SiO2/聚合物核壳型杂化粒子及其空心结构的制备

SiO2/聚合物核壳型杂化粒子及其空心结构以其独特的形貌在药物控制释放、催化剂载体、生物医药等领域应用前景广阔,引起了人们的广泛关注。本文着重从乳液聚合法、仿生矿化法等制备方法角度阐述了SiO2/聚合物核壳型杂化粒子及其空心结构的研究进展。乳液聚合制备SiO2/聚合物核壳型杂化粒子简单易行,一般需要预先合成SiO2纳米粒子,其合成过程通常需要一些非理想的条件,如高温高压、极端pH、昂贵或有毒的有机试剂等,而且预先合成的SiO2粒子无法与聚合物实现100%匹配,即总有纯的聚合物粒子存在。相比之下,原位仿生矿化法制备SiO2杂化粒子不仅在环境条件下可进行,而且能够精确控制其纳米尺度的形态及分级有序结构。目前对材料科学家来讲,要使人工合成SiO2/聚合物杂化粒子实现像自然生物硅那样优异的性能,仍然是很大的挑战。     

疏水高分子介导可动芯SiO2杂化纳米粒子的仿生合成

在疏水高分子胶体模板——含氟丙烯酸酯(FA)共聚物乳胶粒中引入能够介导SiO2原位沉积的聚胺催化活性点-甲基丙烯酰氧乙基三甲基氯化铵(DMC),以四甲氧基硅烷(TMOS)为硅源,在环境条件下可控合成了核壳型FA共聚物/SiO2杂化纳米粒子.高温煅烧除去聚合物核质,可得到中空的SiO2纳米粒子,结合FTIR、EDX、TGA以及XPS等表征数据印证了SiO2的沉积主要发生在聚合物模板的表面.进一步考察了反应条件,如聚胺功能单体DMC的浓度、TMOS的浓度以及反应时间对SiO2杂化纳米粒子的形貌与组成的影响.实验结果表明增加DMC或者TMOS的浓度,适当延长反应时间,均可增加SiO2粒子的沉积速率,导致SiO2壳层的厚度增加,并且杂化粒子的形貌由凹陷多褶皱的核壳结构向可动芯结构转变.由于FA共聚物模板的强疏水性,增加有机核层和无机壳层间的不相容排斥,最终导致核壳层间空腔的形成,得到含可动芯的核壳型SiO2杂化粒子.     

通过RAFT聚合制备SiO2/接枝共聚物纳米杂化粒子

以二氧化硅(SiO2)纳米粒子表面键接的二硫代苯甲酸酯作为可逆加成-断裂-链转移(RAFT)聚合反应的链转移剂, 在室温下引发苯乙烯和马来酸酐进行表面RAFT交替共聚反应, 制得了SiO2/苯乙烯-alt-马来酸酐杂化材料. 通过聚氧化乙烯(PEO)的羟基与马来酸酐的酯化反应, 将PEO接枝到SiO2纳米粒子的表面, 增加了硅粒子的生物相容性. 用FTIR, TGA和TEM对杂化材料的结构、组成和形貌进行了表征.     

聚酰亚胺纳米杂化材料的制备、结构和性能

介绍了聚酰亚胺（PI）纳米杂化材料的四种制备方法：溶胶－凝胶法、插层法、分散法、相转移分散聚合法。纳米粒子在PI材料中分散性良好。由于纳米粒子本身 性和纳米粒子改变了PI材料的应力作用点，随着SiO2,AIN等纳米粒子含量增加，PI杂化的玻璃化温度、热分解湿度、拉伸强度、断裂伸长率、杨式模量、密度增加，线性膨胀系数减少。对介电性能的影响因不同纳米材料而异。     

以微凝胶模板合成P(AM-co-DMC)/SiO2杂化粒子

以聚(丙烯酰胺-co-甲基丙烯酰氧乙基三甲基氯化铵)[P(AM-co-DMC)]微凝胶为模板,TMOS为硅前驱体,中性水环境下合成了一系列P(AM-co-DMC)/SiO2有机-无机杂化粒子.对杂化粒子的大小、形态及表面形貌等进行研究,发现微凝胶对杂化粒子的形态和大小起主导作用,SiO2在模板上沉积,即使经过灼烧依然保持模板的形态;TMOS的用量对杂化粒子的性质也有重要影响——用量少时,得到的杂化粒子表面粗糙,增加用量会使表面变得光滑.杂化粒子经过灼烧后,表面会变得更加粗糙.     

