Cu~(2+)-P(VIm-MMA)壳微胶囊的制备及其化学触发研究

以1-乙烯基咪唑(1-VIm)和甲基丙烯酸甲酯(MMA)为共聚单体,通过溶液聚合反应合成出4种不同比例的无规共聚物.通过锐孔-凝固浴法,将所得共聚物的四氢呋喃溶液滴入到Cu Cl2水溶液中形成Cu2+-P(VIm/MMA)微胶囊.该微胶囊壁材上的组成部分与离子、分子反应,通过壁材的溶解、分解、解聚而使壁材崩溃或者通过溶胀而改变囊壁的渗透性.通过傅里叶红外光谱、元素分析仪、光学显微镜和扫描电子显微镜对4种不同单体比例的共聚物进行了表征,结果表明当PVM-30浓度为20 g/L时制备的微胶囊成球效果最好,其粒径大小约为1 mm,壁厚为350μm.通过核磁共振氢谱(1H-NMR)分析了PVM-30的结构,利用凝胶渗透色谱(GPC)测定了共聚物的分子量,PVM-30平均分子量在16.0×103左右.利用傅里叶红外光谱和热重分析仪对微胶囊的成分进行了研究,结果表明微胶囊壁材是由PVM与Cu2+配位得到的配位聚合物组成.探索了微胶囊在水溶液中对NO3-、SO42-和CO32-3种离子的响应特性,发现只有浸泡在CO32-离子溶液中的微胶囊的壁材出现了裂痕,最终生成了更稳定的蓝色配位离子溶液,实现了对微胶囊的化学触发.     

甲基丙烯酸-3-三甲氧基硅丙酯/苯乙烯共聚乳胶粒微结构

我们曾制备了核-壳结构的杂化乳胶粒, 并用溶剂将核去除得到杂化空心微胶囊. 但由于此乳液聚合过程十分复杂, 在不同条件下反应得到乳胶粒的微结构有较大不同, 目前尚未见到各反应条件下所得产物微结构的表征和形成机理的研究报道. 本文将系统分析在不同反应条下, MPS和St种子乳液聚合过程中, 得到的乳胶粒壳层杂化聚合物的微结构, 并研究了其形成原因.     

基于催化链转移聚合法MMA/MPS共聚物的制备及其表观催化链转移常数测定的研究

以钴Ⅱ肟氟化硼络合物(CoBF)为催化剂,2,2′-偶氮二异丁腈(AIBN)为引发剂,实现了甲基丙烯酸甲酯(MMA)与γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)在60℃甲苯体系中的催化链转移聚合(catalytic chaintransfer polymerization,CCTP),制备出末端含有双键的共聚物.利用核磁共振证明了其末端双键的存在,并通过热重分析证明CCTP产物与自由基聚合产物的结构区别.用凝胶渗透色谱(GPC)对7种单体组成下不同催化剂CoBF用量的聚合产物进行分子量表征,结果表明以催化链转移聚合合成的共聚物具有分子量低及分子量分布较窄,且聚合物的分子量随着催化剂CoBF的增加呈明显下降趋势.又分别采用了基于DPn(数均聚合度)、DPw(重均聚合度)的Mayo方程和基于ΛP、ΛH的链长分布方程计算出催化剂的表观链转移常数,发现基于DPw的Mayo方程和基于ΛP的链长分布方程的计算结果最为接近.并通过对共聚体系中不同单体组成的研究发现,催化剂表观链转移常数随着单体组成中MPS的增加而增加.     

原位聚合法制备厌氧胶固化引发剂微胶囊

采用原位聚合法制备了以脲醛树脂为壁材、过氧化苯甲酰为芯材的厌氧胶固化引发剂微胶囊。研究了乳化剂聚丙烯酸钠、十二烷基苯磺酸钠、阿拉伯树胶、苯乙烯-马来酸酐共聚物的单独使用及阿拉伯树胶与苯乙烯-马来酸酐共聚物的复配组合和其它工艺条件对微胶囊制备的影响;运用FT-IR、TG和SEM等测试技术对微胶囊进行了表征。结果表明,以苯乙烯-马来酸酐共聚物和阿拉伯树胶作为复合乳化剂,反应终点pH值为1.5左右,反应温度70℃,反应时间4 h,搅拌速率1 000 r/m in,可制得分散适中、形貌较好、粒径约为100μm的微胶囊。以实验制备的微胶囊配制成可预涂厌氧胶胶液,性能可以达到国外公司同类产品的技术指标。     

丙烯酸共聚物囊壁的正十八烷微胶囊的制备和性能表征

以二丙烯酸1,4-丁二醇酯为交联剂, 成功制备了甲基丙烯酸甲酯-甲基丙烯酸共聚物为壁材, 正十八烷为囊芯的相变材料微胶囊. 采用扫描电子显微镜(SEM)、差示扫描量热仪(DSC)和热重分析仪(TG)分别考察了单体与芯材投料比、单体浓度和交联剂的含量对微胶囊形貌、相变热性能、热稳定性能的影响. 实验结果表明: 随着单体与芯材投料比或单体浓度的增加, 微胶囊表面均变得致密, 壁厚增加; 随着交联剂含量的增加, 微胶囊的表面变得更加致密光滑, 热稳定性显著增强; 随着单体与芯材投料比的增大, 微胶囊热焓值减小, 被包裹的囊芯含量减少.     

