Facile Preparation of Crosslinked Polymeric Nanocapsules via Combination of Surface-Initiated Atom Transfer Radical Polymerization and Ultraviolet Irradiated Crosslinking Techniques

A facile approach for the preparation of crosslinked polymeric nanocapsules was developed by the combination of the surface-initiated atom transfer radical polymerization and ultraviolet irradiation crosslinking techniques. The well-defined polystyrene grafted silica nanoparticles were prepared via the SI-ATRP of styrene from functionalized silica nanoparticles. Then the grafted polystyrene chains were crosslinked with ultraviolet irradiation. The cross-linked polystyrene nanocapsules with diameter of 20–50 nm were achieved after the etching of the silica nanoparticle templates with hydrofluoric acid. The strategy developed was confirmed with Fourier transform infrared, thermogravimetric analysis, and transmission electron microscopy.     

Synthesis and characterization of polymer grafted graphene oxide sheets using a Ce(IV)/HNO3 redox system in an aqueous solution

We provide here a simple way to synthesize polymer grafted graphene oxide (GO) sheets with intercalated or exfoliated structure by using a redox system with cerium (IV) ammonium nitrate/nitric acid and GO sheets’ hydroxyl groups as the redox couple. Polystyrene, poly (methyl methacrylate) and polyacrylonitrile grafted GO sheets were synthesized in an aqueous solution by this redox-initiated free-radical polymerization strategy, and characterized with Fourier transform infrared spectroscopy, X-ray diffraction, and atomic force microscopy. We investigated the effects of temperature and redox initiator’s concentration on the grafting efficiency. It was found that when a small amount of polymer was grafted onto GO sheets, an intercalated layer structure was formed; while an exfoliated structure was formed with a large amount of polymer grafted.     

Kinetic study of styrene atom transfer radical polymerization from hydroxyl groups of graphene nanoplatelets: Heterogeneities in chains and graft densities

Confinement effect of graphene nanoplatelets on the kinetics of styrene atom transfer radical polymerization was studied by a “grafting from” reaction. Graphene oxide was modified by different amounts of (3‐aminopropyl) triethoxysilane and then alpha‐bromoisobutyryl bromide from the hydroxyl groups. Polymerization of styrene in the presence of modified graphene and free initiator, ethyl alpha‐bromoisobutyrate, was accomplished at 110°C. Then, effect of various graft densities and different graphene loadings on the heterogeneous graft and free polystyrene chains characteristics and also kinetics of polymerization was studied by gas and gel permeation chromatographies. Efficiency of grafting reactions along with the graft contents was studied by X‐ray photoelectron spectroscopy, elemental analysis, and thermogravimetric analysis. Confinement effects of graphene on the relaxation behavior of polystyrene chains and also morphology of the graphenes were studied by differential scanning calorimetry and transmission electron microscopy, respectively. POLYM. ENG. SCI., 55:1720–1732, 2015. © 2014 Society of Plastics Engineers     

Grafting polymer brushes on graphene oxide for controlling surface charge states and templated synthesis of metal nanoparticles

In this article, poly[(dimethylamino)ethyl methacrylate] (PDMAEMA) brushes were grafted onto graphene oxide (GO) sheet via noncovalent modification of pyrene terminated initiator and subsequent in situ surface‐initiated atom transfer radical polymerization (SI‐ATRP). The results of zeta‐potentials, dispersivity measurement as well as the permeability of cationic and anionic redox‐active probe molecules reveal that the as‐prepared GO/PDMAEMA composite exhibits zwitterionicity because of the presence of phenol hydroxyl, carboxyl, and amine groups and the charging state can be manipulated by controlling pH values. Furthermore, by ion exchange and in situ reduction, palladium and gold nanoparticles were successfully uploaded and the catalytic property of the uniformly distributed Pd‐Au nanoparticles on GO sheet was investigated. These results reported in this work may open primarily toward constructing a bridge among GO, charged polymer and metal nanoparticles and secondarily to represent a new strategy for uniformly depositing inorganic nanoparticles. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Modeling of “living” free‐radical polymerization processes. I. Batch,semibatch, and continuous tank reactors

