分散聚合法制备单分散交联聚苯乙烯微球

以苯乙烯为单体、二乙烯基苯为交联剂,通过优化反应条件,制备了平均粒径为3.28～9.04 μm的单分散聚苯乙烯微球和平均粒径为6.60 μm的单分散交联聚苯乙烯微球.探讨了单体浓度、引发剂含量、分散稳定剂用量对微球粒径和分散性的影响.热稳定性分析表明:交联聚苯乙烯微球耐热性明显优于线性聚苯乙烯.     

交联剂加入方式对聚苯乙烯微球形貌和分散性能的影响

以醇水混合液为分散介质,偶氮二异丁腈为引发剂,聚乙烯吡咯烷酮为稳定剂,二乙烯基苯为交联剂,采用分散聚合法一步制备了粒径约为1μm的单分散交联聚苯乙烯微球;采用扫描电镜和激光粒度仪等分析微球表面形貌及粒径分布,研究了滴加交联剂开始时间、交联剂浓度、引发剂浓度等对微球形貌和分散性能的影响.结果表明,在实验进行4h时加入交联剂,且交联剂滴加持续时间为2h的条件下,可制得平均粒径为1μm左右的交联聚苯乙烯微球,其具有较好的单分散性和球形度,且表面光滑.     

改进的种子聚合——单分散交联聚苯乙烯微球的合成

本文结合了种子聚合法和二步溶胀法的特点,提出用改进的种子聚合法以合成粒径大于3微米、粒度呈单分散的交联聚苯乙烯微球。文中采用的粒径为1—2微米的聚苯乙烯胶乳种子是由无皂乳液聚合法制备的。文章研究了溶胀温度、溶胀剂比例、溶胀时间、交联剂、小分子化合物及表面活性剂等因素对生成微球的粒径和分散性的影响。     

单分散、大粒径聚苯乙烯微球的制备

以聚乙烯基吡咯烷酮为分散剂、偶氮二异丁腈为引发剂、醇／水混合物为分散介质进行了苯乙烯的分散聚合，讨论了初始单体浓度、分散剂用量、引发剂浓度、分散介质组成和反应温度等反应条件对所得聚合物颗粒直径和直径分布的影响．通过大量的试验，筛选出了较为理想的分散聚合的条件及配方，制备出了粒径为４８μｍ的单分散聚苯乙烯微球．然后，以分散聚合所制得的聚合物颗粒为种子，用动力学溶胀法制成了粒径增大近四倍的单分散、大粒径聚苯乙烯微球，并讨论了滴水速度和补加分散剂对溶胀的影响     

改进的种子聚合——单分散交联聚苯乙烯微球的合成

 本文结合了种子聚合法和二步溶胀法的特点,提出用改进的种子聚合法以合成粒径大于3微米、粒度呈单分散的交联聚苯乙烯微球。文中采用的粒径为1—2微米的聚苯乙烯胶乳种子是由无皂乳液聚合法制备的。文章研究了溶胀温度、溶胀剂比例、溶胀时间、交联剂、小分子化合物及表面活性剂等因素对生成微球的粒径和分散性的影响。     

单分散多孔St/DVB共聚微球的制备

用分散聚合法制出了粒径约为2μm的单分散聚苯乙烯(PSt)种子,再通过改进的活性二步种子溶胀法制得了粒径约为4．5μm的单分散多孔St／DVB共聚微球。在溶胀阶段,用XSP-8CA生物显微镜观察活化、溶胀温度,1～氯代十二烷(CD,mL)／PSt(g)的比例及单体混合物总体积对溶胀种子粒径及单分散的影响,确定了合适的制备工艺条件。用SEM观察多孔聚合物微球的粒径和形貌,并用BET法考察了不同比例的及甲苯浓度变化对多孔聚合物微球孔结构的影响,实验表明,随着VDVB／Vst的比例的增大和甲苯浓度的提高,多孔微球的比表面积增大,孔分布向小孔区域移动。     