含氟丙烯酸酯共聚物制备超疏水表面及其形成机理的研究

以丙烯酸全氟烷基乙基酯和甲基丙烯酸甲酯为共聚单体, 分别以用微乳液聚合法和溶液聚合法制备的无规共聚物和用可逆加成-断裂链转移制备的嵌段共聚物作为成膜共聚物, 并以1,1,2-三氟三氯乙烷作为溶剂, 采用溶剂挥发成膜法可以直接制备出超疏水膜, 聚合物膜对水的接触角可达160°. 改变聚合物结构和成膜条件, 探讨了该类超疏水膜的形成机理和影响因素. 发现膜的表面形貌和疏水性与共聚物的组成、结构、分子量以及成膜条件密切相关, 随着共聚物中氟含量的增大, 膜的表面形貌都趋于平滑; 而且, 无规共聚物比嵌段共聚物更易形成粗糙度好的膜; 同时, 较大的聚合物分子量和适宜的高的成膜温度都对形成粗糙结构有利.     

PS-b-P4VP/PFOA配合物在氯仿中的自组装及形态表征

全氟辛酸(PFOA)与聚苯乙烯-b-聚-4-乙烯吡啶(PS-b-P4VP)的配合能诱导嵌段共聚物在其共同溶剂氯仿中胶束化. 胶束化不仅能形成棒状聚集体, 还能得到椭球形胶束. 当嵌段共聚物PS-b-P4VP浓度为1.0 g/L时, 使用光散射和扫描电镜研究了MR值(全氟辛酸与聚合物中吡啶环的物质的量比)在1/30到1/10之间的聚集行为及形态. 发现即使当MR值小到1/30时仍然形成稳定的聚集体. 通过扫描电镜观察发现: 改变MR值可以获得不同形态的聚集体.     

具有温度敏感和荧光特性的侧链查尔酮共聚物的研究

采用2,2′-偶氮二异丁腈作为引发剂,将N-异丙基丙烯酰胺和4-甲基丙烯酰氧基-4′-二甲氨基查尔酮单体,在四氢呋喃溶剂中通过自由基共聚制备了一系列具有溶剂和温度双重敏感荧光特性的侧链查尔酮共聚物,并通过红外光谱、核磁共振氢谱和紫外-可见光谱对其结构进行表征,通过吸光度法测定了共聚物中查尔酮单元的含量.研究了侧链查尔酮共聚物的温敏性以及溶剂极性和温度双重敏感的荧光特性.结果表明,侧链查尔酮共聚物是一类具有最低临界溶解温度(LCST)的温敏性聚合物,其LCST温度随着共聚物中查尔酮含量的增加而降低;随着溶剂极性的增加,侧链查尔酮共聚物的紫外-可见最大吸收波长红移,其荧光发光波长红移并且发光强度先增强后降低,具有溶剂极性敏感的荧光特性;同时对比侧链查尔酮共聚物水溶液低温和高温下的荧光,发现低温下几乎无荧光,高温下其荧光得到明显增强,其荧光具有可逆的温度"开/关"特性。     

石蜡/P(MMA-co-AA)核壳结构相变蓄能微胶囊的制备

以熔点在58~60℃的半精炼石蜡作为相变芯材,与单体、分散剂水溶液形成核壳结构分散液,室温下自由基聚合制备甲基丙烯酸甲酯-丙烯酸的共聚物(P(MMA-co-AA))为壳材的微胶囊.分别用相差显微镜、扫描电镜、差示扫描量热分析仪和傅里叶变换红外光谱仪测定了微胶囊的形貌、热性能和壳材化学结构.微胶囊的直径范围为1~5μm,其中相变芯材的含量可达70%左右,具有较高的相变潜热(99 J/g),有望应用于空调、供暖等领域.     

