原子转移自由基聚合法制备聚合物刷

介绍了原子转移自由基聚合法(ATRP)制备聚合物刷(平面刷、球形刷和分子刷)的研究进展及应用前景.聚合物刷子的奇异构象使其具有许多新奇的性质和潜在的应用前景.ATRP是制备具有可控结构的聚合物以及有机/无机杂化材料的一种较好的方法.通过ATRP制备聚合物刷,可以有效地改变聚合物刷的组成和聚合度,从而改变聚合物刷的表面性质,设计出具有新型结构及性能的材料.     

原子转移自由基聚合(ATRP)制备聚合物刷的研究进展

从聚合物刷的概念和ATRP技术的提出入手,概述了聚合物刷的基本理论、合成方法及应用,并着重介绍了ATRP法制备聚合物刷方面的研究进展.     

原子转移自由基聚合及其在共聚物分子设计中的应用

原子转移自由基聚合 (ATRP)方法是一种新发展起来的可控 /“活性”聚合方法。本文对原子转移自由基聚合及其反应机理作了简要介绍 ,并对其近期进展进行了评述 ,着重介绍了其在共聚物分子结构设计中的一些应用。     

利用开环聚合和原子转移自由基聚合在纳米二氧化硅表面接枝聚合物

利用硅烷偶联剂KH-550处理纳米二氧化硅(SiO_2)表面,得到氨基化的SiO_2,再通过溴异丁酸缩水甘油酯与氨基的开环反应,在SiO_2表面同时键接了开环聚合(ROP)的引发剂-OH和原子转移自由基聚合(ATRP)的引发剂-Br(SNPs-fOH/Br)。以SNPs-f-OH/Br为引发剂,分别进行ROP和ATRP,在纳米SiO_2表面接枝了聚己内酯(PCL)和聚苯乙烯(PS)混合聚合物刷(Mixed brush)。采用红外光谱、透射电镜、热失重、凝胶渗透色谱等方法对所得到的复合粒子进行了表征和测试。研究结果表明,混合聚合物刷成功接枝到了纳米SiO_2表面,通过控制聚合时间可以控制2种接枝聚合物的相对分子质量。本方法为纳米粒子表面接枝混合聚合物刷提供了一种简便的方法。     

"活性"/可控自由基聚合制备含糖聚合物的研究进展

含有糖单元的聚合物因其在药学和生物技术等领域的潜在应用价值吸引了科研工作者的广泛关注.文中介绍了原子转移自由基聚合(ATRP),氮氧稳定自由基聚合(NMP),可逆加成断裂链转移聚合(RAFT)等"活性"/可控自由基聚合在制备含糖聚合物中的应用进展,重点介绍了上述三种聚合方法对含糖聚合物分子量和结构的控制.     

原子转移自由基聚合的最新研究进展

介绍了关于原子转移自由基聚合(ATRP) 引发-活化-失活过程的最新研究进展,包括RATRP 体系克服了常规ATRP 体系中低价态过渡金属催化剂容易氧化的问题,AGET ATRP 体系显著降低了过渡金属化合物的用量,ARGET ATRP体系中残存的过渡金属催化剂仅为(1～50)×10-6, 很多情况下不需要进行后处理,使其适合工业化生产成为可能.同时介绍了ATRP在表面接枝上的应用,表面引发ATRP反应能改善材料的表面特性,同时具有接枝链分子量及分布可控和高接枝率的优点,使其在很多方面都获得了广泛的应用,包括使材料表面图案化、提高材料表面的生物相容性、制备梳型的聚合物刷以及在纳米磁铁矿和真丝表面引发的ATRP反应.     

原子转移自由基溶液聚合制备聚合物纳米粒子

使用2-氯丙酰氯对第四代聚丙烯亚胺树枝状大分子(DAB-32)进行改性,成功合成了树枝状大分子引发剂DAB-32-Cl,并使用红外光谱(FT-IR)、核磁共振光谱(1H-NMR)对引发剂的结构进行了表征。以此引发剂,CuCl/Bpy为催化剂,成功实现了丙烯酸(AA)和苯乙烯(St)的原子转移自由基(ATRP)溶液聚合,制备出树枝状大分子/聚丙烯酸和树枝状大分子/聚苯乙烯纳米粒子。采用光子相关光谱(PCS)和透射电子显微镜(TEM)对聚合物纳米粒子的形貌、粒径和粒径分布进行了表征,结果表明,合成的聚合物纳米粒子大小均一,小于121 nm,分散性较好。     

可控活性自由基聚合制备端基官能化聚合物研究进展

端基官能化聚合物是指那些在聚合物末端或悬垂端含有活性官能团的聚合物。它们可发挥交联剂或扩链剂的作用,从而制备出不同结构特点的嵌段聚合物、接枝聚合物、星型、超支化或树状聚合物。文章主要对引发转移终止剂(Iniferter)法、原子转移自由基聚合(ATRP)、氮氧自由基调控聚合(NMRP)和可逆加成-断裂链转移自由基聚合(RAFT)等可控活性自由基聚合方法在制备端基官能化聚合物中的应用进行了介绍。最后对可控活性自由基聚合在功能性聚合物制备中的应用前景进行了展望。     

