苯丙共聚微乳液粒径增长机理研究

自从1980年Stofer[1]首次进行微乳液聚合研究以来,微乳液聚合法作为制备纳米聚合物乳液的主要方法,已广泛应用于生物医药、涂料、胶黏剂和造纸工业等领域.随着微乳液的广泛应用,要求人们对微乳液聚合深入研究,然而大多数的报道都是关于微乳液聚合速率的研究,对微乳液聚合的过程和粒子分散变化的研究报道很少.虽然乳液聚合和微乳液聚合具有许多相似点,但是由于微乳液聚合过程中需要加入大量的乳化剂,导致微乳液聚合的反应动力学不同于乳液聚合.     

核壳型聚丙烯酸酯乳胶粒子及其乳液的研究进展

综述了目前制备核壳型聚丙烯酸酯乳胶粒子的常用方法,如种子乳液聚合法、无皂乳液聚合法、反相乳液聚合法、细乳液聚合法以及种子分散聚合法;分析了聚合工艺、单体种类、温度、乳化剂和引发剂种类及用量等因素对聚丙烯酸酯核壳乳液合成及性能的影响;并对聚丙烯酸酯核壳乳液的研究现状进行了归纳;最后,展望了聚丙烯酸酯核壳乳液的发展方向。     

种子乳液聚合的研究进展

种子乳液聚合法因具有乳液稳定性更好、粒径分布窄、易控制等优点,在乳胶粒子设计及制备各种功能性胶乳方面具有重要作用,是制备高固含量乳液及具有核壳结构乳液的最常见最简便的方法.本文综述了近年来种子乳液的聚合工艺、聚合机理, 包括接枝机理、互穿聚合物网络机理、聚合物沉积机理、种子表面聚合机理和离子键合机理等,以及种子乳液聚合在乳胶粒子设计方面的应用研究进展,并讨论了影响种子乳液聚合的各种因素.     

乳液原子转移自由基聚合*

原子转移自由基聚合(ATRP)应用于乳液聚合体系的主要挑战在于如何同时保证乳液的稳定性和聚合反应的可控性。本文主要对乳液ATRP体系中影响聚合反应可控性和乳液稳定性的各种因素、乳液ATRP的机理和乳液ATRP的应用等方面进行了综述。表面活性剂亲水亲油性及其亲水亲油基团的化学性质、催化剂/配体在油/水两相之间的分配行为、引发剂的溶解性、反应温度以及各组分的浓度是影响反应可控性和乳液稳定性的主要因素。各组分在油/水两相中的分配行为使得乳液ATRP的机理比传统乳液聚合更加复杂。乳液原子转移自由基聚合结合了活性自由基聚合和乳液聚合的优点,在理论研究和工业生产上具有很大的应用前景。     

乳液聚合的最新进展（上）

本文对近１０多年中发展起来的与乳液聚合相关的聚合技术，如无皂乳液聚合、细乳液聚合、微乳液聚合、分散聚合等，也对其实施方法、理论研究结果和应用作了介绍；还针对近年来已经成为热点的核壳乳液、单分散聚合物微球及表面官能化的乳液微球的制备方法及应用进行了综述。     

反应性乳化剂在无皂硅溶胶苯丙乳液聚合中的应用

反应性乳化剂;硅溶胶;苯丙乳液;乳液聚合     

有机硅改性丙烯酸酯乳液的合成

乳液聚合;涂料;有机硅改性丙烯酸酯乳液的合成     

微滴乳液聚合及其应用

微滴乳液聚合的显著特征是珠滴成核的比例增加甚至占主导地位。珠滴成核几乎不需要水相传质过程,因此,可制备多种通过其它聚合方式无法轻易得到的材料,如超顺磁性乳胶粒、高固含量低粘度乳液、胶囊化无机粒子等。本文主要阐述微滴乳液聚合的基本原理、方法以及单体微滴乳液的制备和聚合,并介绍了微滴乳液聚合的应用。     

超声辐照引发MMA微乳液聚合

研究了超声波引发甲基丙烯酸甲酯(MMA)的微乳液聚合.辐照40min时单体转化率高达90%.透射电镜观察发现,PMMA微乳液平均粒径为36.5nm,粒径分布窄,表明超声波引发是制备PMMA微乳液的有效方法.采用分光光度计对微乳液聚合过程中乳胶粒的形成和大小进行了间接表征,研究了超声功率输出、乳化剂、助乳化剂、单体和引发剂对MMA微乳液聚合的影响.     