单分散聚苯乙烯微球的制备及影响因素研究

以聚乙烯吡咯烷酮为分散剂，无水乙醇为反应介质，偶氮二异丁腈为引发剂，采用分散聚合工艺，通过优化反应条件，制备出了粒径为5μm单分散（分散系数≤5％）聚苯乙烯微球。所制备的聚苯乙烯微球标准偏差δ＝0．16μm，分散系数ε＝0．02，且具有良好的球形度，表面非常光滑，无破损，无缺损。对影响单分散聚苯乙烯微球的因素进行了研究，结果表明：随着分散稳定剂用量的增加，聚苯乙烯微球的粒径减小；随着单体和引发剂用量的增加，聚苯乙烯微球的粒径增大。分散稳定剂和单体用量是影响聚苯乙烯微球粒径分布的两个主要因素。     

分散聚合-种子溶胀聚合法制备中空微球的研究

采用分散聚合法制备聚苯乙烯(PSt).以甲苯一正辛醇作致孔溶剂,过氧化苯甲酰为引发剂,PSt为单分散种球,反应单体苯乙烯和交联单体二乙烯基苯(DVB)通过种子溶胀聚合法,在水介质中制备了呈单分散的中空聚合物微球[P(St-DVB),粒径5 μm-8μm],其形态及热力学行为经SEM,DSC和TGA表征.讨论了DVB用量及溶剂组成对P(St-DVB)形态的影响.     

苯乙烯/二乙烯基苯在乙醇/乙二醇单甲醚中分散共聚合速率及粒子大小的研究

以乙醇 乙二醇单甲醚 (EOH EGME)为介质 ,羟丙基纤维素 (HPC)为稳定剂 ,偶氮二异丁腈 (AIBN)为引发剂进行了苯乙烯和二乙烯基苯的分散共聚合研究 .制得粒径在 6～ 10 μm范围内的单分散交联聚苯乙烯微球 (CPS) .探讨了不同介质配比 ,以及苯乙烯、二乙烯基苯、引发剂的浓度对微球大小、粒径分布、聚合速率及稳定性的影响 .当苯乙烯和AIBN浓度增加时 ,聚合速率和平均粒子尺寸增加 ,而粒子分布变宽 ,粒子数先增加 ,而后降低 .随着EOH EGME比例的增加 ,平均粒子尺寸增加 ,而分布指数降低 ,稳定剂增加 ,粒子尺寸降低和粒子数增加 ,但对聚合速率及粒子分布影响不太明显 .另外还探讨了单体和交联剂的后滴加法对微球大小、粒径分布的影响     

聚苯乙烯单分散微球粒径可控性探讨

在系统研究分散聚合反应中的原料组成(分散稳定剂、单体、引发剂)和反应条件(反应介质极性、反应体系温度、搅拌速度)对所制备的聚合物微球的粒径大小及粒径分布和聚合反应速率影响的基础上,根据各因素的影响效应,优化设计分散聚合的反应条件,成功地制备出1μm~10μm粒径范围内不同粒径级别的微米级单分散聚合物微球,实现了不同粒径大小及粒径分布的微米级单分散聚合物微球制备的控制设计。     

混杂聚合

混杂聚合是指同一体系内有两种或两种以上不同类型的聚合反应同时进行的过程,如自由基聚合与阳离子聚合,自由基聚合与缩聚等。混杂聚合能够在原位形成高分子合金,并有可能得到互穿网络结构（ＩＰＮ）,从而使聚合产物具备较好的综合性能。     

Kinetic study of the nitroxide‐mediated controlled free‐radical polymerization of n‐butyl acrylate in aqueous miniemulsions