UV界面聚合法制备含磷环氧微胶囊及其性能研究

通过双酚A环氧与DOPO反应,合成含磷环氧树脂,并以此为囊芯,环氧丙烯酸酯和可聚合乳化剂共聚物为囊壁,通过UV界面自由基聚合制备兼具阻燃性和自修复性能的含磷环氧微胶囊,并对产物微胶囊的性质进行了进一步研究。用红外光谱(FT-IR)和扫描电镜(SEM)表征了含磷环氧微胶囊的核―壳化学结构和表面形态。采用差热扫描(DSC)分析了囊芯环氧树脂与固化剂的反应活性。通过热重分析法(TG)和极限氧指数法(LOI)研究了含磷环氧微胶囊的热稳定性及其在环氧复合材料中的阻燃性。结果表明:通过UV界面自由基聚合,在相分离作用下,能方便地实现微胶囊化,且所制含磷环氧微胶囊囊芯具明显的反应活性,其热稳定性和阻燃性能满足自修复复合材料性能要求。     

Particle structure of suspension poly(vinyl chloride) and its origin in the polymerization process

The initial stage of the suspension polymerization of poly(vinyl chloride) (PVC) is characterized by the formation of colloidally stable micron-sized grains of PVC inside the polymerizing ca. 150 μm vinyl chloride droplets. The fate of these micron-sized PVC grains depends upon the agitation conditions. If no agitation is employed, they serve as growth centers for further polymerization to give a final particle possessing a uniform internal bead morphology. In agitated systems, these grains coagulate early in the conversion to give a more irregular structure in the interior of the PVC particle. The formation of these stable growth centers appears to be unique to PVC. The polymerization of acrylonitrile, also insoluble in its monomer, is characterized by rapid agglomeration of the precipitated polymer throughout the polymerization. In PVC, the colloidal stability of the polymerizing grains is demonstrated to be electrical in nature. A pericellular membrane or skin formed by polymerization in both the water and vinyl phase completely surrounds the polymerizing droplet after about (1–2)% conversion. This skin is responsible for the charge retention of the PVC grains inside the polymerizing monomer droplets.     

Adaption of the Mechanism of Emulsion Polymerization to New Experimental Results

Summary: New experimental investigations of the 'classical' batch ab-initio emulsion polymerization of styrene reveal the important role of monomer droplets for the whole process. Monomer droplets with a size between a few and some hundreds of nanometers, which are formed by spontaneous emulsification as soon as styrene and water are brought into contact, have a strong influence on the particle nucleation, the particle morphology, and the swelling of the particles. Experimental results confirm that micelles of low molecular weight surfactants are not a major locus of particle nucleation. Brownian dynamics simulations show that the capture of matter by the particles (monomer or radicals) strongly depends on the polymer volume fraction and the size of the captured species (primary free radicals, oligomers, single monomer molecules, or clusters).     

Towards a consistent mechanism of emulsion polymerization—new experimental details

The application of atypical experimental methods such as conductivity measurements, optical microscopy, and nonstirred polymerizations to investigations of the ‘classical’ batch ab initio emulsion polymerization of styrene revealed astonishing facts. The most important result is the discovery of spontaneous emulsification leading to monomer droplets even in the quiescent styrene in water system. These monomer droplets with a size between a few and some hundreds of nanometers, which are formed by spontaneous emulsification as soon as styrene and water are brought into contact, have a strong influence on the particle nucleation, the particle morphology, and the swelling of the particles. Experimental results confirm that micelles of low-molecular-weight surfactants are not a major locus of particle nucleation. Brownian dynamics simulations show that the capture of matter by the particles strongly depends on the polymer volume fraction and the size of the captured species (primary free radicals, oligomers, single monomer molecules, or clusters).     

Suspension Polymerization of Methyl Methacrylate Stabilized Solely by Palygorskite Nano Fibers简

A kind of fibrous clay, palygorskite(PAL), was used as the sole stabilizer in suspension polymerization without the using of any other stabilizer usually used, especially polymeric stabilizers. In order to improve the compatibility with the organic monomer, PAL nano fibers were organically modified with silane coupling agent methacryloxypropyltrimethoxysilane(MPS). Transmission electron microscopy(TEM) and Fourier-transform infrared(FTIR) spectroscopy results show that the hydrolyzed MPS was attached onto PAL surface through Si―O―Si bonds formation without morphology change of PAL. At a loading amount of PAL to monomer as low as 0.36 wt%, effective stabilization could be achieved. After suspension polymerization, spherical poly(methyl methacrylate)(PMMA) particles were obtained. Scanning electron microscopy(SEM) analysis on both the outer surface and the inner cracked surface of the spherical PMMA particles indicates that the PAL particles reside on the surface of the PMMA spheres. The densely stacked PAL together with attached silane coupling agent stabilized the droplets throughout the suspension polymerization.     

