Functionalization of iron oxide magnetic nanoparticles with poly(methyl methacrylate) brushes via grafting‐from atom transfer radical polymerization

A key problem with nanomaterials is the difficulty of controlling the dispersion of nanoparticles inside an organic medium. To overcome this problem, functionalization of the nanoparticle surface is required. Poly(methyl methacrylate) (PMMA) brushes were grown on the surface of iron oxide magnetic nanoparticles with atom transfer radical polymerization and a grafting‐from approach. Modified magnetic nanoparticles with a graft density of 0.1 PMMA chains/nm² were obtained. Cu(II), used as a deactivating complex, allowed good control of the polymerization along with a narrow polydispersity of the polymer chains. The functionalized magnetic nanoparticles were characterized with Fourier transform infrared spectroscopy, thermogravimetric analysis, gel permeation chromatography, and atomic force microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 925–932, 2007     

Role of adsorbed chain rigidity in reinforcement of polymer nanocomposites

The thermomechanical behavior of polymer nanocomposites is mostly governed by interfacial properties which rely on particle–polymer interactions, particle loading, and dispersion state. We recently showed that poly(methyl methacrylate) (PMMA) adsorbed nanoparticles in poly(ethylene oxide) (PEO) matrices displayed an unusual thermal stiffening response. The molecular origin of this unique stiffening behavior resulted from the enhanced PEO mobility within glassy PMMA chains adsorbed on nanoparticles. In addition, dynamic asymmetry and chemical heterogeneities existing in the interfacial layers around particles were shown to improve the reinforcement of composites as a result of good interchain mixing. Here, the role of chain rigidity in this interfacially controlled reinforcement in PEO composites is investigated. We show that particles adsorbed with less rigid polymers improve the mechanical properties of composites. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 9–14     

Infrared study of the kinetics and mechanism of adsorption of acrylic polymers on alumina surfaces

In this paper, we studied the kinetics of the adsorption of poly(methyl methacrylate), PMMA, onto native aluminum oxide surfaces by X-ray photoelectron spectroscopy and reflection-absorption infrared spectroscopy, with the intent of tracking the various changes observed in the infrared spectrum of the adsorbed polymer layer as a function of adsorption time. Specifically, we utilized the relative changes in the absorption bands of the carbonyl, carboxylic acid, and carboxylate groups to determine the sequence of events that culminate in the formation of bonds between carboxylate groups on hydrolyzed PMMA and specific sites on the aluminum oxide surface. We have shown that the adsorption process involves the hydrolysis of a fraction of the methoxy groups of the PMMA to generate COOH groups. Unlike previous assumptions, the formation of COOH groups on the PMMA chains does not constitute a sufficient condition for the actual chemisorption of the polymer chains onto the metal oxide surface. To promote bonding, the acid groups must undergo dissociation to form the carboxylate groups, followed subsequently by actual bond formation, that is, active anchoring, on the surface. This process is mediated by the aluminum oxide sites on the surface in the presence of water. Hence, the adsorption process occurs via a two-step mechanism, in which the first step, that is, the hydrolysis step, is a necessary but insufficient condition and the second step, that is, the anchoring step, is largely dependent on the type of interfacial chemistry possible for a particular polymer-metal oxide surface, the polymer conformation, the molecular weight, and the flexibility of the adsorbing molecules.     

Mass spectroscopy and SEC of SRM 1487, a low molecular weight poly(methyl methacrylate) standard

Matrix Assisted Laser Desorption Ionization (MALDI) Time of Flight (TOF) Mass Spectrometry (MS) was used to study the molecular weight distribution (MWD) and the number of α-methyl styrene (α-MeSty) repeat units in SRM 1487, a narrow MWD poly(methyl methacrylate) (PMMA) standard reference material of about 6300 g/mol, which was initiated with α-MeSty. It was found that each PMMA polymer chain had from zero to seven α-MeStys per chain. The MWD of the polymer chains containing a fixed number of α-MeStys was obtained. The MWD, M_w, and the average number of α-MeSty at a given molecular weight from MALDI TOF MS compare well with those obtained from more traditional methods such as ultracentrifugation and Size Exclusion Chromatography (SEC). The implications of the number of α-MeStys per chain is discussed in terms of the chemistry of anionic polymerization. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2409–2419, 1997     

