大粒径自消光核-壳丙烯酸树脂涂饰剂的合成与表征

以半连续投料法,通过种子乳液聚合-三次连续核长大-壳聚合的方式制备了具有核-壳结构、大粒径自消光丙烯酸树脂乳液。研究了不同投料方式对种子乳胶粒粒径的影响,探索了乳胶粒粒径连续长大的方法,同时还研究了乳胶粒粒径、乳胶粒的核-壳结构以及交联度等因素对丙烯酸树脂涂层消光性能的影响。结果表明,半连续法投料方式能够得到较大粒径的种子乳胶粒,控制乳化剂浓度和单体浓度使得种子乳液聚合遵循低聚物成核机理,并且反应中乳胶粒长大占据主导,从而得到大粒径的种子乳胶粒(200 nm左右)。种子乳胶粒经过3次长大后,粒径可达到700 nm左右,最后经过壳聚合反应,核-壳乳胶粒粒径进一步增大至800 nm左右。不同乳胶粒粒径、核-壳结构、交联度对涂层光泽产生重要影响,大的乳胶粒粒径使得涂层产生球形粒子状微粗糙表面,涂层光泽度降低;软核-硬壳结构导致成膜时乳胶粒变形困难,也可提高涂层表面粗糙度和消光度;壳层交联使得壳层结构致密度上升,自由度降低,乳胶粒难以变形和融合,涂层粗糙度进一步提高,光泽度进一步降低,最终所制备的皮革涂层光泽度可调控至1.2°。     

单分散聚苯乙烯微球的制备及二维胶体晶体的自组装

以苯乙烯为原料、过硫酸钾为引发剂,采用无皂乳液聚合法成功地制备出具有良好球形度的单分散聚苯乙烯微球.研究了在聚苯乙烯微球合成过程中单体浓度、引发剂浓度、聚合时间对粒径及分布的影响.实验结果表明,适当改变单体浓度、引发剂浓度、聚合时间可以得到不同粒径的聚苯乙烯微球,且微球单分散性良好.采用自组装技术组装单分散聚苯乙烯微球,获得了二维有序聚苯乙烯胶体晶体.     

聚苯乙烯-银胶体晶体的制备及自组装行为

利用冠醚可与银离子复合的特性,制备了聚苯乙烯-冠醚乳胶粒,采用原位还原的方法在乳胶粒表面引入银纳米颗粒,通过垂直沉降,乳胶粒子可自组装成紧密堆积具有面心立方的聚苯乙烯-银胶体晶体。结果表明:引入聚苯乙烯-银乳胶粒表面的银为胶粒总质量的6.7%,乳胶粒具有以银纳米颗粒为壳,聚苯乙烯为核的核壳结构,乳胶粒大小为260 nm,并具有很好的单分散性。由于Bragg散射,该胶体晶带隙位于580 nm,在可见光区域产生明显的光子带隙而呈现出亮丽的绿色。     

普通乳液聚合法制备丙-苯纳米核壳乳液

文中通过预乳化-半连续的加料工艺制备出了以聚丙烯酸丁酯为核,聚苯乙烯-甲基丙烯酸甲酯为壳的丙-苯纳米核壳乳液,分析了这种乳液聚合的方法制备纳米乳液的机理。通过粒度分布仪测定的乳胶粒的粒径分布为93.4 nm～95.6 nm,分布很窄,乳胶粒的平均粒径为94.5 nm;通过透射电境(TEM)对乳液进行观察,所制的丙-苯纳米乳胶粒具有明显的正向核壳结构,实验证明这种核壳结构是稳定的。     

P(S-SS)/CdS核壳粒子的制备与表征

采用超声辐照乳液聚合得到聚(苯乙烯-苯乙烯磺酸钠)(P(S-SS))乳胶粒,用直接沉淀法在乳胶粒表面原位生成硫化镉(CdS)纳米粒子,得到P(S-SS)/CdS核壳粒子。用元素分析和XPS研究了共聚物的组成及磺酸基(-SO3-)的分布,结果表明,-SO3-主要分布在乳胶粒表面,有利于CdS纳米粒子在乳胶粒表面的沉积。用XRD、TEM及UV-v is表征了共聚物乳胶粒及P(S-SS)/CdS核壳粒子的结构及CdS的量子效应。结果表明,所制备的CdS纳米粒子为六方晶型,平均粒径为6 nm,在P(S-SS)乳胶粒外层形成多层包覆,P(S-SS)/CdS核壳粒子平均粒径为70 nm,CdS纳米粒子表现出明显的量子尺寸效应。     