Gemini表面活性剂在合成纳米乳液中的应用

以过硫酸铵为引发剂,通过种子微乳液聚合的方法研究了阴离子型Gemini表面活性剂在形成涂料或胶粘剂用乳液中的功能。研究发现阴离子型Gemini表面活性剂在微乳液聚合中是高效的乳化剂,可以提供典型的粒径控制及良好的乳液稳定性,只需1%左右就可以得到固含量45%左右的透明纳米级聚丙烯酸酯乳液,并维持平均粒径在31nm左右。     

环硅氧烷开环聚合反应的机理及动力学研究

环硅氧烷在亲核或亲电催化剂、温度或辐射作用下,可开环聚合生成线型聚硅氧烷,聚合方法主要有本体聚合和乳液聚合.本体聚合可分为阴离子聚合和阳离子聚合,阴离子聚合就是在碱性催化剂(亲核试剂)作用下,使环硅氧烷开环聚合成线型聚硅氧烷的过程;阳离子聚合就是环硅氧烷在酸性催化剂(亲电试剂)作用下的开环聚合反应.乳液聚合则是单体和水(或其它分散介质)并用乳化剂配成乳液状态进行聚合,按所采用的乳化剂种类不同,主要有阴离子型和阳离子型两种类型.本文总结了近几年国内外环硅氧烷本体聚合和乳液聚合的开环聚合机理及动力学研究情况,并对今后此方面的研究进行了展望.     

A new approach for the characterization of insoluble amphiphilic copolymers based on their emulsifying properties

The purpose of the present study was to propose a new approach for the characterization of insoluble amphiphilic copolymers using their emulsifying properties. The capacity of four newly-synthesized block copolymers to stabilize a model emulsion formed by mixing equal volumes of water and ethyl acetate was investigated. The copolymers were composed of dextran or heparin and poly(isobutylcyanoacrylate) and were obtained either by anionic or by radical polymerization of isobutylcyanoacrylate in emulsion, initiated on dextran or heparin. A quantitative analysis of the stability of the emulsion obtained with the different copolymers was evaluated using a Turbiscan MA 2000. The results suggested that this approach provides a new methodology for investigating emulsifying properties of polymers that are insoluble in pure solvents, allowing quantitative comparisons to be made between them.     

在无机SiO2纳米粒子存在下的苯丙乳液共聚合

研究了在无机SiO₂纳米粒子存在下的苯丙乳液共聚合.选择了能使苯丙乳液稳定存在的乳化剂体系,研究了温度和SiO₂的加入对聚合过程转化率的影响,结果表明,SiO₂的加入对聚合过程有阻聚作用,使单体的转化率降低.SEM照片证明SiO₂粒子已经进入苯丙乳液粒子中,而且SiO₂的加入对乳液制成的膜断面形态有一定影响.实验发现在无机SiO₂纳米粒子存在下,苯丙乳液共聚合时有较多残渣出现,对此通过改进乳液聚合进行了有效地改善.同时对制成的复合材料进行了力学性能和热学性能的测定.     

反相乳液聚合法合成高分子量聚丙烯酸钠

以丙烯酰氧基Span-80为乳化剂,采用反相乳液聚合法合成了高分子量聚丙烯酸钠.研究了乳化剂和中和度对聚合体系稳定性的影响,以及(NH4)2S2O8—甲基丙烯酸-N、N-二甲氨基乙酯(DMAEMA)—NaHSO3引发剂和单体浓度对聚合物分子量的影响.结果表明,最佳的实验条件:中和度为90%;乳化剂用量为3%(油相);引发剂占单体的质量分数分别为(NH4)2S2O80.06%、DMAEMA0.04%、NaHSO30.02%;单体在水相的质量分数为40%(水相).在最佳实验条件下,合成聚合物分子量超过2.6×107,且溶解性能优于溶液聚合所得产品.     

Morphology and grafting in polybutylacrylate-polystyrene core-shell emulsion polymerization

The morphology of polybutylacrylate–polystyrene (PBA–PS) core-shell latex particles prepared by seeded emulsion polymerization was investigated as a function of the addition method of styrene (St). The thin layer chromatography/flame ionization detector (TLC–FID) technique was used to characterize the morphology of the core-shell latexes. It was found that grafting PS to the PBA core occurs during seeded emulsion polymerization. The percentage of grafting depended on the method of addition of St, being greatest for the batch reaction, less for the preswollen batch reaction, and least for the semibatch reaction. Upon aging the PBA core-polymer migrated out of the latex particles with a low degree of grafting to form dumbellshaped particles, whereas the PBA–PS core-shell particles with a high degree of grafting remained spherical because of the emulsifying ability of graft copolymer.     