A comprehensive mathematical model is developed for “living” free‐radical polymerization carried out in tank reactors and provides a tool for the study of process development and design issues. The model is validated using experimental data for nitroxide‐mediated styrene polymerization and atom transfer radical copolymerization of styrene and n‐butyl acrylate. Simulations show that the presence of reversible capping reactions between growing and dormant polymer chains should boost initiation efficiency when using free nitroxide in conjunction with conventional initiator and also increase the effectiveness of thermal initiation. A study shows the effects of the value of the capping equilibrium constant and capping reaction rate constants for both nitroxide‐mediated styrene polymerization (using alkoxyamine as polymer chain seeds) and atom transfer radical polymerization of n‐butyl acrylate (using methyl 2‐bromopropionate as chain extension seeds). Also the effect of introducing additional conventional initiator into atom transfer radical polymerization of n‐butyl acrylate is studied. It is found that the characteristics of long chain growth are determined by the fast exchange of radicals between growing and dormant polymer chains. Polymerization results in batch, semibatch, and a series of continuous tank reactors are analyzed. The simulations also show that a semibatch reactor is most flexible for the preparation of polymers with controlled architecture. For continuous tank reactors, the residence time distribution has a significant effect on the development of chain architecture. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1630–1662, 2002     

Preparation and characterization of grafting polyacrylamide from PET films by SI‐ATRP via water‐borne system

The grafted homopolymer and comb‐shaped copolymer of polyacrylamide were prepared by combining the self‐assembly of initiator and water‐borne surface‐initiated atom transfer radical polymerization (SI‐ATRP). The structures, composition, properties, and surface morphology of the modified PET films were characterized by FTIR/ATR, X‐ray photoelectron spectroscopy (XPS), contact angle measurement, and scanning electronic microscopy (SEM). The results show that the surface of PET films was covered by equable grafting polymer layer after grafted polyacrylamide (PAM). The amount of grafting polymer increased linearly with the polymerization time added. The GPC date show that the polymerization in the water‐borne medium at lower temperature (50°C) shows better “living” and control. After modified by comb‐shaped copolymer brushes, the modified PET film was completely covered with the second polymer layer (PAM) and water contact angle decreased to 13.6°. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of monodispersed and lipophilic attapulgite and polystyrene nanorods via surface‐initiated atom transfer radical polymerization

A new kind of initiator, 3‐(2‐bromo‐2‐methylacryloxy)propyltriethysiliane (MPTS‐Br), was prepared with a simply hydrobrominated commercial silane coupling agent (3‐methacryloxy‐proplytriethysilane, MPTS). It has been one‐step self‐assemble onto the surface of attapulgite (ATP) nanorods in the dispersion system, and by using this initiator‐modified nanorod (MPTS‐Br‐modified ATP nanoparticles, ATP‐MPTS‐Br) as macroinitiator for atom transfer radical polymerization (ATRP). Structurally well‐defined homopolymer polystyrene (PS) and block polymer poly(styrene‐b‐methyl methacrylate) (PS‐b‐PMMA) chains were then grown from the needle‐shaped nanorods surface to yield monodispersed nanorods composed of ATP core and thick‐coated polymer shell (ATP and PS). The graft polymerization parameters exhibited the characteristics of a controlled/”living” polymerization. The PS‐grafted ATP nanorods could be dispersed well in organic solvent with nanoscale. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface‐initiated atom transfer radical polymerization (ATRP) of styrene from silica nanoparticles under UV irradiation

Diethyldithiocarbamyl‐modified silica nanoparticles were prepared and used as macroinitiator for the surface‐initiated atom transfer radical polymerization (SI‐ATRP) of styrene under UV irradiation. Well‐defined polymer chains were grown from the nanoparticle surfaces to yield particles composed of a silica core and a well‐defined, densely grafted outer PS layer with a mass ratio of styrene to silica, or percentage grafting, of 276.3% after an UV irradiation time of 5 h. Copyright © 2004 Society of Chemical Industry     

