O／W微乳液催化苯乙烯聚合动力学研究

Ｏ／Ｗ微乳液催化苯乙烯聚合动力学研究１）郝京诚孙海英汪汉卿２）（中国科学院兰州化学物理研究所兰州７３００００）尤进茂（曲阜师范大学化学系曲阜２７３１６５）关键词微乳液催化苯乙烯聚合动力学分类号Ｏ６４３．１３微乳液作为聚合反应介质，催化单体聚合反应研究...     

添加剂对十二烷基磺酸钠溶液性质影响的研究

添加剂对十二烷基磺酸钠溶液性质影响的研究＊鲁润华郝京诚汪汉卿（中国科学院兰州化学物理研究所兰州７３００００）关键词表面张力电导添加剂Ａｓ中图分类号Ｏ５５２．４添加剂对表面活性剂溶液物理化学性质影响的研究是人们极感兴趣的研究内容［１］，因为表面活性剂实...     

微乳液中超氧化物歧化酶的催化活性

微乳液中超氧化物歧化酶的催化活性马成松李干佐石元昌（山东大学化学院济南２５０１００）汪汉卿（中国科学院兰州化学物理研究所兰州７３００００）关键词微乳液超氧化物歧化酶催化活性分类号Ｏ６４３．３２在生物细胞内，酶主要作用在“水／油界质”的界面上或其附近（...     

冲击波处理结晶氧化镁的催化性能研究

冲击波处理结晶氧化镁的催化性能研究１）刘建军徐康２）（中国科学院兰州化学物理研究所兰州７３００００）贺红亮谭华（西南流体物理研究所冲击波物理与爆轰物理实验室成都６１０００３）张菊郑小明（杭州大学催化研究所杭州３１００２８）关键词冲击波氧化镁ＴＰＤＥＳ...     

非螯合型手性双膦在苯乙烯的不对称催化氢甲酰化中的应用

非螯合型手性双膦在苯乙烯的不对称催化氢甲酰化中的应用吕士杰，成克军，周宏英，郑燕，傅宏祥（中国科学院兰州化学物理研究所羰基合成和选择氧化国家重点实验室，兰州７３００００）黄梁仁（中国科学院福建物质结构研究所，福州３５０００２）关键词手性双膦，不对称氢...     

以非离子型表面活性剂形成微乳液的碳原子数相关性研究

由非离子型表面活性剂、助表面活性剂（醇）、水和油形成微乳液,用拟三角相图中微乳区的面积确定形成微乳液的最佳条件,实验证明,油的碳原子数加上醇的碳原子数等于表面活性剂的碳原子数对为微乳液形成最佳条件,也符合ＢＳＯ规律。     

阳离子表面活性剂中相微乳的形成和特性

自1943年SdriAn。等人山发现微乳液体系并予以命名以来，对微乳液研究不断深入·微乳液是由油、水、表面活性剂和助表面活性剂组成的各向同性、透明的、热力学稳定的分散体系，微乳液可分为单相微乳液和多相微乳液问．中相微乳液是多相微乳液中，与过剩盐水相和过剩油相达到三相平衡的Winsor皿型微乳液，它在三次采油、日用化工、微环境、酶催化等方面具有特殊重要的应用I‘，‘］．近年来对阴离子表面活性剂中相微乳液的形成和特性进行了较多研究［5。8］．但对阳离子表面活性剂中相微乳液的研究，目前尚未见报导，本文以澳代十四烷基毗…     

粒径可控阳离子型聚苯乙烯纳米粒子的制备及表征

在采用阳离子型双子（gemini）表面活性剂作为乳化剂,不使用任何助乳化剂的条件下,通过改进微乳液聚合工艺制备了窄分布粒径可控的阳离子型聚苯乙烯（PS）纳米乳液。 改进微乳液聚合的主要特点是：大部分苯乙烯以预乳液的形式恒速滴入引发聚合的微乳液中,使用具有高乳化性能的gemini表面活性剂作为乳化剂能明显降低乳胶粒粒径。 实验结果表明,少量阳离子单体三甲基烯丙基氯化铵作为共聚单体能够明显减小Z均粒径、降低粒度分布,乳化剂用量、引发剂用量和反应温度均能影响制备乳胶粒的粒径及其粒度分布。 乳化剂和引发剂用量分别为苯乙烯质量的5%~10%和1.0%~1.5%、反应温度为70~75 ℃时,能够制备粒径小分布窄的阳离子型聚苯乙烯纳米粒子。 Z均粒径与苯乙烯质量之间的线性关系表明,Z均粒径可以通过苯乙烯用量来控制。 不同聚合工艺下制备的聚合物粒度分布曲线表明,改进微乳液聚合工艺（半连续预乳化工艺）在制备窄分布的聚合物纳米粒子方面具有很强的优越性。     