硅烷偶联剂核交联聚丙烯酸酯多元醇乳液的合成及表征

以硅烷偶联剂作为交联剂,制备了具有核交联结构的聚丙烯酸酯多元醇乳液(Si-PHA),并用FTIR、TEM、粒径分布仪对乳液进行结构表征.FTIR、TEM和粒径分布仪均证实,硅烷偶联荆在聚合过程中发生了部分水解、缩合反应,得到具有核交联结构的Si-PHA.Si-PHA乳胶粒为表面具有凹陷结构的近似球体,且粒径呈单分散分布.Si-PHA乳胶粒内的硅氧烷在贮存期间会继续发生水解、缩合反应,乳胶粒粒径进一步变小.     

微波辐照辅助核/壳型聚硅氧烷/聚丙烯酸酯复合乳液的制备与表征

微波辐照乳液聚合技术具有产率高、节能省时等优点.本工作利用微波辐照,采用半连续种子乳液聚合法制备了具有明显核壳结构的聚硅氧烷/聚丙烯酸酯复合乳液;利用傅里叶变换红外光谱、粒度分析、核磁分析、透射电镜、热重分析等技术手段对产物进行了系统化表征,研究了偶联剂(γ-甲基丙烯酰氧基丙基三异丙氧基硅氧烷,C-1757)的用量对乳液聚合和复合胶膜性能的影响.结果表明:复合乳胶粒的平均粒径均小于100 nm,具有明显的核/壳结构;随着偶联剂用量的增加,复合乳胶粒粒径增大,分布变窄,制备的复合胶膜吸水率明显降低,力学性能和热稳定性显著提高.     

PMMA纳米微球的制备与表征

以甲基丙烯酸甲酯(MMA)为单体、过硫酸钾为引发剂、十二烷基硫酸钠为乳化剂,采用分散乳液聚合法制备分散聚甲基丙烯酸甲酯(PMMA)微球,并自组装得到有序的空间结构。用粒度仪和扫描电子显微镜(SEM)分析PMMA微球的粒径尺寸和形貌,采用响应面分析法结合单因素趋势变化研究单体、引发剂、乳化剂、搅拌速度以及温度对PMMA微球粒径和分布的影响。结果表明,通过控制实验条件制备出平均粒径为115nm的PMMA微球,其分布集中,粒径随着引发剂量、单体量、温度的增加而增加,但是粒径大小却随着搅拌速度、乳化剂的增加而减小。     

PHMS为反应性助稳定剂制备高固含量苯丙共聚细乳液

以含氢聚硅氧烷(PHMS)为反应性助稳定剂,采用一步法和半连续法细乳液聚合制备了固含量为50%苯丙共聚乳液。考察了不同细乳液聚合体系中反应稳定性、单体转化率、共聚乳胶粒子粒径及粒径分布变化、粒子数目变化及乳液稳定性的不同。结果表明,与一步法细乳液聚合相比,半连续细乳液聚合过程中单体转化率增长缓慢,聚合稳定性好;乳胶粒径由156.8 nm增大到215.3 nm;粒径分布指数在0.151~0.254之间,乳胶粒子数目相对稳定;制备高固含量苯丙乳液贮存稳定性、冻融及钙离子稳定性比一步法细乳液聚合体系好。     

聚醋酸乙烯酯反向核壳结构乳胶粒制备及形成机制

以马来酸酐(MA)作为接枝共聚单体,亲水性的聚醋酸乙烯酯(PVAc)为核,疏水性的聚苯乙烯(PSt)为壳,成功构建出一种新颖的PVAc-MA/PSt反向异形核壳结构乳胶粒,从而解决了因竞聚率差异大而无法实现醋酸乙烯酯(VAc)与苯乙烯(St)复合的难题。同时,利用接枝共聚所形成的过渡层,能够很好地抑制核壳翻转,从而成功地解决了反向核壳结构乳胶粒容易发生核壳翻转的问题。所制备出的反向核壳结构乳胶粒子平均粒径为330 nm左右,粒径大小均一。通过热力学分析发现所制备的乳胶粒呈明显的相分离结构,且存在PVAc-MA-PSt过渡层结构;乳胶粒的形貌随着MA含量的变化发生明显的衍变趋势,且粒子形貌变化可控。提出了PVAc-MA/PSt反向核壳乳胶粒子的形成机制。     