In‐plane functionalizing graphene nanolayers with polystyrene by atom transfer radical polymerization: Grafting from hydroxyl groups

Graphene oxide (GO) was prepared from the oxidation of graphite and then it was functionalized with (3‐aminopropyl)triethoxysilane (APTES) from hydroxyl groups by a coupling reaction. Subsequently, alpha‐bromoisobutyryl bromide (BiBB) was attached to the APTES groups to yield initiator anchored graphene nanolayers (GOHBr). Then, GOHBr was used in different amounts as the precursor for atom transfer radical polymerization of styrene to evaluate the effect of graphene loading along with the graft density on the properties of final product. Successful in‐plain attachment of APTES, BiBB, and polystyrene to GO was evaluated by Fourier transform infrared spectroscopy. Graphene interlayers expansion by oxidation and functionalization processes was evaluated using X‐ray diffraction. The ordered and disordered crystal structures of carbon were evaluated by Raman spectroscopy. Morphology of graphene nanolayers was studied by scanning electron microscopy and also transmission electron microscopy. POLYM. COMPOS., 35:386–395, 2014. © 2013 Society of Plastics Engineers     

Uniform star‐polystyrene nanoparticles prepared by emulsion atom transfer radical polymerization

Pentaerythritol (PT) was converted into four‐arm initiator pentaerythritol tetrakis(2‐chloropropionyl) (PT‐Cl) via reaction with 2‐chloropropionyl chloride. Uniform (monodisperse) star‐polystyrene nanoparticles were prepared by emulsion atom transfer radical polymerization of styrene, using PT‐Cl/CuCl/bpy (bpy is 2,2′‐dipyridyl) as the initiating system. The structures of PT‐Cl and polymer were characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The morphology, size and size distribution of the star‐polystyrene nanoparticles were characterized by transmission electron microscopy, atomic force microscopy and photon correlation spectroscopy. It was found that the average diameters of star‐polystyrene nanoparticles were smaller than 100 nm (30–90 nm) and monodisperse; moreover, the particle size could be controlled by the monomer/initiator ratio and the surfactant concentration. The average hydrodynamic diameter (D_h) of the nanoparticles increased gradually on increasing the ratio of styrene to PT‐Cl and decreased on enhancing the surfactant concentration or increasing the catalyst concentration. Copyright © 2011 Society of Chemical Industry     

Graphene oxide modification with graft polymers via nitroxide mediated radical polymerization

We demonstrate a method to modify the surface of graphene oxide (GO) by grafting polymer chains using nitroxide mediated radical polymerization (NMRP). Surface modification by NMRP was achieved using GO functionalized with 2,2,6,6-tetramethyl-piperidine 1-oxyl (TEMPO, T) to produce graphene oxide-TEMPO (GO-T). GO prepared from graphite by the Hummer's method was facilely functionalized in one step with T. Graft polymerization reactions of styrene and isoprene were carried out using nitroxide chemistry to control the polymerization and the ‘grafting from the surface’ polymerization technique. GO-T acts as a multifunctional macroalkoxyamine initiating and controlling the polymerization in the presence of monomer. The grafting reactions were performed by dispersing GO-T in dimethylformamide and heating at 130 °C in the presence of monomer to form graphene oxide-g-polystyrene-TEMPO (GO-g-PS-T) and graphene oxide-g-polyisoprene-TEMPO (GO-g-PI-T). FT-IR, Raman, XPS, XRD, TGA and TEM data are consistent with the attachment of the TEMPO group to the GO surface and with polystyrene and polyisoprene being grafted onto the GO surface. The amount of PS and PI grafted to GO-T was estimated from TGA data to be approximately 34% for a 7 h reaction time and 68% for a 144 h reaction time, respectively.     