O／W微乳液中聚邻甲苯胺超微粒子的制备

聚邻甲苯胺具有较高的电导率、较好的贮存电荷的能力和良好的环境稳定性，因而具有较大的应用价值［’－‘j，其合成方法主要有电化学合成法和化学合成法［‘·’J．化学会成法所得聚邻甲苯肢的粒子一般大于100urn．近年来，以表面活性剂聚集体微乳液、溶致液晶为介质，制备超微粒子材料已为人们所关注「’－’］．以微乳液为介质进行聚合反应亦引起重视，但大部分微乳液聚合都是在四组分微乳液（表面活性剂、助表面活性剂、单体和水）中进行‘”·“‘．近年来，某些油溶性单体已成功地在无助表面活性剂的三组分微乳液中聚合［‘’·‘’1…     

SDBS/n-C8H18/n-C4OH/盐水体系中相微乳液双连续结构

微乳液是指由水（盐水）、油（烃）、一种或几种表面活性剂组成的热力学稳定体系,这类体系具有低粘度、各向导性、透明或半透明的性质[1],微乳液在许多工业实际问题中,例如润滑、以洗涤、催化等方面得到了应用[2],近年来,微乳液和反向胶束中酶催化技术的开发[3]以及分离蛋白质中的应用[4],使微乳液在生化技术研究中倍受青睐．与过剩盐水相和过剩油相达三相平衡时的微乳液即为中相微乳液。中相微乳液具有既可增溶水又可增溶油的特殊性质,并且微乳液与过剩水相和过剩油相间的界面张力（飞uw和7;n。;）极低顺干2．0。10－’1liN·111…     

Microemulsion polymerization of acrylamide and styrene: Effect of the structures of reaction media

Isothermal phase diagrams of the system cetyltrimethylammonium bromide (CTAB)/n‐butanol/n‐octane/water were constructed, and the effect of the oil (n‐octane) contents on the microemulsions was studied at 40 °C. We determined the microemulsion structures of two systems, CTAB/n‐butanol/10% n‐octane/water and sodium dodecyl sulfonate (As)/n‐butanol/20% styrene/water, by conductivity measurements to investigate the polymerization of acrylamide and styrene in the two microemulsion systems. The polymerization kinetics of the water‐soluble monomer acrylamide in CTAB micelles and the different CTAB/n‐butanol/10% n‐octane/water microemulsion media [water‐in‐oil (W/O), bicontinuous (BC), and oil‐in‐water (O/W)] were studied with water‐soluble sodium bisulfite as the initiator. The maximum polymerization rate in CTAB micelles was found at the second critical micelle concentration. A mechanism of polyacrylamide formation and growth was proposed. A connection between the structures of the microemulsions and the polymerization rates was observed; the maximum polymerization rate occurred at two transition points, from W/O to BC and from BC to O/W, and the polyacrylamide molecular weights, which depended on the structures of the microemulsions, were also found. A square‐root dependence of the polymerization rates on the initiator concentrations was obtained in CTAB micelles and O/W microemulsion media. The polymerization of the oil‐soluble monomer styrene in different As/n‐butanol/20% styrene/water microemulsion media (W/O, BC, and O/W) was also investigated with different initiators: water‐soluble potassium persulfate and oil‐soluble azobisisobutyronitrile. A similar connection between the structures of the microemulsions and the conversions of styrene in CTAB/n‐butanol/10% n‐octane/water for the polymerization of acrylamide was observed again. The structures of the microemulsions had an important role in the molecular weights and sizes of polystyrene. The polystyrene particles were 10–20 nm in diameter in BC microemulsion media and 30–60 nm in diameter in O/W microemulsion media according to transmission electron microscopy. We determined the solubilization site of styrene in O/W microemulsion drops by ¹H NMR spectra to analyze the results of the microemulsion polymerization of styrene. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3320–3334, 2001     