Study of the Second Order Transitions and Acid-Base Properties of Polymers Adsorbed on Oxides by Using Inverse Gas Chromatography at Infinite Dilution

In Part I, we gave the details concerning inverse gas chromatography (IGC) at infinite dilution and the methods and models that will be used to characterize solid substrates. This technique proved to be an excellent technique to determine not only the glass transitions, but also beta-transition and liquid-liquid transitions of polymers adsorbed on solid substrates. In this second part, we used the IGC technique to determine the second order transitions of the systems' polymethyl methacrylate (PMMA)/SiO(2) and PMMA/Al(2)O(3), at various covered surface fractions and for various tacticities of the polymer. The maxima of the dispersive component of the surface energy gamma(s)(d) of our two systems, obtained by IGC at infinite dilution, indicated clearly the presence of transition temperatures (glass or local transitions). In general, we observed with PMMA three principal maxima that reflect the changes in motions leading to reorganization and rearrangement of the various groups or chain segments of the polymer. The change in the retention mechanism of the probes at the transition temperatures is attributed to an increased molecular mobility of the polymer segments, allowing for the penetration of the probes into the polymer layer. The study of the chemical physical properties of PMMA/SiO(2) and PMMA/Al(2)O(3) revealed an important difference in the acidic and basic behavior, in Lewis terms, of oxide covered by various concentrations of PMMA. This study also highlighted an important effect of the tacticity of the polymer on the acidic basic character of PMMA adsorbed on oxides. Copyright 2001 Academic Press.     

Surface properties of bottle-brush polyelectrolytes on mica: effects of side chain and charge densities

Surface properties of a series of cationic bottle-brush polyelectrolytes with 45-unit-long poly(ethylene oxide) side chains were investigated by phase modulated ellipsometry and surface force measurements. The evaluation of the adsorbed mass of polymer on mica by means of ellipsometry is complex due to the transparency of mica and its birefringence and low dielectric constant. We therefore employed a new method to overcome these difficulties. The charge and the poly(ethylene oxide) side chain density of the bottle-brush polymers were varied from zero charge density and one side chain per segment to one charge per segment and no side chains, thus spanning the realm from a neutral bottle-brush polymer, via a partly charged brush polyelectrolyte, to a linear fully charged polyelectrolyte. The adsorption properties depend crucially on the polymer architecture. A minimum charge density of the polymer is required to facilitate adsorption to the oppositely charged surface. The maximum adsorbed amount and the maximum side chain density at the surface are obtained for the polymer with 50% charged segments and the remaining 50% of the segments carrying poly(ethylene oxide) side chains. It is found that brushlike layers are formed when 25-50% of the segments carry poly(ethylene oxide) side chains. In this paper, we argue that the repulsion between the side chains results in an adsorbed layer that is non-homogeneous on the molecular level. As a result, not all side chains will contribute equally to the steric repulsion but some will be stretched along the surface rather than perpendicular to it. By comparison with linear polyelectrolytes, it will be shown that the presence of the side chains counteracts adsorption. This is due to the entropic penalty of confining the side chains to the surface region.     

Effect of nanoparticles on the thermal stability of PMMA nanocomposites prepared by in situ bulk polymerization

Al₂O₃ and ZnO filled poly(methyl methacrylate) nanocomposites were synthesized by free radical (bulk) polymerization. Efficient dispersion was achieved by predispersing the nanoparticles in propylene glycol methyl ether acetate (PGMEA) followed by ultrasonication of nanoparticles into the PMMA syrup. Thermal analysis confirms chemisorption between PGMEA and metal oxide particles. The addition of nanoparticle affects degradation mechanism and consequently improves thermal stability of PMMA. The reduction of polymer chain mobility and the tendency of nanoparticles to eliminate free radicals are the principal effects responsible for these enhancements.     

Synthesis and characterization of silver—poly(methylmethacrylate) nanocomposites

The optical properties of silver nanoparticles embedded in poly(methylmethacrylate) (PMMA) was investigated as well as the influence of silver nanoparticles on the thermal properties of polymer matrix. The average size and particle size distribution of silver nanoparticles was determined using transmission electron microscopy. The obtained transparent nanocomposite films were optically characterized using UV-Vis and FTIR spectroscopy. Thermal stability of polymer matrix was improved upon incorporation of small amount of silver nanoparticles. Also, silver nanoparticles have pronounced effect on thermo-oxidative stability of PMMA matrix. The glass transition temperatures of nanocomposites are lower compared to the pure polymer.     