Emulsion polymerization of vinyl stearate

The polymerization of vinyl stearate in aqueous emulsions with a non-ionic emulsifying agent and potassium peroxydisulfate as initiator has been investigated by use of a dilatometric method to follow the reaction. In general, the reaction kinetics do not follow the pattern established for styrene. Variation of initiator concentration produced latices containing approximately equal numbers of latex particles, even though the rate of reaction was almost directly proportional to the peroxydisulfate concentration. For a given initiator and monomer concentration polymerization occurs very slowly when the monomer is completely solubilized but as the number of micelles is reduced and the number of emulsion droplets increased, the rate increases to an optimum value, whereafter it decreases. A mechanism is proposed by which the sparsely soluble vinyl stearate reacts and redistributes itself into latex particles of a different size range from the micelles and emulsion droplets originally present.     

醇溶性聚丙烯酸酯乳液的合成及性能研究

以丙烯酸乙酯(EA)、甲基丙烯酸甲酯(MMA)和甲基丙烯酸(MAA)为主单体,采用过硫酸盐作引发剂,经预乳化乳液聚合工艺合成了聚丙烯酸酯乳液.讨论了乳化剂种类、单体种类以及功能性单体、引发剂加入工艺对乳液聚合过程及乳液产品性能的影响.结果表明:单体组成为m(MMA)∶m(EA)∶m(MAA)=45∶40∶15所得乳液聚合物能满足使用性能要求;种子引发剂加入质量控制在单体总质量的0.3%,而总的引发剂用量占单体总质量的0.8%较适宜.用差热分析仪和凝胶渗透色谱仪对乳液聚合物进行了表征.     

STABILITY OF HATER IN OIL EMULSIONS USING HIGH MOLECULAR WEIGHT EMULSIFIERS

Excellent stability of water-in-oil emulsions could be obtained by partial crosslinking of the fatty chain in several polyglycerol fatty esters. Such products were capable of emulsifying and stabilizing up to 50 wt% water in vegetable oils at a level of 3-5% emulsifier per total emulsion weight. The corresponding non-crosslinked products require at least 20-25% emulsifier to give the sane level of stability, with much higher viscosity.

Degree of polymerization, molecular weight distribution, viscosity, dielectric constant and refractive index of the emulsifier were correlated to the emulsion stability. The most remarkable result is a clear correlation between the molecular weight of the emulsifier and emulsion stability; best emulsions were prepared with polymeric emulsifier with MW of Ca. 40000.     

Block Copolymers in Emulsion and Dispersion Polymerization

Summary: This article deals with recent progress including the authors' work concerning the application of block copolymers as polymeric surfactants in heterophase polymerizations. The synthesis methods for preparing block copolymers by emulsion and dispersion techniques are outlined, with emphasis on recently developed controlled free radical polymerizations in aqueous media. Specific characteristics of amphiphilic block copolymers are described, for example, micellization and emulsifying effects. A general overview of emulsion and dispersion polymerization in an aqueous and organic medium with ionic and nonionic block copolymers is presented for the preparation of electrosteric and sterically stabilized latex particles. Typical examples of microemulsion, miniemulsion, oil‐in‐oil emulsion, and micellar polymerizations are provided. Current and potential developments of so‐called “hairy latexes”, inverse‐, multiple‐, and solid emulsions, as well as of nonaqueous polymeric dispersions are also discussed.

PS foam obtained by free radical polymerization of water‐in‐styrene, stabilized with a PS–PEO diblock copolymer.     

环硅氧烷负离子乳液聚合中活性中心浓度的变化规律

以八甲基环四硅氧烷(D4)为单体,十二烷基二甲基苄基氢氧化铵(BDAH)为乳化剂兼催化剂,进行环硅氧烷负离子乳液聚合,采用凝胶色谱(GPC)测定聚合产物的转化率及分子量.在此基础上,分析基元反应,提出活性中心生成机理,并应用环硅氧烷开环聚合普适动力学模型计算乳液聚合平衡之前的活性中心浓度变化规律.结果发现,聚合温度较低时,活性中心浓度随时间逐渐增加,最终恒定;聚合温度较高时,活性中心浓度随时间仅单调递增.结果与机理相符.