SYNTHESIS AND CHARACTERIZATION OF CONTROLLED SIZES: POLYSTYRENE LATEXES

Several parameters and their limitations to prepare monodisperse polystyrene particles were discussed. Polystyrene latexes B, C and D of diameter 129.8, 142.8 and 264.5 nm, respectively, were synthesized by emulsion polymerization method. The latex D is almost monodisperse with very low polydispersity of 0.005 while B and C are having polydispersity of 0.1837 and 0.1601. The particle size and particle size distribution of the latexes were determined by a TEM and Brookhaven particle size analyzer. It was observed that the particle size of the latexes decreased with increasing initiator (ammonium persulfate) or surfactant (SDS) concentrations. The surface area of the latexes were calculated by using BET equation on the basis of the amount of nitrogen gas adsorbed at the surface of the particles to form a monolayer. It was observed that the surface area of latex D is less than B and C because of the bigger size of the particles. The average molecular weights, zeta potentials and densities of the latexes were also presented.     

Nanoparticles of latexes from commercial polystyrene

Nanoparticles of polystyrene (PS) (Mw = 1.0-3.0 x 10(6) g/mol) latexes have been successfully prepared from their respective dilute PS (commercial) solutions in cyclohexane, toluene/methanol, or cyclohexane/toluene at each theta temperature. The cationic surfactant cetyltrimethylammonium bromide (CTAB) was used to stabilize the formed PS latex particles. By varying different concentrations of CTAB and PS solution of various Mw, we have successfully produced, for the first time, stable bluish-transparent latex particles ranging from about 10 to 30 nm in diameter (Dw). The number of polymer chains per latex particle (np) is directly proportional to the volume occupied by each latex particle and hence associated to its Dw. The characteristics of these preformed PS latex particles are quite similar to those obtained from the microemulsion polymerization of styrene as reported in literature. These PS latex particles could be further grown by seeding polymerization of styrene to about 50 nm (Dw) with a monodisperse size distribution of Dw/Dn = 1.08.     

Encapsulation of magnetic nanoparticles with polystyrene via emulsifier-free miniemulsion polymerization

Magnetite nanoparticles (Fe₃O₄), with an average size of about 10 nm, were encapsulated with polystyrene using a new method based on emulsifier-free miniemulsion polymerization in the presence of 2, 2′ azobis (2-amidinopropane) dihydrochloride (V-50) as a cationic ionizable water-soluble initiator and hexadecane as a hydrophobe. Transmission electron microscopy (TEM) proved the presence of magnetite in polymer particles which appeared to be monodisperse in size, approximately 100-300 nm in diameter, through TEM and scanning electron microscopy (SEM). Thermogravimetric analysis (TGA) measurement was used to determine the percentage of magnetite in the products. The results of emulsifier-free miniemulsion polymerization were compared with those of conventional emulsifier-free emulsion polymerization using (V-50) as the initiator in both cases.     

微米级聚苯乙烯微球合成过程反应条件的优化

用分散聚合法合成4~8μm的单分散聚苯乙烯微球,实验考察反应温度对体系的黏度、微球分子量及微球密度等结构参数的影响,同时考察反应温度以及单体、引发剂和稳定剂等分散聚合的主要组分对所合成的聚合物微球粒径及粒径分布的影响。结果表明,反应温度为70℃时,制备的单分散聚苯乙烯微球结构最致密,微球产率较高,微球耐有机溶剂的能力较强;随着初始单体浓度、引发剂用量的增加和反应温度的升高,最终得到的聚苯乙烯微球粒径虽有所增大,但微球粒径分布变宽;随着稳定剂用量的增加,最终微球粒径减小,粒径分布变窄。     

Preparation of magnetic polymeric composite nanoparticles by seeded emulsion polymerization

Seeded emulsion polymerization was used to prepare magnetic polymeric composite nanoparticles (MPCNPs) with the aim to successfully encapsulate magnetite particles and to improve particle size distribution (PSD). Microscopical morphology and number-average diameter of hydrophilic magnetite particles (HMPs), magnetic seed latex nanoparticles (MSLNPs) and MPCNPs were observed and analyzed by transmission electron microscope (TEM). Weight-average diameter and PSD of MSLNPs and MPCNPs were also analyzed by TEM. Magnetic properties of MPCNPs were investigated by Vibrating Sample Magnetometry (VSM). The results showed that the encapsulation of magnetite particles was not complete by conventional emulsion polymerization but very successful by seeded emulsion polymerization, the resulted MPCNPs were nanoparticles with much narrower PSD than that of MSLNPs, and exhibited superparamagnetism and possessed a certain level of magnetic response.     