Preparation and properties of polymer/zinc oxide nanocomposites using functionalized zinc oxide quantum dots

Poly(methyl methacrylate) (PMMA)/zinc oxide (ZnO) or carbazole polymer (PCEM)/ZnO nanocomposites, which are composed of high molecular weight PMMA or PCEM with narrow molecular weight distributions and ZnO nanoparticles, were successfully prepared by atom transfer radical polymerization (ATRP) initiated by 2-bromo-2-methylpropionyl (BMP) group (ZnBM) introduced onto the ZnO nanoparticle surfaces. Introduction of the BMP group onto the ZnO surfaces was achieved by esterification of OH group of the ZnO surfaces. The chemically attached OH group-having ZnO nanoparticles (ZnHM) were fabricated by sol-gel reaction from zinc acetate dihydrate, followed by treatment of the ZnO nanoparticles with 2-hydroxypropionic acid (HPA). The ZnHM nanoparticles showed one UV absorption and two emission bands: UV emission peak and broad visible emission band, while the ZnBM exhibited broad UV absorption and no emission spectra. The PMMA/ZnO nanocomposites displayed UV absorption and photoluminescent (PL) band with blue emission on the basis of the ZnHM nanoparticles, where the ZnO nanoparticles dispersed homogeneously in the PMMA matrix. The PCEM/ZnO nanocomposites depicted UV emission peak due to the carbazole unit in the UV range, but no visible emission. Thermal properties of the PMMA/ZnO nanocomposites were improved by dispersion of the ZnO nanoparticles into the PMMA, but the PCEM/ZnO nanocomposites showed no improvement of the thermal properties.     

Facile control of surface wettability in TiO2/poly(methyl methacrylate) composite films

A facile method to produce very hydrophobic surface was developed simply using the mixture of TiO(2) nanoparticles and poly(methyl methacrylate) (PMMA). When the volume ratio of TiO(2) to PMMA is between 35 vol.% and 50 vol.%, the mixture of two hydrophilic materials became very hydrophobic. Analysis of the molecular structure by infrared spectroscopy shows that the preferential orientation and attachment of a carbonyl group of a polymer molecule to the surface of TiO(2) nanoparticles play a critical role in the appearance of the strong hydrophobicity. When this composite was exposed to UV light, PMMA on the surface of the mixture film was decomposed through a photocatalytic reaction and the very hydrophobic surface turned to the superhydrophilic one. The superhydrophilic property of UV-irradiated composite lasts as long as several months. This long lasting superhydrophilicity is ascribed to the porous structure, which provides high roughness and strong capillary interaction. Easy transition from strong hydrophobicity to superhydrophilicity in TiO(2)/PMMA composites could be applied to designing high contrast hydrophilic/hydrophobic patterns.     

具有温度响应壳层的金纳米粒子的制备

利用可逆-加成断裂链转移聚合得到全亲水性的嵌段共聚物(PEO-b-PNIPAM), 通过"grafting to"使其接枝到金纳米粒子表面. 通过透射电子显微镜、 紫外-可见吸收光谱、 能谱分析及动态光散射研究了杂化的金纳米粒子的壳层结构及温度响应行为. 实验结果表明, 得到核壳结构的金纳米粒子, 同时其壳层具有温度响应行为. 随着温度的升高, 其流体力学半径略有减小. 在整个升温过程中, 由于外层PEO链段的抑制作用, 没有发生粒子间的聚集.     

Hydrophilic magnetic polymer latexes. 1. Adsorption of magnetic iron oxide nanoparticles onto various cationic latexes

With a view to preparing monosized hydrophilic functional magnetic latex particles based on a two-step strategy using anionic iron oxide and cationic polymer latexes, the adsorption step was systematically investigated for a better control of the subsequent encapsulation step. The iron oxide nanoparticles were first obtained according to the classical precipitation method of ferric and ferrous chloride salt using a concentrated sodium hydroxide solution, whereas the polystyrene (PS), P(S/N-isopropylacrylamide (NIPAM)) core–shell and PNIPAM latexes were produced via emulsion and precipitation polymerizations, respectively. The polymer and inorganic colloids were then characterised. The adsorption of iron oxide nanoparticles onto the three types of polymer latexes via electrostatic interaction was studied as a function of iron oxide particle concentration, charge density and the cross-linking density of the hydrophilic layer. The maximum amounts of magnetic nanoparticles adsorbed onto the various latexes were found to increase in the following order: PS < P(S/NIPAM) < P(NIPAM). This significant difference is discussed by taking into account the charge distribution in the hydrogel layer and diffusion phenomena inside the cross-linked hydrophilic shell. Received: 28 December 1998 Accepted in revised form: 15 April 1999     

