马来酸类可聚合乳化剂的合成及其在细乳液聚合中的应用

采用三步法合成了可聚合乳化剂马来酸单十六醇酯丙基磺酸钠.并用正交实验法优化了马来酸单十六醇酯合成工艺条件,结果表明反应的最佳条件为:催化剂质量分数1%,反应时间3.0h,反应温度90℃,马来酸酐与十六醇的摩尔比1.1:1.苯乙烯-丙烯酸丁酯细乳液聚合使用该乳化剂与传统乳化剂相比,在较低温度下(65℃)具有较高的转化率,且所得乳液具有较好的电解质稳定性,乳胶膜的耐水性也得到提高.     

马来酸类可聚合乳化剂及其在乳液聚合中应用

使用可聚合乳化剂可以很好地解决传统乳化剂的缺点,提高乳液的应用性能.马来酸类乳化剂其可聚合基团反应活性适中,可以很好地键合在乳胶粒表面上,且更为突出的是这类乳化剂不易发生均聚,而是倾向于与单体发生共聚.研究表明,马来酸类可聚合乳化剂应用到乳液聚合中,可以改善乳胶液的性能,提高乳胶膜的耐水性等.文章介绍了这一类新型的乳化剂,并根据其亲水基团进行了分类,分别介绍其合成路线,总结了马来酸类乳化剂的特点,概述了在常见乳液聚合体系中的应用与研究.     

可聚合非离子型乳化剂稳定的聚丙烯酰胺反相胶乳

近年来，新型可聚合乳化剂的研制及应用引起了人们的极大兴趣［１～４］．目前报道的可聚合乳化剂都是水溶性的，用于正相乳液聚合中改善聚合物膜的性能及聚合物的加工性能［１］，提高聚合物胶乳的稳定性以及制备功能化乳胶粒子等［５，６］．本文合成了油溶性可聚合非离...     

可聚合乳化剂合成苯乙烯-丙烯酸丁酯-α-烯烃磺酸钠共聚物乳液

以工业原料α-烯烃磺酸钠(AOS)作为可聚合乳化剂,苯乙烯(St)和丙烯酸丁酯(BA)为单体,采用预乳化种子乳液聚合合成了St-BA-AOS共聚物乳液.通过测定AOS与两种单体的竞聚率确定了半连续加料法的聚合方式.探讨了单体的加料方式、反应温度、反应时间、AOS用量等工艺条件对胶乳的影响,获得了最佳聚合条件.IR,NMR和DSC测试结果分析表明:St,BA与AOS发生了自由基共聚反应,形成的P(St-BA-AOS)共聚物结构中含有磺酸基等亲水性基团有利于乳液的稳定.在此基础上考察了AOS用量对乳液的固含量及乳胶粒粒径等的影响.结果表明:随着AOS用量的增加,乳液的固含量增加、乳胶粒的平均粒径减少.当AOS含量为2%时乳液的固含量为45.01%,平均粒径为74 nm,粒径分布指数为0.08,玻璃化温度为23.17℃.TEM测试结果显示,用相同量的AOS代替十二烷基硫酸钠可得到粒径更小和粒径分布更为均匀的乳液体系.     

非离子型可聚合聚氨酯/苯乙烯的超浓乳液聚合

研究了以非离子型可聚合聚氨酯(PUAG)和苯乙烯(St)为混合单体的超浓乳液聚合, 并且考察了n(NCO)/n(OH)摩尔比、复合乳化剂体系质量浓度[E]、不同乳化剂的种类、引发剂质量浓度[I]、单体体积分数(或分散相体积分数, 也称内相比Φ)、聚合温度等因素对聚合稳定性、动力学的影响. 同时结合光相关光谱(PCS)测定了聚合物乳胶粒子大小和粒径分布, 用透射电子显微镜(TEM)观察了粒子形态, 结果表明: 当n(NCO)/n(OH)＝2∶1, T＝328 K, Φ＝80.39%, [I]＝0.8% g/g (PUAG-St), [E]＝0.22 g/mL H₂O, m(MS-1)/m(CA)＝2∶1, PVA＝0.01 g/mL H₂O时, 超浓乳液不仅有较好的聚合稳定性和较快的聚合速率, 而且粒径小分布均匀. 同时, 在此条件下的表观动力学表达式和表观活化能分别确定为R_p＝k[I]^0.50[E]^0.73[M]^0.54和 E_a＝29.7 kJ/mol. 热失重分析(TGA)进一步表明: 调节PUAG的含量可以达到对聚苯乙烯的改性, 提高聚苯乙烯的热稳定性.     