"活性"/可控自由基聚合的研究进展

对聚合物分子的组成和结构进行精密控制是当前聚合物研究的重要领域,“活性”／可控自由基聚合可以对自由基聚合进行控制,其综合了自由基聚合和离子聚合的优点。本文介绍了实现“活性”／可控自由基聚合的5种途径,认为利用“活性”／可控自由基聚合可以合成新型确定构造的聚合物。     

原子转移自由基聚合制备ABA型嵌段共聚物

以α，α’－二溴代二甲苯为引发剂，CuBr/2,2‘－联吡啶为催化体系，制备了双溴端基的分子量分布窄的聚苯乙烯（MWD＝1．21）。再以此作为大分子引发剂，实现了甲基丙烯酸甲酯的原子转移自由基聚合，制得了分子量可控且分子量分布窄的ABA型嵌段共聚物，即聚甲基丙烯酸甲酯－b－聚苯乙烯－b－聚甲基丙烯酸甲酯。     

Preparation and characterization of optical-functional diblock copolymer brushes on hollow sphere surface via atom transfer radical polymerization

The optical-functional poly(methyl methacrylate)-block-Tb complex diblock copolymer brushes grafted from hollow sphere surface via atom transfer radical polymerization were investigated in this work. A sufficient amount of azo initiator was introduced onto hollow sphere surface firstly. Then the monomer methyl methacrylate was polymerized via surface-initiated reverse atom transfer radical polymerization using azo group modified hollow sphere as initiator. Following, the poly(methyl methacrylate) modified hollow sphere was used as maroinitiator for surface-initiated atom transfer radical polymerization of Tb complex. The samples were characterized by Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, gel permeation chromatographer and transmission electron microscopy, respectively. The results indicated that the poly(methyl methacrylate) had grafted from hollow sphere surface and the average diameter of hollow core was about 1 μm. The optical properties of the poly(methyl methacrylate)-block-Tb copolymer modified hollow sphere were also reported.     

Controlled fabrication of theophylline imprinted polymers on multiwalled carbon nanotubes via atom transfer radical polymerization

Theophylline imprinted polymers were synthesized on the surface of multiwalled carbon nanotubes via atom transfer radical polymerization using brominated multiwalled carbon nanotubes as an initiator. The nanotube-based initiator was prepared by directly reacting acyl chloride-modified multiwalled carbon nanotubes with 2-hydroxylethyl-2'-bromoisobutyrate. The grafting copolymerization of 2-hydroxyethyl-2-methyl-2-propenoate and ethylene glycol dimethacrylate in the presence of template theophylline led to thin molecularly imprinted polymer films coating multiwalled carbon nanotubes. The thickness of molecularly imprinted polymer films prepared in this study was about 5 nm as determined by transmission electron microscopy. Fourier-transform infrared spectroscopy was utilized to follow the introduction of initiator groups as well as polymers on the carbon nanotube surfaces. Thermogravimetric analysis indicated that the molecularly imprinted polymers were successfully grown from the carbon nanotube surfaces, with the final products having a polymer weight percentage of ca. 50 wt%. The adsorption properties, such as adsorption dynamics, special binding and selective recognition capacity, of the as-prepared molecularly imprinted polymer films were evaluated. The results demonstrated that the composite of molecularly imprinted polymers and multiwalled carbon nanotubes not only possessed a rapid dynamics but also exhibited a good selectivity toward theophylline, compared to caffeine.     

Fabrication of hollow polyelectrolyte nanospheres via surface-initiated atom transfer radical polymerization

Novel polyelectrolyte-grafted core-shell organic/inorganic hybrid nanospheres which possess hard backbone of silica nanoparticles and soft shell of cross-linked poly(ionic liquids) (PILs) have been synthesized via a surface-initiated atom transfer radical polymerization (SI-ATRP). After removal of the core templates of the core-shell nanospheres, nearly monodispersed hollow polyelectrolyte nanospheres were obtained. Various characterization techniques including FT-IR, XPS, and TEM were used to characterize the resulting core-shell and hollow polyelectrolyte nanospheres. The results showed that the hollow nanosphere has a hollow core of an average diameter of ca. 200 nm with a shell thickness of ca. 25 nm. The obtained hollow polyelectrolyte nanospheres could be applied in release-control systems.     