SiO2交联剂交联MMA聚合制备PMMA/SiO2纳米复合材料

用SiO2交联剂(SiO2HPA)交联甲基丙烯酸甲酯(MMA)自由基聚合制备PMMA SiO2纳米复合材料。采用两步法将可聚合乙烯基单体以化学键的形式键接到SiO2表面合成SiO2交联剂,首先利用过量的甲苯2,4二异氰酸酯(TDI)对SiO2纳米粒子表面进行化学修饰合成出表面带有高反应活性NCO基团的功能化SiO2粒子(SiO2TDI),SiO2TDI与丙烯酸羟丙酯(HPA)反应合成SiO2交联剂。系统研究了MMA单体与SiO2交联剂投料比及聚合时间对聚合反应的影响。此外,利用红外光谱(FT IR)、DSC、TGA、可见光光谱仪等实验手段对纳米复合材料进行了表征分析。结果表明,纳米SiO2粒子在复合材料中起着物理交联点和化学交联点作用,复合材料玻璃化转变温度(Tg)明显地高于其纯PMMA的玻璃化转变温度,随着纳米SiO2粒子含量的增加,复合材料玻璃化温度升高,而透明度明显降低。     

RAFT聚合制备PBMA/AA-SiO2杂化纳米材料

以三硫代二[4-(甲氧羰基)苄基]碳酸酯为链转移剂(CTA),甲基丙烯酸丁酯(BMA)为单体,通过可逆加成-断裂链转移自由基聚合(RAFT)法修饰丙烯酸(AA)功能化的纳米二氧化硅(SiO2),制备了PBMA/AA-SiO2有机/无机杂化纳米材料。并通过FT-IR、GPC、TGA、TEM表征和分析了杂化材料的结构、分子量、SiO2纳米粒子在基体中的分散性以及杂化材料的热稳定性。结果表明,PBMA/AA-SiO2杂化微球粒径约为22 nm,分布均匀;TGA分析表明此杂化材料的热稳定性良好,PBMA接枝率为19%。     

可聚合纳米SiO2杂化材料的制备及其性能研究

利用异佛尔酮二异氰酸酯(IPDI)和纳米SiO2表面-OH基团反应的特点,制备了表面含-NCO基团的纳米SiO2,用端羟基聚丙二醇醚(PPG)对其扩链并进一步和丙烯酸羟乙酯(HEA)反应,制备了丙烯酸酯封端、IPDI和PPG连接纳米SiO2粒子的纳米SiO2杂化材料.用红外光谱(FTIR)、热失重(TGA)和扫描电镜(...     

二氧化硅纳米粒子表面修饰及其表征

采用溶胶-凝胶法合成粒径在50—150nm范围内的二氧化硅（SiO2）纳米粒子。用甲基丙烯酸-3-（三甲氧基硅基）丙酯（MPS）对SiO2纳米粒子表面进行修饰,使其表面接枝能参与自由基聚合反应的碳碳双键基团。用元素分析、FTIR、^13C CP／MASNMR和^29Si CP／MASNMR等手段对修饰过的SiO2纳米粒子进行表征,以确证MPS接枝在SiO2纳米粒子上。分析修饰过的SiO2纳米粒子的^29Si CP／MASNMR和FTIR谱图,还可初步推断MPS接枝在SiO2纳米粒子表面的机理：MPS首先发生水解缩合反应形成低聚物,然后通过氢键作用吸附到SiO2纳米粒子表面,最后MPS低聚物中未缩合的硅羟基与SiO2纳米粒子表面的硅羟基发生缩合反应。     

Poly(St-co-DMC)/SiO_2杂化及空心杂化纳米粒子的合成及表征

采用无皂乳液聚合法合成了聚(苯乙烯-co-甲基丙烯酰氧乙基三甲基氯化铵)(poly(St-co-DMC))纳米粒子,平均粒径约为100 nm.以此纳米粒子为模板,在接近室温及p H为中性的温和条件下,以四甲氧基硅烷(TMOS)为硅源,合成了poly(St-co-DMC)/Si O2杂化纳米粒子,TEM结果显示该纳米粒子具有明显的核壳结构,Si O2主要沉积在壳层.进一步通过四氢呋喃溶解制备得到具有空心结构的纳米粒子,这种空心结构纳米粒子的FTIR图谱中既有Si O2的信号,也有poly(St-co-DMC)的信号,说明空心纳米粒子的壳层不完全是Si O2,对空心纳米粒子的TGA结果分析计算得到Si O2的含量仅为69.7%,说明纳米粒子的壳层为杂化壳层,并且,这种壳层的厚度随着反应温度的升高、反应时间的延长、TMOS用量的增加及聚合物模板中DMC含量的增加而增大.     