丙烯酰胺在聚乙二醇水溶液中聚合产品的微观形态

采用偶氮类水溶性引发剂2,2′-偶氮二异丙基咪唑啉二盐酸盐(VA044)引发丙烯酰胺(AM)在聚乙二醇(PEG)水溶液中的双水相聚合;研究了引发剂、单体、聚乙二醇浓度及温度对最终产品中聚丙烯酰胺(PAM)液滴形态、尺寸的影响.随着引发剂浓度的增加,液滴由球状变为细长条状;随着温度的上升,球状液滴逐渐趋于条状,然后又重新趋于球状;在初始单体浓度较低时,PAM液滴滴径分布较窄,当其浓度增加后,滴径呈多峰分布;随着PEG浓度的增加,聚合物液滴趋于球状。     

高分散性SiO2/PMMA复合材料的制备与表征——纳米SiO2在MMA中的分散

用硅烷偶联剂3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)对分散于乙醇中的纳米SiO2进行偶联改性,再通过介质置换和原位本体聚合制得SiO2/甲基丙烯酸甲酯(MMA)单体分散液和SiO2/PMMA复合材料.红外光谱分析(FTIR)和热重分析(TG)结合洗提实验考察了SiO2表面MPS的偶联率和偶联效率,透射电镜(TEM...     

二氧化硅/聚苯乙烯单分散性核/壳复合球的制备

采用无皂乳液聚合包覆 ,制备了二氧化硅 聚苯乙烯单分散核 壳 (SiO2 PS)复合颗粒 ,包覆层厚度达到 10 0nm .选择 80～ 2 5 0nm二氧化硅粒径作为核颗粒 .为提高包覆效率 ,二氧化硅颗粒先用偶联剂甲基丙烯酰 (3 三甲氧基硅烷 )丙酯 (MPS)进行不同程度的表面改性 .控制MPS的结合率和单体的初始浓度可提高包覆效率 ,同时得到了单分散性复合颗粒 ,用透射电镜 (TEM)观察复合粒子的核 壳形态 .用动态光散射法 (DLS)测量表明所得复合颗粒具有单分散性 .     

Size control of phase‐separated liquid crystal droplets in a polymer matrix based on the phase diagram

When a mixture of liquid crystal (LC) and photo reactive monomer is irradiated by UV light, polymerization occurs and LC droplets form through phase separation, producing polymer dispersed LCs (PDLCs). Although size control of LC droplets and reduced amounts of LC in PDLC films are important in applications, precise size control of LC droplets at a low LC fraction has not yet been accomplished. In this study, the phase diagrams of the LC/initial monomer and the LC/polymer during polymerization were used to control LC droplet size at various LC fractions. Both the relative position of the sample in the initial phase diagram and the shift of the phase separation line during polymerization were shown to be important in determining the size of LC droplets. Our results are expected to provide a new strategy for precise size control of LC droplets especially at a low LC fraction range, which would be a great help for PDLC applications. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Sterically stabilized emulsion polymerization of styrene: Pseudo‐semicontinuous approach

The sterically stabilized emulsion polymerization of styrene initiated by a water‐soluble initiator at different temperatures has been investigated. The rate of polymerization (R_p) versus conversion curve shows the two non‐stationary‐rate intervals typical for the polymerization proceeding under non‐stationary‐state conditions. The shape of the R_p versus conversion curve results from two opposite effects—the increased number of particles and the decreased monomer concentration at reaction loci as the polymerization advances. At elevated temperatures the monomer emulsion equilibrates to a two‐phase or three‐phase system. The upper phase is transparent (monomer), and the lower one is blue colored, typical for microemulsion. After stirring such a multiphase system and initiation of polymerization, the initial coarse polymer emulsion was formed. The average size of monomer/polymer particles strongly decreased up to about 40% conversion and then leveled off. The initial large particles are assumed to be highly monomer‐swollen particles formed by the heteroagglomeration of unstable polymer particles and monomer droplets. The size of the “highly monomer” swollen particles continuously decreases with conversion, and they merge with the growing particles at about 40–50% conversion. The monomer droplets and/or large highly monomer‐swollen polymer particles also serve as a reservoir of monomer and emulsifier. The continuous release of nonionic (hydrophobic) emulsifier from the monomer phase increases the colloidal stability of primary particles and the number of polymer particles, that is, the particle nucleation is shifted to the higher conversion region. Variations of the square and cube of the mean droplet radius with aging time indicate that neither the coalescence nor the Ostwald ripening is the main driving force for the droplet instability. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 804–820, 2003     

水溶性和油溶性引发剂引发γ-甲基丙烯酰氧基丙基三甲氧基硅烷/苯乙烯细乳液共聚合的比较

分别用水溶性的过硫酸钾(KPS)和油溶性的2,2′-偶氮二异丁腈(AIBN)为引发剂引发γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPS)/苯乙烯(St)细乳液共聚合反应.比较了两类引发剂对MPS/St共聚合动力学(包括硅氧烷水解动力学和MPS/St的自由基共聚合动力学)、乳胶粒稳定性和共聚产物微结构的影响.