卟啉铝催化下二氧化碳与氧化环己烯共聚反应研究

利用四苯基卟啉氯化铝(TPPAlCl)与双三苯基膦氯化铵(PPNCl)组成的二元催化剂催化二氧化碳与氧化环己烯共聚合,80℃下反应9h,二氧化碳-氧化环己烯共聚物(PCHC)的收率为97.2％,分子量分布窄(Mw/Mn=1.12),但数均分子量仅为6.8×103.研究发现溶剂的浓度和极性变化对聚合过程中的链转移反应影响...     

Synthesis of well‐defined polymer brushes on the surface of zinc antimonate nanoparticles through surface‐initiated atom transfer radical polymerization

Zinc antimonate nanoparticles consisting of antimony and zinc oxide were surface modified in a methanol solvent medium using triethoxysilane‐based atom transfer radical polymerization (ATRP) initiating group (i.e.,) 6‐(2‐bromo‐2‐methyl) propionyloxy hexyl triethoxysilane. Successful grafting of ATRP initiator on the surface of nanoparticles was confirmed by thermogravimetric analysis that shows a significant weight loss at around 250–410 °C. Grafting of ATRP initiator onto the surface was further corroborated using Fourier transform Infrared spectroscopy (FT‐IR) and X‐ray photoelectron spectroscopy (XPS). The surface‐initiated ATRP of methyl methacrylate (MMA) mediated by a copper complex was carried out with the initiator‐fixed zinc antimonate nanoparticles in the presence of a sacrificial (free) initiator. The polymerization was preceded in a living manner in all examined cases; producing nanoparticles coated with well defined poly(methyl methacrylate) (PMMA) brushes with molecular weight in the range of 35–48K. Furthermore, PMMA‐grafted zinc antimonate nanoparticles were characterized using Thermogravimetric analysis (TGA) that exhibit significant weight loss in the temperature range of 300–410 °C confirming the formation of polymer brushes on the surface with the graft density as high as 0.26–0.27 chains/nm². The improvement in the dispersibility of PMMA‐grafted zinc antimonate nanoparticles was verified using ultraviolet‐visible spectroscopy and transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

A combinatorial approach to study solvent-induced self-assembly of mixed poly(methyl methacrylate)/polystyrene brushes on planar silica substrates: effect of relative grafting density

This article reports the study of the effect of relative grafting densities of two polymer chains on solvent-induced self-assembly of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes through a combinatorial approach. Gradient-mixed PMMA/PS brushes were synthesized from a gradient-mixed initiator-terminated monolayer by combining atom transfer radical polymerization (ATRP) and nitroxide mediated radical polymerization (NMRP) in a two-step process. The gradient-mixed initiator-terminated monolayer was fabricated by first formation of a gradient in density of an ATRP initiator through vapor diffusion followed by backfilling of an NMRP-initiator-terminated trichlorosilane. After treatment of a gradient-mixed brush whose PS Mn was slightly lower than that of PMMA with glacial acetic acid, a selective solvent for PMMA, relatively ordered nanodomains were observed in the region where the ratio of PS to PMMA grafting density (number of polymer chains/nm2) was in the range from 0.67 to 2.17 and the overall grafting density was approximately 0.85 polymer chains/nm2. Contact angle hysteresis were high (> or =40 degrees ) in this region and XPS studies confirmed that the PMMA chains were enriched at the outermost layer. The nanodomains are speculated to be of a micellar structure with PS chains forming the core shielded by PMMA chains.     