可控/活性聚合在无机粒子表面接枝研究进展

介绍了一些主要的可控／活性自由基聚合法,包括氮氧调解自由基聚合法（NMRP）、原子转移自由基聚合法（ATRP）、可逆加成断裂链转移聚合法（RAFT）在粒子表面接枝聚合形成无机纳米粒子／聚合物的壳核结构,达到了对粒子改性的目的。并提出了一些目前研究中存在的问题,对可控／活性聚合应用的发展进行了展望。     

Microencapsulated self-healing polymers via controlled,surface initiated atom transfer radical polymerization from the surface of graphene oxide

Polymers were grown directly on the surface of graphene oxide (GO). The method involved the covalent attachment of an atom transfer radical polymerization (ATRP) initiator on the surface of GO followed by the polymerization of methylmethacrylate, styrene or t-butyl acrylate using it as the macroinitiator. The surface initiated poly(methylmethacrylate) (PMMA-IGO) was embedded with microcapsules containing glycidyl methacrylate (GMA) to introduce self-healing property. The polymeric chains grown on the surface of the GO exhibited self-healing behaviour on rupture of the microcapsules. These polymer chains on the surface of GO preserved living characteristics and was able to resume copolymerization with released GMA on rupture of the microcapsules and get infiltrated into the cracks. As a result, the cracked planes were covalently re-bonded, offering almost 92% recovery of strength.     

Controlled atom transfer radical polymerization of MMA onto the surface of high-density functionalized graphene oxide

We report on the grafting of poly(methyl methacrylate) (PMMA) onto the surface of high-density functionalized graphene oxides (GO) through controlled radical polymerization (CRP). To increase the density of surface grafting, GO was first diazotized (DGO), followed by esterification with 2-bromoisobutyryl bromide, which resulted in an atom transfer radical polymerization (ATRP) initiator-functionalized DGO-Br. The functionalized DGO-Br was characterized by X-ray photoelectron spectroscopy (XPS), Raman, and XRD patterns. PMMA chains were then grafted onto the DGO-Br surface through a ‘grafting from’ technique using ATRP. Gel permeation chromatography (GPC) results revealed that polymerization of methyl methacrylate (MMA) follows CRP. Thermal studies show that the resulting graphene-PMMA nanocomposites have higher thermal stability and glass transition temperatures (T_g) than those of pristine PMMA.     

Surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) of methyl methacrylate from carbon fibre

Surface modification of carbon fibre (CF) by well‐defined polymer brushes was carried out using the ‘grafting from’ method. Poly(methyl methacrylate)‐grafted carbon fibre (CF‐PMMA) was successfully prepared by surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) of methyl methacrylate (MMA) from the macro‐initiator, bromo‐acetic ester‐modified carbon fibre (CF‐BrA), with the complex of 1,10‐phenanthroline and Cu(I)Br as catalyst. The percentage of grafting (PG%) and the conversion of monomer (C%) increased linearly with increasing of polymerization time, and reached 24.0 % and 6.7 %, respectively, after a polymerization time of 6 h, calculated from the elemental analyses (EA). The structural and surface morphological analyses were conducted with Fourier‐transform infrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Copyright © 2005 Society of Chemical Industry     

Synthesis of Polymer Grafted Magnetite Nanoparticle with the Highest Grafting Density via Controlled Radical Polymerization

Abstract  The surface-initiated ATRP of benzyl methacrylate, methyl methacrylate, and styrene from magnetite nanoparticle is investigated, without the use of sacrificial (free) initiator in solution. It is observed that the grafting density obtained is related to the polymerization kinetics, being higher for faster polymerizing monomer. The grafting density was found to be nearly 2 chains/nm² for the rapidly polymerizing benzyl methacrylate. In contrast, for the less rapidly polymerizing styrene, the grafting density was found to be nearly 0.7 chain/nm². It is hypothesized that this could be due to the relative rates of surface-initiated polymerization versus conformational mobility of polymer chains anchored by one end to the surface. An amphiphilic diblock polymer based on 2-hydroxylethyl methacrylate is synthesized from the polystyrene monolayer. The homopolymer and block copolymer grafted MNs form stable dispersions in various solvents. In order to evaluate molecular weight of the polymer that was grafted on to the surface of the nanoparticles, it was degrafted suitably and subjected to gel permeation chromatography analysis. Thermogravimetric analysis, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to confirm the grafting reaction. Graphical Abstract   Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Dendrigraft polystyrene initiated by poly(p-chloromethyl styrene): synthesis and properties

