy revealed that not all the water droplets in the system were converted into the continuous phase at the PIP and that some small water drops were trapped within the waterborne structure. Received: 15 March 2000/Accepted: 16 May 2000     

Preparation of waterborne dispersions of epoxy resin by the phase-inversion emulsification technique. 2. Theoretical consideration of the phase-inversion process

 A theoretical consideration of the phase-inversion technique to prepare waterborne particles based on the experimental facts of the phase inversion process given in part 1 of this series is presented. The deformation and breakup of the water droplets dispersed in an epoxy resin phase under shear action are analyzed in terms of microrheology. The interaction and coalescence dynamics among the water droplets stabilized by an interfacial layer formed by the emulsifier molecules are discussed in terms of Derjaguin–Landau–Verwey–Overbeek theory and effective collision theory, respectively. A criterion for the completion of phase-inversion is that the attraction among the water droplets exceeds the entropic repulsion. Thus, a physical model of phase-inversion is proposed to predict the effects of some control variables on the phase-inversion process as well as the structural features of the waterborne particles, by which the experimental results could be well interpreted. It is indicated that the achievement of phase inversion is determined by the dynamic coalescence among the water droplets before the phase-inversion point (PIP). If the dynamic coalescence among the water droplets is ignored, phase inversion is achieved completely and sub- micron-sized particles are prepared. In comparison, if the dynamic coalescence is significant, phase inversion is achieved incompletely and a large complex water-in-oil-in-water structure is prepared. In the case of complete phase inversion, it is shown that the size of the waterborne particles is comparable with the size of the water droplets before the PIP. Received: 15 March 2000/Accepted: 16 May 2000     

相反转乳化技术制备环氧树脂交联多孔微球

多孔微球在分离吸附、催化、涂料印刷等多方面具有潜在应用价值 .最近研究表明 ,当微孔孔径在 2 0 0～ 80 0ｎｍ范围时 ,由于强烈的光散射作用 ,多孔微球可以作为遮光剂使用[1] .Ｏｋｕｂｏ等用酸碱逐步处理法制备了一些共聚物的亚微米级多孔球[2～ 4] .Ｏｋｕｂｏ又用动态溶胀种子聚合法制备了微米级的聚合物微球 ,用类似的方法得到了多孔结构[5,6] .但这种方法涉及了许多烦琐过程并且产生了很多副产物需要处理 ,使得其费时费力而且成本相当高 .Ｓｃｈｌａｒｂ等发展了一种新的制备方法 ,在乳液聚合过程中引入有机溶剂 ,在实验后期除掉有机…     

Waterborne Dispersions of a Polymer‐Encapsulated Inorganic Particle Nanocomposite by Phase‐Inversion Emulsification

Inorganic silica nanoparticles were encapsulated with an epoxy resin to give waterborne nanocomposite dispersions, using the phase‐inversion emulsification technique. Sub‐micron‐sized waterborne particles with narrow size distribution were prepared such. Microscopy results indicate that all the silica nanoparticles are encapsulated within the composites and uniformly dispersed therein. Curing of the nanocomposite dispersions proceeded in a controlled manner.     

PREPARATION OF BISPHENOL A EPOXY RESIN WATERBORNE DISPERSIONS BY THE PHASE INVERSION EMULSIFICATION TECHNIQUE*

The phase inversion emulsification technique (PIET) is an effective physical method for preparing waterbornedispersions of polymer resins. Some results concerning the preparation of bisphenol A epoxy resin waterborne dispersions byPIET in our laboratory were summarized. Electrical properties, rheological behavior and morphological evolution duringphase inversion progress were systematically characterized. The effects of the emulsifier concentration and emulsificationtemperature on phase inversion progress and the structural features of the waterborne particles were studied as well. Thedeformation and break up of water drops in a shear field were analyzed in terms of micro-rheology, while the interaction andcoalescence dynamics of water drops were discussed in terms of DLVO theory and Smoluchowski effective collision theory,respectively. Based on the experimental results and theoretical analysis, a physical model of phase inversion progress wassuggested, by which the effects of the parameters on phase inversion progress and the structural features of the waterborneparticles were interpreted and predicted.     

不完全相反转发展过程的流变行为

以动态应力流变仪ＤＳＲ（ＤｙｎａｍｉｃＳｔｒｅｓＲｈｅｏｍｅｔｅｒ）对双酚Ａ型环氧树脂在低乳化剂浓度（２３３ｗｔ％）下的相反转乳化过程进行了稳态应力扫描及动态频率扫描实验．实验结果表明,体系在相反转点前表现为牛顿流体行为,粘度几乎不变;相反转点时,体系粘度增加幅度很小,体系的有关动态流变参数（剪切储能模量、损耗模量和复数粘度）均出现极小值,将此归于局部连续水相的润滑作用;进一步加水,体系的动态流变量增加,意味着相反转在相反转点后仍在继续进行．所以,体系在低乳化剂浓度时,发生了不完全相反转．     

HYDRODYNAMIC AND THERMODYNAMIC EFFECTS IN PHASE INVERSION EMULSIFICATION PROCESS OF EPOXY RESIN IN WATER

The mechanism of phase inversion emulsification process （PIE） was studied for waterborne dispersion of highly viscous epoxy resin using non-ionic polymeric surfactants. Drop deformation and breakup, rheological properties, conductivity, and particle size measurements reveal the micro-structural transition amid emulsification. It is revealed that strong flow causes water drop to burst with the formation of droplets and huge interface. Phase inversion corresponds to an abrupt rheological transition from a type of viscous melt with weak elasticity to a highly elastic type of aqueous gel. This implies that the phase inversion equivalent to a curvature inversion. Based on this, a geometric model is postulated to correlate process variables to the particle size. The coverage and conformation of the surfactant plays key role for the particle size of the final emulsion. The interactions of thermodynamic and hydrodynamic effects are also discussed. It is concluded that the thermodynamics control the PIE while the hydrodynamics drives the creation of interface and involves every step of PIE.