Poly(methyl methacrylate) composites prepared by in situ polymerization using organophillic nano-to-submicrometer zinc oxide particles

Nano- and submicrometer zinc(II) oxide particles were synthesized by the polyol method and were used for the preparation of ZnO/poly(methyl methacrylate) (ZnO/PMMA) composite materials by the chain polymerization of methyl methacrylate (MMA) in bulk. ZnO particles with an organophilic surface layer were homogeneously dispersed in the PMMA matrix. Very low concentrations (0.1 wt.%) of nano zinc oxide absorbed over 98% of UV light as determined by UV-vis spectroscopy. Nano zinc oxide (75 nm) increased the initial decomposition temperature of the PMMA matrix by 30-40 °C at concentrations of 0.1% and above. This was explained by the changes in the termination mechanism of MMA polymerization resulting in a reduced concentration of vinylidene chain ends. Nano ZnO also increased the MMA polymerization reaction rate and reduced the activation energy. Submicrometer ZnO showed lower UV absorption, thermal stabilization and no influence on the reaction kinetics indicating that average particle size is of vital importance for the properties of PMMA nanocomposites and for MMA polymerization.     

Segmental orientations of trains versus loops and tails: the adsorbed polymethylmethacrylate system when the surface coverage is incomplete

We measure, for the first time, the separate surface coverage-dependent orientations of trains and of loops/tails in the structure of an adsorbed polymer, and show that these have different average orientations. The system was PMMA (atactic polymethylmethacrylate) adsorbed onto oxidized silicon from dilute solution in carbon tetrachloride at 25.0°C. The method was FTIR-ATR (infrared spectroscopy in attenuated total reflection). With increasing surface coverage, train segments were observed to maintain constant average anisotropy with respect to the solid surface. Free segments were preferentially flattened when the surface coverage was low, but with increasing surface coverage became progressively more random in orientation. Free and bound segments were separated according to shifts of the vibrational frequencies of carbonyl segments upon hydrogen-bonding to the surface silanol groups. The dependence of segmental orientation on molecular weight of the chain is also discussed.     

Correlation of infinite dilution activity coefficients of solvents in polymer solutions using connectivity indices

In this work, correlations for the estimation of the infinite dilution activity coefficients of non-polar solvents in polystyrene (PS), poly(vinyl acetate) (PVAc), poly(n-butyl methacrylate) (PBMA), poly(dimethyl siloxane), poly(methyl methacrylate) (PMMA), poly(ethylene oxide) (PEO), poly(vinyl chloride) (PVC), polyisobutylene and polyethylene (PE), and that of polar solvents in PS, PVAc, PBMA, PMMA, PEO, PVC and PE are proposed. A total of 205 polymer/non-polar solvent systems with 1708 data points, and 118 polymer/polar solvent systems with 695 data points were used to develop the correlations. The overall average errors were 9.6% and 11.3%, respectively, significantly lower than other predictive models. Since the new correlations require only the connectivity indices of the solvents in the calculations, and the connectivity indices can be calculated easily once the molecular structure of the substance in question is known, they are easy to apply, and are useful for process design and development.     

Synthesis of block copolymer-stabilized Au-Ag alloy nanoparticles and fabrication of poly(methyl methacrylate)/Au-Ag nanocomposite film

[Poly(2-(N,N-dimethylamino)ethyl methacrylate)]-b-poly(methyl methacrylate)-b-[poly(2-(N,N-dimethylamino)ethyl methacrylate)] (M(n)=45,000; 20K-5K-20K; PDI = 1.2) block copolymer surfactant stabilized amphiphilic gold-silver alloy nanoparticles (Au-Ag(PDMA-b-PMMA-b-PDMA)) has been synthesized in both water and in organic medium. The block copolymer stabilized pre-made alloy nanoparticles were successfully dispersed in hydrophobic poly(methyl methacrylate) homopolymer matrix (PMMA) of molecular weight 30,000. The successful synthesis of alloy nanoparticles was accessed by Transmission Electron Microscope (TEM), Energy Dispersed X-ray (EDX), and UV-visible spectrophotometric analysis. The surface functionality of the nanoparticles was confirmed by quantitative determining the grafting density of polymer chain around the nanoparticle surface using combination of thermo gravimetric (TGA) and TEM analysis. The hydrodynamic diameter of the alloy particles including the polymer chains was obtained from dynamic light scattering measurement (DLS). The mechanism of synthesis of high concentration of Au-Ag alloy particles from HAuCl(4) and AgNO(3) (in presence of Cl(-) from reduction of gold salt) metal particles precursors and the successful preparation of poly(methyl methacrylate)/gold-silver nanocomposite films have been discussed.