Dendrigraft polystyrene was prepared using poly(p-chloromethyl styrene) as the multicentre initiator by atom transfer radical polymerization (ATRP). The resulting polymer was characterized with light scattering, intrinsic viscosity, thermal analysis and atomic force microscopy (AFM) imaging. The AFM image showed there were two kinds of different structural dendrigraft polystyrenes in the product, ie the ‘coupling’ dendrigraft polystyrene and ‘free’ dendrigraft polystyrene. The ‘coupling’ structure might result from the coupling reaction of growing radical chain ends. The second virial coefficient A₂ and intrinsic viscosity of the dendrigraft polystyrene were smaller than those of the relative linear and twelve-arm star polystyrene, and the thermal analysis showed that the initial decomposition temperature was a little higher than that of linear polystyrene. © 1999 Society of Chemical Industry     

End-capped polystyrene with 8-hydroxyquinoline group by ATRP method

8-Hydroxyqunioline end-capped polystyrene was prepared through atom transfer free radical polymerization (ATRP) with 8-(5-chloromethyl) quinolyl acetate as initiator. The results indicated that this polymerization is a first order reaction with respect to monomer conversion. The molecular weight increased linearly with monomer consumption and very narrow distribution of molecular weight was obtained (polydispersity index less than 1.2). The FT-IR and NMR results show that the 8-hydroxyquinloine group was chemically bonded to the polymer end and there is nearly one 8-hydroxyquinoline group in per polymer chain. All those data show that polymerization of styrene at such conditions displayed living characters. The polymer with 8-hydroxyqquinoline end group reacted with triethylaluminum to form polymeric light-emitting complex and single layer LED was prepared by common spin-coating method. The peak wavelength of LED based on synthesized polymeric complex was around 570 nm.     

星状支化PS的合成与表征

利用原子转移自由基聚合方法,以α-溴代苯乙烷为引发剂,CuBr／2,2'-联二吡啶作为催化体系,合成星状支化聚苯乙烯(PS)。引发二苯甲烷双马来酰亚胺／苯乙烯电荷转移络合物体系就地优先生成多官能团引发剂,再引发苯乙烯聚合。采用核磁共振、凝胶渗透色谱、多角度激光散射和特性黏数等分析方法对聚合过程、聚合物结构、聚合物相对分子质量及其分布进行分析与表征。由多角度激光散射法测定的绝对重均分子量是由凝胶渗透色谱测定的4倍左右,相同相对分子质量的线型PS的特性黏数是星状PS的20倍,证实聚合产物确实具有支化结构。     

Synthesis of Cellulose-graft-Polychloromethylstyrene-graft-Polyacrylonitrile Terpolymer/Organoclay Bionanocomposite by Metal Catalyzed Living Radical Polymerization and Solvent Blending Method

A bionanocomposite of grafted cellulose and organo-modified clay was synthesized through solution intercalation method. For this purpose, chloromethylstyrene was grafted onto cellulose using acryloylchloride and the subsequent free radical polymerization. The synthesized cellulose-graft-polychloromethylstyrene was used as an atom transfer radical polymerization macroinitiator of acrylonitrile in the presence of CuCl/2,2′-bipyridine catalyst system, to prepare the cellulose-graft-polychloromethylstyrene-graft-polyacrylonitrile terpolymer. For preparing the modified clay, Na-montmorillonite was mixed with hexadecyl trimethyl ammonium chloride salt. Finally, cellulose-graft-polychloromethylstyrene-graft-polyacrylonitrile/organoclay bionanocomposite was prepared in CCl₄ by solution intercalation method.