微乳液中苯乙烯聚合反应的研究

测定了十二烷基磺酸钠(As)/正丁醇/20%苯乙烯/水体系相平衡。用油溶性偶氮二异丁腈(AIBN)和水溶性过二硫酸钾(K~2S~2O~8)为引发剂,研究了油包水(W/O)、双连续(BC)和水包油(O/W)型微乳液介质中苯乙烯的聚合反应。得到了苯乙烯转化率和聚苯乙烯分子量与体系水含量之间的关系,讨论了微乳液结构对聚合作用的影响。并通过电镜观察了聚苯乙烯的形貌,求得了聚苯乙烯的粒径,同时用^1HNMR研究了苯乙烯在微乳液液滴中的增溶位置,分析了聚合作用的实验结果。     

Effect of the structures of microemulsions on chemical reactions

Two kinds of chemical reactions were studied in two different microemulsion systems: cetyltrimethylammonium bromide/1-butanol/10 and 25% n-octane/water and sodium dodecyl sulfonate/1-butanol/20% styrene/water. One reaction is a hydrolysis reaction, in which aspirin and 2,4-dinitrochlorobenzene were used as the hydrolysis substrates. The second reaction is the polymerization of styrene, which was initiated by using two initiators, water-soluble K₂S₂O₈ and oil-soluble 2,2′-azobis(isobutyronitrile), and, at the same time, the polymerization of acrylamide, which was initiated by NaHSO₃, was also studied. All the hydrolysis reaction experimental results show that the hydrolysis is greatly affected by the structures and the structural transitions of microemulsions. The hydrolysis rates are higher in water-in-oil (W/O) microemulsion media and decrease with the addition of water. The rates increase in bicontinuous (BC) microemulsions and decrease in oil-in-water (O/W) microemulsions. The transition points of the hydrolysis rates occurred at the two microemulsion structural transition points from W/O to BC and from BC to O/W. The polymerization relationships between the conversions of styrene, the molecular weights of polystyrene and the water contents of the microemulsion system were obtained. The effects of microemulsion structures on the sizes of the polystyrene particles and on the molecular weights of the polymers are discussed. Polystyrene particles with diameters of 10–60 nm were observed by microscopy. Our experimental polymerization results show that microemulsions are suitable as media for the production of polymers, the molecular weights and the particle sizes of which can be controlled and predicted by variations in microemulsion structures. Received: 11 July 1999/Accepted: 26 July 1999     

反相微乳液模板法合成介孔聚苯乙烯

提出并实施了反相微乳液为模板合成介孔聚合物的新方法. 通过考察氯仿/CTAB/水三元系反相微乳液的稳定性, 以及均相微乳液粒径变化规律, 得到了三元反相微乳液体系的稳定区域. 以(NH4)2S2O8为引发剂, 利用此反相微乳液为模板合成得到介孔聚苯乙烯材料. 产物的XRD图谱中有两个明显的衍射峰, 对应的晶面间距离d分别为2.6和1.3 nm, 1/d值之比等于1:2, 为层状结构. N2气吸附/脱附曲线表明大部分孔径为1.7 nm, 与动态光散射测得的微乳液液滴的尺寸相一致.     

微乳液结构的研究

测定了十二烷基磺酸钠／正丁醇／２０％苯乙烯／水体系的相平衡，用冷冻刻蚀、ＥＳＲ、ＦＴ－ＩＲ研究了上述体系微乳液的结构，研究表明，苯乙烯含量恒定时，随着体系中水含量增加，电导确定的双连续结构的微乳液经历着从油包水到以连续再到水包油变化，ＦＴ－ＩＲ测定表明，Ｗ／Ｏ微乳兴较Ｏ／Ｗ微乳液的ＯＨ伸缩振动和弯曲振动频率有显著减小，说明Ｗ／Ｏ微乳兴中氢键缔合要比Ｏ／Ｗ强得多。ＥＳＲ测定表明Ｏ／Ｗ微乳液的旋转相关     

Particle nucleation and monomer partitioning in styrene O/W microemulsion polymerization

Particle nucleation in the polymerization of styrene microemulsions was found to take place throughout the polymerization as indicated by measurements of the particle number as a function of conversion. A mechanism based on the nucleation in the microemulsion droplets was proposed to explain the experimental findings although homogeneous nucleation and coagulation during polymerization were not completely ruled out. A thermodynamic model was developed to simulate the partitioning of monomer in the different phases during polymerization. The model predicts that the oil cores of the microemulsion droplets were depleted early in the polymerization (4% conversion). Due to the high monomer/polymer swelling ratio of the polymer particles, most of the monomer resides in the polymer particles during polymerization. The termination of chain growth inside the polymer particles was attributed to the chain transfer reaction to monomer. The low n? (less than 0.5) of the microemulsion system was attributed to the fast exit of monomeric radicals.     