原子转移自由基聚合用于聚砜膜的疏水改性研究

利用原子转移自由基聚合(ATRP)方法,将疏水单体2,2,2-三氟乙基甲基丙烯酸酯(TFEMA)接枝到氯甲基化聚砜(CMPSF)材料上,得到不同反应时间的接枝共聚物PSF-g-PTFEMA,并用FT-IR、19F-NMR对产物的结构进行了表征。最后,采用涂覆法对PSF膜表面进行改性,通过测定涂覆后的膜表面静态水接触角,考察了接枝产物对膜的疏水性能的影响。     

乙基纤维素接枝偶氮苯聚合物的合成与研究

通过原子转移自由基聚合(ATRP)技术合成乙基纤维素接枝偶氮苯聚合物.以功能化乙基纤维素作为大分子引发剂,在CuBr/N,N,N′,N″,N″-五甲基二亚乙基三胺(PMDETA)催化体系下,以苯甲醚为溶剂,引发对甲氧基偶氮苯单体6-[4-(4-甲氧基苯基偶氮)酚氧基]己基甲基丙烯酸酯(MMAzo)的ATRP反应,构筑接枝共聚物.通过多种手段接枝共聚物结构、热行为与液晶性进行表征.接枝共聚物在紫外-可见光照射下发生可逆的顺反异构化反应,具有作为光学材料的潜力.     

Preparation of polymer nanocomposites of core-shell structure via surface-initiated atom transfer radical polymerizations

Polymer nanocomposites of core-shell structure were prepared by grafting poly(tert-butyl acrylate) (Pt-BA) from SiO₂ nanoparticle via the surface-initiated polymerization (SIP) strategy. This new organic inorganic hybrid particle has been extensively characterized by XPS (X-ray Photoelectron Spectroscopy), SEM (Scanning Electron Microscopy), TEM (Transmission Electron Microscopy), and TGA (ThermoGravimetric Analysis).     

原子转移自由基聚合与高分子膜亲水化/功能化构造

原子转移自由基聚合(ATRP)对膜的亲水化/功能化改性包括对膜基体材料的共聚改性和对膜的表面改性.膜基体材料的改性最多见于PVDF为主链的两亲性聚合物.ATRP对膜的表面改性尤其是膜的表面引发方法,可实现将不同功能性单体接枝到聚合物膜表面,得到了抗污染能力强,生物相容性好,开关响应迅速等多种功能性表面层.直接的表面引发改性是一种高效,灵活的表面修饰/功能化方法,也是目前应用最广泛的改性技术.     

电子转移活化再生催化剂原子转移自由基聚合(ARGET ATRP)的研究进展

ARGET ATRP可将反应中催化剂用量降至ppm级,是目前最具工业化应用前景的原子转移自由基聚合(ATRP)之一。综述了ARGET ATRP的反应机理、引发剂、催化体系、还原剂、反应条件及其在污水处理、纤维素改性、燃料电池方面的应用,并对ARGET ATRP技术的前景进行了展望。     

Self-assembly of well-defined polyacrylamide-polystyrene copolymer on fibrillar clays via ultrasonic-assisted surface-initiated atom transfer radical polymerization

Well-defined polyacrylamide-polystyrene copolymers were grafted from the fibrillar clay, attapulgite, by a four-step self-assembly process: (i) the gamma-aminopropyltriethoxyl silane was self-assembled onto the surfaces of the attapulgite; (ii) the surface amino groups were amidated with bromoacetylbromide; (iii) the bromo-acetamide modified attapulgite was used as macro-initiator for the surface-initiated atom transfer radical polymerization of styrene with the catalyst of the complex of 1,10-phenanthroline and Cu(I)Br; (iv) the polystyrene grafted attapulgite was then used as macroinitiator for the polymerization of acrylamide. The two steps of the surface-initiated atom transfer radical polymerizations were all conducted under ultrasonic irradiation at room temperature. The product, polyacrylamide-polystyrene copolymers grafted attapulgite, had been characterized with elemental analysis, Fourier transform infrared spectroscopy, Thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy.     

Poly(n-isopropylacrylamide)-based hydrogel coatings on magnetite nanoparticles via atom transfer radical polymerization

Core magnetite (Fe(3)O(4)) nanoparticles have been functionalized with a model intelligent hydrogel system based on the temperature responsive polymer poly(n-isopropyl acrylamide) (PNIPAAm) to obtain magnetically responsive core-shell nanocomposites. Fe(3)O(4) nanoparticles were obtained from a one-pot co-precipitation method which provided either oleic acid (hydrophobic) or citric acid (hydrophilic) coated nanoparticles. Subsequent ligand exchange of these coatings with various bromine alkyl halides and a bromo silane provided initiating sites for functionalization with NIPAAm using atom transfer radical polymerization (ATRP). The bromine alkyl halides that were used were 2-bromo-2-methyl propionic acid (BMPA) and 2-bromopropionyl bromide (BPB). The bromo silane that was used was 3-bromopropyl trimethoxysilane (BPTS). The intelligent polymeric shell consists of NIPAAm crosslinked with poly(ethylene glycol) 400 dimethacrylate (PEG400DMA). Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) were used to confirm the presence of the polymeric shell. Dynamic light scattering (DLS) was used to characterize the nanocomposites for particle size changes with temperature. Their magnetic and temperature responsiveness show great promise for further biomedical applications. This platform for functionalizing magnetic nanoparticles with intelligent hydrogels promises to impact a wide range of medical and biological applications of magnetic nanoparticles.