The controlled free‐radical homopolymerization of n‐butyl acrylate was studied in aqueous miniemulsions at 112 and 125 °C with a low molar mass alkoxyamine unimolecular initiator and an acyclic β‐phosphonylated nitroxide mediator, N‐tert‐butyl‐N‐(1‐diethylphosphono‐2,2‐dimethylpropyl) nitroxide, also called SG1. The polymerizations led to stable latices with 20 wt % solids and were obtained with neither coagulation during synthesis nor destabilization over time. However, in contrast to latices obtained via classical free‐radical polymerization, the average particle size of the final latices was large, with broad particle size distributions. The initial [SG1]₀/[alkoxyamine]₀ molar ratio was shown to control the rate of polymerization. The fraction of SG1 released upon macroradical self‐termination was small with respect to the initial alkoxyamine concentration, indicating a very low fraction of dead chains. Average molar masses were controlled by the initial concentration of alkoxyamine and increased linearly with monomer conversion. The molar mass distribution was narrow, depending on the initial concentration of free nitroxide in the system. The initiator efficiency was lower than 1 at 112 °C but was very significantly improved when either a macroinitiator was used at 112 °C or the polymerization temperature was raised to 125 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4410–4420, 2002     

Simple polymerization through oxygen at reduced volumes using oil and water

An enduring question is: what is the simplest and easiest way to obtain tailored polymers? This communication explores a robust photoiniferter polymerization with only two active ingredients that requires no prior deoxygenation and can be performed on the milliliter scale or sub-milliliter scale. Rather than leaving headspace in the polymerization vessel or scaling reactions up to fill the vessel, this approach fills the headspace of the reaction vessel with mineral oil or inert solvents. This approach can also be applied to polar monomers in aqueous media, using oil as the inert solvent, or to hydrophobic monomers with water as the inert solvent. This method removes enough ambient oxygen that the photoiniferter reaction proceeds with no deoxygenation step, and achieves high conversion and good molecular weight control in 10–20 h in both aqueous and organic solvents. Complex polymer architectures such as multiblock copolymers and gradient polymers were successfully synthesized by this approach.     

丙烯酸2-乙基己酯/丙烯酸辐射乳液聚合——乳胶中羧基的分布

本文用辐射法引发丙烯酸2-乙基己酯/丙烯酸(EHA/AA)乳液共聚合,用酸碱反滴定法研究了剂量率、剂量、乳化剂浓度、固含量、共聚物分子量、丙烯酸浓度、丙烯酸加料方式及丙烯酸预先中和程度等反应条件对乳胶中羧酸可滴定百分比的影响。并对聚合机理作了初步探讨。     

Reverse Iodine Transfer Polymerization (RITP) in Emulsion

Reverse iodine transfer polymerization (RITP) is a new controlled radical polymerization technique based on the use of molecular iodine I₂ as control agent. This paper aims at presenting the basics of RITP and the strategy that we have followed for the development of this process in the past three years, from the validation in homogeneous solution polymerization up to recent results in heterogeneous aqueous polymerization processes. Typical examples of RITP of butyl acrylate in emulsion and RITP of styrene in miniemulsion are discussed.     

再活化链式聚合

基于传统的链式聚合和逐步聚合二种高分子链增长过程,提出了再活化链式聚合。按此聚合机理,高分子的链增长是通过将一个非活性或睡眠状态的链(Mm)重新活化为活性种(Mm*),活性种再和一个单体(M)反应,生成一个较大分子量的休眠产物(Mm 1)来实现的。再活化链式聚合主要例子包括苯胺和或许其它芳香族单体的氧化聚合,活性自由基聚合,以及核酸和蛋白质合成中的生物聚合。     

烯烃配位活性聚合研究的新进展

从活性聚合的特征、催化剂的结构和特点、聚合单体的种类、以及控制工艺条件的重要性4个方面．评述了近年来烯烃配位活性聚合研究的进展状况。     

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。     

Liquid-Crystalline Polymer Particles Prepared by Classical Polymerization Techniques

Liquid-crystalline polymer particles prepared by classical polymerization techniques are receiving increased attention as promising candidates for use in a variety of applications including micro-actuators, structurally colored objects, and absorbents. These particles have anisotropic molecular order and liquid-crystalline phases that distinguish them from conventional polymer particles. In this minireview, the preparation of liquid-crystalline polymer particles from classical suspension, (mini-)emulsion, dispersion, and precipitation polymerization reactions are discussed. The particle sizes, molecular orientations, and liquid-crystalline phases produced by each technique are summarized and compared. We conclude with a discussion of the challenges and prospects of the preparation of liquid-crystalline polymer particles by classical polymerization techniques.