Solubilization of Styrene and Acrylamide Monomers in Microemulsions

Abstract

Phase diagrams of sodium dodecyl sulfonate (DS)/n‐butanol/styrene/water systems with variable amounts of styrene were constructed at 40°C, and the effects of styrene on microemulsion stability were studied. The solubilization of styrene in these O/W microemulsion systems was investigated by ¹H NMR methods. The results show that the solubilization site shifts from the palisade layer to the inner core of microemulsion droplets when the molar fraction of styrene reaches 0.312. The solubilization of acrylamide in cetyltrimethylmethyl ammonium bromide (CTAB)/n‐butanol/10% n‐octane/water reverse microemulsions (W/O) was studied with a ¹³C NMR method. It was found that the acrylamide was mainly solubilized in the Stern layer of droplets at low acrylamide levels. However, when the mole fraction of acrylamide approaches 0.428, the acrylamide penetrates into the palisade layer and is distributed along the hydrocarbon chain of the surfactant.     

丙烯酰胺微乳液聚合

由乳化剂聚乙二醇壬基苯基醚ＯＰ、聚乙二醇壬基苯基醚（ＴＸ—４）、丙烯酸胺、水和煤油组成微乳液时，体系中水相丙烯酸胶浓度及体系温度对乳化剂最小量有明显的影响；而ＯＰ、ＴＸ—４比例及油水比例的影响不大．本文研究了辐射引发微乳液聚合的动力学，得到如下表达式：聚合速率及聚合物特性粘数的表观活化能分别为５３．２ＫＪ／ｍｏｌ，－３３．２ＫＪ／ｍｏｌ．聚丙烯酸胺微乳液具有特殊的增稠性能，与聚电解质增稠剂相比，电解质对增稠效果的影响不大，而其他表面活性剂的影响较大．     

枯基醇/三氟化硼在含水介质中引发苯乙烯可控正离子聚合的研究

研究了含水介质中,以枯基醇(CumOH)/三氟化硼(BF3)为引发体系的苯乙烯正离子聚合的特征,探讨了CumOH用量、体系中的水含量对苯乙烯正离子聚合转化率、聚合速率以及产物分子量及其分布的影响;并从分子模拟、分子量末端结构等角度探讨含水介质中苯乙烯正离子聚合的反应机理.结果表明,[H2O]≤0.11 mol/L条件下,苯乙烯正离子聚合具有可控聚合的特征;水对聚合速率、单体转化率以及分子量影响较小;[H2O]>0.11 mol/L,正离子聚合不能顺利进行.根据计算结果,CumOH/BF3引发体系相对于CumOH/H2O引发体系在参与引发所需要的活化能垒更小,说明CumOH/BF3更容易引发苯乙烯正离子聚合,这与实验结果一致.CumOH/BF3引发体系是通过活化C—O键来引发苯乙烯正离子聚合,水作为可逆终止剂有利于进行可控聚合,并得到了末端含有羟基的聚合物.     

Microemulsion polymerization of styrene

Initiation of polymerization in styrene oil-in-water microemulsions by water-soluble potassium persulfate of oil-soluble 2,2′-azobis-(2-methyl butyronitrile) at 70°C gave stable latexes which were bluish and less translucent than the original microemulsions. The effects of initiator concentration, polymerization temperature, and monomer concentration on the kinetics, particle size distributions, and molecular weight distributions were investigated. The kinetics of polymerization were measured by dilatometry. In all cases, the polymerization rate shows only two intervals, which increased to a maximum and then decreased. There was no apparent constant rate period and no gel effect. A longer nucleation period was found for polymerizations initiated by potassium persulfate as compared to 2,2′-azobis-(2-methyl butyronitrile). The small latex particle size (20–30 nm) and high polymer molecular weight (1–2 × 10⁶) implies that each latex particle consists of two or three polystyrene molecules. The maximum polymerization rate and number of particles varied with the 0.47 and 0.40 powers of potassium persulfate concentration, and the 0.39 and 0.38 powers of 2,2′-azobis-(2-methyl butyronitrile) concentration, respectively. This is consistent with the 0.4 power predicted by Smith–Ewart Case 2 kinetics. Microemulsion polymerizations of styrene–toluene mixtures at the same oil-water phase ratio gave lower polymerization rates and lower molecular weights, but the same latex particle size as with styrene alone. A mechanism is proposed, which comprised initiation and polymerization in the microemulsion droplets, by comparing the kinetics of microemulsion polymerization with conventional emulsion and miniemulsion polymerization systems.