《二氧化硅孔材料的模板合成》化学综合实验的建设

化学综合实验"二氧化硅孔材料的模板合成"是为大学化学专业本科生开设的一个实验教学课程。其实验的主要内容是,首先合成制备单分散的聚苯乙烯乳胶粒子,然后以此单分散的聚苯乙烯乳胶粒子为初始材料,利用胶体晶模板法制备二氧化硅三维有序孔材料。利用透射电子显微镜和扫描电子显微镜对所制备的各级样品进行表征。教学实践发现,当作为初始材料的聚苯乙烯乳胶粒子尺寸较大时,三维有序孔材料的制备成功率高。文中介绍了此实验的建立以及对其进行改进的过程。     

PBA/PMMA型核壳结构增韧剂的合成及表征

采用传统乳液聚合、无皂乳液聚合及其扩径聚合的方法,得到了粒径从０．０７８ｕｍ至１．３８ｕｍ的窄分布的ＢＡ（丙烯酸丁酯）为主单体的ＰＢＡ橡胶核,然后,进行ＰＭＭＡ的壳层种子接枝乳液聚合,得到ＰＢＡ／ＰＭＭＡ核壳结构胶乳,乳液经破乳过滤干燥后得到核壳结构增韧剂,发现随着橡胶相交联剂用量的增加,ＰＢＡ胶粒表现双键含量增加;核壳复合粒子表观羧基的含量可以用电位滴定法获得。实验表明,进行壳层混合单体（ＭＭＡ、ＭＡＡ）接枝时羧基主要分布在胶粒的浅层;核壳比对复合粒子的形态有较大影响。利用ＬＳ激光粒径仪测得胶粒的大小及其分布;同时,ＴＥＭ照片显示了核壳粒子的形态和尺寸。     

硅溶胶存在下的聚丙烯酸酯无皂乳液聚合

采用无皂乳液聚合法合成了粒径分布单一的硅溶胶/聚丙烯酸酯复合乳液。讨论了硅溶胶对无皂乳液聚合成核过程、乳胶粒粒径及其分布、乳液稳定性的影响。结果表明,硅溶胶的加入减小了乳胶粒粒径,并且对乳液有稳定作用。通过透射电镜(TEM)对复合乳胶粒结构进行观察,表明乳胶粒具有两相复合结构。结合实验结果,提出了该体系无机有机两相复合机理,即无皂乳液聚合初期的聚丙烯酸酯初始微粒不稳定,易与硅溶胶粒子聚并。     

溶胶-凝胶模板法制备三维有序大孔Y2O3微球

采用无皂乳液聚合法制备了纳米级单分散P（St-HEA）微球,然后在二甲基硅油中自组装形成微米级胶体晶体大球,利用溶胶-凝胶模板法制备了三维有序大孔Y2O3微球。采用红外光谱（FT-IR）,扫描电镜（SEM）,X射线衍射（XRD）等测试方法对P（St-HEA）微球单分散性及有序大孔Y2O3微球结构和物相组成进行了表征。结...     

高固含量丙烯酸酯共聚物乳液的单体组成与流变行为

合成了一系列固体含量为70%的丙烯酸丁酯/甲基丙烯酸甲酯/α-甲基丙烯酸(BA/MMA/MAA)共聚物乳液,研究了软(BA)、硬(MMA)段单体用量比对乳液体系流变行为的影响,并对其乳胶粒的粒径分布和微观形态进行了表征。结果表明,所合成乳液乳胶粒的粒径在50nm~650nm范围内,呈宽分散分布状态。当BA/MMA<60/40时,乳液可保持低黏度;而当BA/MMA>60/40时,乳液的黏度急剧增加。随着乳液中软、硬段单体比的不同,乳液的乳胶粒分布状态和凝聚形态均有显著变化。