Biomimetic synthesis of raspberry-like hybrid polymer–silica core–shell nanoparticles by templating colloidal particles with hairy polyamine shell

The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core–shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core–shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 °C for 2.5 h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA–silica hybrid shell. The resulting hybrid silica core–shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core–shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA–silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core–shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules.     

Novel superhydrophobic silica/poly(siloxane‐fluoroacrylate) hybrid nanoparticles prepared via two‐step surface‐initiated ATRP: Synthesis,characterization, and wettability

Poly(siloxane‐fluoroacrylate)‐grafted silica hybrid nanoparticles were prepared by surface‐initiated atom transfer radical polymerization (SI‐ATRP). The silica nanoparticles with α‐bromo‐ester initiator group for copper‐mediated ATRP were prepared by the self‐assembled monolayers of (3‐aminopropyl)triethoxysilane and 2‐bromoisobutyrate bromide. Well‐defined diblock copolymer brushes consisting of poly(methacryloxypropyltrimethoxysilane) and poly(2,2,3,3,4,4,4‐heptafluorobutyl methacrylate) blocks were obtained by using initial homopolymer brushes as the macroinitiators for the SI‐ATRP of the second monomer. Chemical compositions and structures of the nanoparticles were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. Surface properties and morphology of the nanoparticles were investigated with X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, and water contact angle measurement. It is revealed that the surfaces of the nanocomposites are rough at the microscale and nanoscale. The formation reason of the superhydrophobic surfaces was also discussed in this work. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Synthesis of UV‐cured acrylic–silica hybrid nanocomposites from dendritic acrylic oligomer and acrylic‐functionalized silica

An acrylic–silica hybrid polymeric nanocomposite, comprising well‐distributed silica nanoparticles in acrylic matrix, has been synthesized at a markedly rapid rate from a dendritic acrylic oligomer (DAO) and an acrylic‐functionalized silica (A‐silica) via UV‐curing. A‐silica was made by functioning colloidal silica nanoparticles with 3‐methacryloxypropyltrimethoxysilane (MATMS) and DAO was formed by reacting 1,5‐diamino‐2‐methylpentane (MPMDA) with trimethylopropane triacrylate (TMPTA). The MATMS has been found either doubly or singly bonded to silica nanoparticles but not triply bonded, and the inclusion of MATMS into the siloxane network structure increases the size of silica nanoparticles. The well distribution of A‐silica and its good compatibility with DAO cause an increase in T_d of the acrylic–silica hybrid material. Silica nanoparticles are too small to cause any significant light scattering, and do not have deleterious effects on transparency. The “hybrid‐on‐polyethylene terephathalate” films exhibited satisfactory hardness and surface roughness because of silica nanoparticles. The preparation as well as the characterization of the constituting species and the final hybrid material are described in detail. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8149–8158, 2008     

Facile strategy for synthesis of silica/polymer hybrid hollow nanoparticles with channels

The silica/polymer hybrid hollow nanoparticles with channels and gatekeepers were successfully fabricated with a facile strategy by using thermoresponsive complex micelles of poly(ethylene glycol)-b-poly(N-isopropylacrylamide) (PEG-b-PNIPAM) and poly(N-isopropylacrylamide)-b-poly(4-vinylpyridine) (PNIPAM-b-P4VP) as the template. In aqueous solution, the complex micelles (PEG-b-PNIPAM/PNIPAM-b-P4VP) formed with the PNIPAM block as the core and the PEG/P4VP blocks as the mixed shell at 45 °C and pH 4.0. After shell cross-linking by 1,2-bis(2-iodoethoxyl)ethane (BIEE), tetraethylorthosilicate (TEOS) selectively well-deposited on the P4VP block and processed the sol-gel reaction. When the temperature was decreased to 4 °C, the PNIPAM block became swollen and further soluble, and the PEG-b-PNIPAM block copolymer escaped from the hybrid nanoparticles as a result of swelled PNIPAM and weak interaction between PEG and silica at pH 4.0. Therefore, the hybrid hollow silica nanoparticles with inner thermoresponsive PNIPAM as gatekeepers and channels in the silica shell were successfully obtained, which could be used for switchable controlled drug release. In the system, the complex micelles, as a template, could avoid the formation of larger aggregates during the preparation of the hybrid hollow silica nanoparticles. The thermoresponsive core (PNIPAM) could conveniently control the hollow space through the stimuli-responsive phase transition instead of calcination or chemical etching. In the meantime, the channel in the hybrid silica shell could be achieved because of the escape of PEG chains from the hybrid nanoparticles.     