新型可聚合蒽醌染料单体及其共聚物乳液的制备及性能

通过多步有机反应合成了新型蒽醌染料单体1-(间(2-(2-(丙烯酰氧基)乙氧基)乙基砜基)苯胺基)蒽醌(AVSAQ),对其化学结构进行了表征;然后将其与苯乙烯(St)、丙烯酸丁酯(BA)和甲基丙烯酸(MAA)进行半连续乳液共聚合,制备出了共价键合型P(St-BA-MAA-AVSAQ)橙红色聚合物乳液,并对乳液以及乳胶膜的性能进行了表征,系统考察了AVSAQ和过硫酸铵(APS)用量对单体总转化率以及乳液胶体性质的影响.结果表明,当AVSAQ用量不高于单体总量的4.0 wt%、APS用量不低于单体总量的0.5 wt%时,聚合反应可以平稳进行,所得乳胶粒水合粒径均在60 nm左右.总单体转化率和AVSAQ转化率随着AVSAQ用量的增加而降低,当AVSAQ用量达到4.0 wt%时,二者分别为95.0%和93.6%.P(St-BA-MAA-AVSAQ)的UV-Vis吸收光谱特性与AVSAQ完全一致,最大吸收波长均为486.8 nm.与相应非共价键合型橙红色聚合物乳液相比,P(StBA-MAA-AVSAQ)聚合物乳液具有良好的储存稳定性和保色性,乳胶膜的光色牢度和耐溶剂牢度也显著提高.     

复合微乳液聚合制备P(MMA-UA)纳米乳胶粒子的研究

将聚氨酯预聚体可聚合乳化剂 (APUA)和甲基丙烯酸甲酯 (MMA)的复合微乳液体系 ,分别用水溶性过硫酸钾 (K2 S2 O8)和油溶性偶氮二异丁腈 (AIBN)作引发剂 ,进行微乳液聚合研究 ,制备了P(MMA UA)复合纳米乳胶粒子 .研究了APUA用量、聚合温度对聚合动力学的影响 ;用透射电子显微镜 (TEM)观察了不同乳化剂浓度及引发剂体系对胶粒形态、大小及分布的影响 .结果表明 ,用可聚合乳化剂APUA可制得稳定性很好的P(MMA UA)纳米级核 壳型乳胶粒子 ,乳胶粒径在 5 0nm左右 .随着乳化剂用量增加 ,粒子变小 ;不同类型的引发剂对胶乳的性质有较大影响 ,以APUA为乳化剂 ,K2 S2 O8为引发剂 ,在聚合反应过程中或在聚合反应后的放置中 ,会出现P(MMA UA)的纳米水凝胶 (Nanogel)现象 .     

纳米醋丙乳液的合成与性能表征

以醋酸乙烯酯(VAc)为原料,丙烯酸丁酯(BA)和丙烯酸(AA)为改性单体,过硫酸钾(KPS)为引发剂,OP-10,SDS和可聚合乳化剂丙烯氧基壬基酚聚氧乙烯(10)醚硫酸铵为乳化剂体系,采用半连续种子乳液聚合法制备了纳米粒径的醋丙乳液.对得到的乳液进行了分子量,热性能,红外光谱,乳液稳定性等测试,用激光散射粒度仪和透...     

单一阳离子乳化剂对D4细乳液制备及聚合的影响

无助稳定剂十六醇(HD)时,以十八烷基双聚氧乙烯基苄基氯化铵(OEBA)为单一阳离子乳化剂,制备粒径为200 nm左右的D4细乳液.选OEBA浓度相同、有无HD添加的两对照D4细乳液,经KOH引发进行开环聚合,动态光散射法(DLS)追踪聚合中粒径变化过程.同时借助紫外可见分光光度计,考察合成的聚二甲基硅氧烷(PDMS)细乳液对强酸HCl、强碱KOH和电解质NaCl的相对稳定性.结果显示,单一乳化剂OEBA时,不但制备的D4细乳液稳定性良好,而且合成的PDMS细乳液具优良的耐强酸、强碱和电解质能力;单一乳化剂时不仅聚合中粒径变化与添加HD相一致,而且反应速率随转化率和时间的变化规律也相似.     

可聚合表面活性剂的研究进展

在乳液聚合中，表面活性剂发挥着非常关键的作用，但同时它们也存在不足的方面，一个比较有前景的方法就是使用可聚合表面活性剂。可聚合表面活性剂以牢固的共价键键合到聚合物粒子上，有效避免了表面活性剂的解析及其在膜中的迁移。本文综述了近年来可聚合表面活性剂的进展，主要讨论了阴离子、非离子、阳离子可聚合表面活性剂的特征和性质及其在乳液聚合中的应用。     

Miniemulsion polymerization of styrene: Evolution of the particle size distribution