Polystyrene‐Core–Silica‐Shell Hybrid Particles Containing Gold and Magnetic Nanoparticles

Polystyrene‐core–silica‐shell hybrid particles were synthesized by combining the self‐assembly of nanoparticles and the polymer with a silica coating strategy. The core–shell hybrid particles are composed of gold‐nanoparticle‐decorated polystyrene (PS‐AuNP) colloids as the core and silica particles as the shell. PS‐AuNP colloids were generated by the self‐assembly of the PS‐grafted AuNPs. The silica coating improved the thermal stability and dispersibility of the AuNPs. By removing the “free” PS of the core, hollow particles with a hydrophobic cage having a AuNP corona and an inert silica shell were obtained. Also, Fe₃O₄ nanoparticles were encapsulated in the core, which resulted in magnetic core–shell hybrid particles by the same strategy. These particles have potential applications in biomolecular separation and high‐temperature catalysis and as nanoreactors.     

Photoreactive azido-containing silica nanoparticle/polycation multilayers: durable superhydrophobic coating on cotton fabrics

In this study, we report the functionalization of silica nanoparticles with highly photoreactive phenyl azido groups and their utility as a negatively charged building block for layer-by-layer (LbL) electrostatic assembly to produce a stable silica nanoparticle coating. Azido-terminated silica nanoparticles were prepared by the functionalization of bare silica nanoparticles with 3-aminopropyltrimethoxysilane followed by the reaction with 4-azidobenzoic acid. The azido functionalization was confirmed by FTIR and XPS. Poly(allylamine hydrochloride) was also grafted with phenyl azido groups and used as photoreactive polycations for LbL assembly. For the photoreactive silica nanoparticle/polycation multilayers, UV irradiation can induce the covalent cross-linking within the multilayers as well as the anchoring of the multilayer film onto the organic substrate, through azido photochemical reactions including C-H insertion/abstraction reactions with surrounding molecules and dimerization of azido groups. Our results show that the stability of the silica nanoparticle/polycation multilayer film was greatly improved after UV irradiation. Combined with a fluoroalkylsilane post-treatment, the photoreactive LbL multilayers were used as a coating for superhydrophobic modification of cotton fabrics. Herein the LbL assembly method enables us to tailor the number of the coated silica nanoparticles through the assembly cycles. The superhydrophobicity of cotton fabrics was durable against acids, bases, and organic solvents, as well as repeated machine wash. Because of the unique azido photochemistry, the approach used here to anchor silica nanoparticles is applicable to almost any organic substrate.     

A Simple Approach to Fabricate CdS-SiO2 Hybrid Microspheres by Producing CdS Nanoparticles on the Surface of Thiolated SiO2 Microspheres

IntroductionSemiconductor nanoparticles show a quantum sizeeffect and have attracted much attention because oftheir unique photochemical and photophysical proper-ties[1—4].In recent years,quantumdots of CdS and in-organic nanoparticles hybrid composites …     

Photocuring kinetics of UV‐initiated free‐radical photopolymerizations with and without silica nanoparticles

We used photodifferential scanning calorimetry to investigate the photocuring kinetics of UV‐initiated free‐radical photopolymerizations of acrylate systems with and without silica nanoparticles. Two kinetics parameters—the rate constant (k) and the order of the initiation reaction (m)—were determined for hybrid organic–inorganic nanocomposite systems containing different amounts of added silica nanoparticles (0–20 wt %) and at different isothermal temperatures (30–100 °C) using an autocatalytic kinetics model. The kinetic analysis revealed that the silica nanoparticles apparently accelerate the cure reaction and cure rate of the UV‐curable acrylate system, most probably due to the synergistic effect of silica nanoparticles during the photopolymerization process. However, a slight decrease in polymerization reactivity that occurred when the silica content increased beyond 15 wt % was attributed to aggregation between silica nanoparticles. We also observed that the addition of silica nanoparticles lowered the activation energy for the UV‐curable acrylate system, and that the collision factor for the system with silica nanoparticles was higher than that obtained for the system without silica nanoparticles, indicating that the reactivity of the former was greater than that of the latter. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 658–670, 2005