The mechanism of the miniemulsion polymerization of styrene was investiaged through a combination of calorimetry to monitor the polymerization rate and transmission electron microscopy (TEM) to follow the evolution of the particle size distribution. These techniques proved to be a powerful combination for gaining detailed mechanistic information regarding these polymerizations. Particle size analysis of the latexes withdrawn during the course of the reaction revealed that most of the polymer particles were formed by a relatively low conversion (i.e., 10% conversion). However, nucleation continued well past this point (to 40-60% conversion). In fact, it was observed that nucleation in miniemulsion polymerizations using cetyl alcohol continued past the maximum in the rate of polymerization. As a result of these long nucleation periods, the latex particle size distributions produced from these miniemulsion polymerizations were broader than their conventional emulsion polymerization counterparts, and were negatively skewed with a tail of small particles. The amount of negative skewing of the particle size distributions was found to decrease with increasing initiator (potassium persulfate) concentration. Finally, a correlation was observed between the length of time to the maximum polymerization rate and the breadth of the particle size distribution as reflected in the standard deviation. © 1995 John Wiley & Sons, Inc.     

Synthesis of large,high‐solid‐content latexes by miniemulsion polymerization

Multiple and diverse applications have been recently found for miniemulsions and miniemulsion polymerization. In this work, miniemulsion polymerization is presented as a suitable technique for the preparation of high‐solid‐content latices with large particle sizes. Monomer miniemulsions were prepared with a high‐pressure homogenizer, and droplet sizes of 200–700 nm were obtained. Latexes with particle sizes larger than the sizes commonly accepted for miniemulsion polymerization were obtained. With fixed operational conditions of the homogenizer, the type of stabilizer was the key parameter determining the droplet size and the droplet size distribution. The particle size of the latices obtained by miniemulsion polymerization indicated that the particles were mainly formed by droplet nucleation. Latexes obtained by this process have multiple applications, including use as seeds in the polymerization of high‐solid‐content latices. This article shows that potential new applications for miniemulsion polymerization are far from being exhausted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4222–4227, 2004     

Particle nucleation in high solids batch miniemulsion polymerization stabilized with a polymeric surfactant

The nucleation of polymer particles in the miniemulsion polymerization of vinyl acetate/VeoVa10 (VAc/VeoVa10) stabilized with PVOH was studied. The effect of costabilizer type, PVOH concentration, and type (thermal water‐soluble and oil‐soluble; and redox water‐soluble) and concentration of initiator on the extent of droplet nucleation were studied. Droplet nucleation was maximized by improving miniemulsion stability and using efficient initiators. These high solids dispersions could not be obtained by using a conventional batch emulsion polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6407–6415, 2008     

Formation of Nonspherical Particles with Uneven Surface in Emulsion Copolymerization of Styrene and Methacrylic Acid with Nonionic Emulsifier

Summary: Emulsion copolymerization of styrene and methacrylic acid with nonionic emulsifier and potassium persulfate as initiator gave nonspherical copolymer particles having uneven surface. The formation was based on the coagulation of byproduct nano-sized (ca. 35 nm) particles, which were formed throughout the copolymerization until monomer phase disappeared, onto main submicron-sized (234 ∼ 445 nm) particles.     

On the Reaction Characteristics of Miniemulsion Polymerization with Aqueous Phase Initiation – Experiments and Modeling

Miniemulsions, consisting of submicron droplets of very hydrophobic lauryl methacrylate or 4‐tert‐butyl styrene, are successfully polymerized using water‐soluble sodium persulfate. Monitoring the calorimetric profile as well as the droplet and particle size distribution with conversion manifests a process of monomer redistribution, droplet disappearance, and narrowing of the particle size distribution. The observed reaction characteristics could be modeled adequately, using thermodynamic principles. The results of the work presented do not only have predicting value, but also enfeeble the idea of a one‐to‐one translation of monomer droplets into polymer particles in miniemulsion polymerization.     

On the miniemulsion polymerization of very hydrophobic monomers initiated by a completely water‐insoluble initiator: thermodynamics,kinetics, and mechanism

Successful miniemulsion polymerizations of very hydrophobic monomers, such as lauryl methacrylate and 4‐tert‐butyl styrene, initiated by very hydrophobic (i.e., completely water‐insoluble) lauroyl peroxide, are reported. Conversion‐time histories, as well as final latex properties, for example, the particle size distribution, are different from similar miniemulsion polymerizations in the presence of water‐soluble initiators. The observed differences can be attributed to the average number of radicals inside a miniemulsion particle; the system obeys Smith‐Ewart case I rather than Case II kinetics. Albeit the pairwise generation of radicals in the monomer droplets, substantial polymerization rates are observed. Water, present in the droplet interfacial layer, is supposed to act as chain transfer agent. The product of a chain transfer event is a hydroxyl radical, exit of this hydroxyl radical allows for the presence of single radicals in particles. The proposed mechanisms allow for agreement between initial droplet and final particle size distributions in miniemulsion polymerization initiated by lauroyl peroxide. © 2016 The Authors Journal of Polymer Science Part A: Polymer Chemistry Published by Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2731–2745