两亲接枝共聚物PECA-g-PEG胶束的CMC及表面带电性

两亲接枝共聚物PECA-g-PEG胶束的CMC及表面带电性;两亲共聚物;聚氰基丙烯酸乙酯-g-聚乙二醇;临界胶束浓度;聚沉     

Structure and Percolation of Inverted Cylindrical Branched Micelles

There have been strong indications that lecithin with trace amounts of water in isooctane forms branched cylindrical micelles at relatively high water content. At a certain volume fraction these micelles percolate to form a connected network. Here this phenomenon is studied by viscometry and dielectric spectroscopy as a function of volume fraction and temperature. The observed percolation threshold is used to estimate the mean length between, and the size of, branch points. There is however a discrepancy with the theoretical model which can be explained by a water content dependent ratio of branch points and end-caps. It is argued that this is related to the water induced change from dynamic to static percolation, indicated by the observed scaling exponents. From the temperature dependence of the phase boundary the free energy of a branch point is estimated. As a function of the water content branch point formation changes from driven entirely by enthalpy towards more entropically driven.     

SDS和CTAB水溶中胶束扩散系数及第一、第二CMC测定

在无探针条件下用循环伏安法测定了不同形状SDS和CTAB胶束的扩散系数，进而得到第一CMC和第二CMC（SDS：第一CMC和第二CMC分别为8．0×10－3和5．6×10－2mol·L-1;CTAB：第一CMC和第二CMC分别为8．9×10－4和2．1×10－2mol·L－1）．此法为表面活性剂体系物理化学性质的研究，特别是为第二CMC测定提供了一个新的研究方法．     

Nanoparticle‐Loaded Cylindrical Micelles from Nanopore Extrusion of Block Copolymer Spherical Micelles

Hybrid cylindrical micelles loaded with nanoparticles are fabricated via extrusion of spherical micelles in solution phase through small long cylindrical pores. Small gold nanoparticles (AuNPs) are pre‐coated with thiol‐terminated polystyrene and then further encapsulated in the core part of block copolymer spherical micelles by a precipitation method. By varying the starting mass ratio of AuNPs and the diblock copolymers polystyrene‐b‐polyisoprene (PS‐b‐PI) during the encapsulation, the AuNPs loading density along the cylindrical micelles can be controlled. The mechanism for this sphere‐to‐cylinder transition induced by extruding hybrid spherical micelles through small cylindrical nanopores is discussed. These findings provide a novel way to manufacture high‐quality and functional polymeric nano­wires, which may open the door to new applications such as in plasmonic waveguides.

     

Cylindrical and Branched Micelles at Low Temperature: A Rheological Study

We investigate the consequence of decreasing the temperature on the rheological behavior of the cylindrical and branched micelles of the ternary system of DDAB (dodecyldimethylammonium bromide)/STDC (sodium taurodeoxycholate)/water system. An isotropic cylindrical micelle-to-hexagonal liquid crystalline phase is optically (as a birefringence) and rheologically (gel like) detected on the STDC rich part at 6°C. On the other hand, branched micellar solution does not show any birefringence upon decreasing the temperature; however, it mainly exhibits disordered-ordered transition under shear. Such transition is more pronounced as the DDAB concentration increases as a consequence of the decrease in the curvature, and hence a sponge phase formation at low temperature.     

On the kinetics of styrene emulsion polymerization above CMC. I. A mathematical model

A detailed mathematical model of the kinetics of styrene emulsion polymerization has been proposed. Its main features/assumptions are compartmentalization, micellar and homogeneous nucleation, particle formation by both initiator‐derived and desorbed radicals, dependence on the particle size of the rate coefficients, thermodynamic considerations, and aqueous phase kinetics. The model predicts that micellar nucleation dominates over homogeneous nucleation and that the evolution of the nucleation rate reaches a maximum, where desorbed radicals have an important contribution. Initiator‐derived radicals with only one monomeric unit have also a significant contribution on the rate of capture in particles. The results suggest that the correctness of the instantaneous termination approach depends not only on the size of the particle, but also on the type of entering radical (initiator‐derived or monomeric). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2201–2218, 2000     

Influence of Monomer and Initiator Concentrations on the Simultaneous Grafting of Several Monomers onto Insoluble Collagen

Simultaneous grafting of 2-hydroxyethyl methacrylate and methyl methacrylate (3:1 and 3:2 mole ratios) onto insoluble collagen with ceric ammonium nitrate as initiator was attempted with a view to optimizing conditions for the preparation of hydrogels. The influence of monomer and initiator concentrations on the grafting reactions was investigated. The grafting results are discussed in the light of grafting efficiency and percentage of grafting. They were found to be lower when the 3:1 mole ratio of monomers was used.     

Styrene Emulsion Polymerization above the CMC: New Evidence on Particle Nucleation by means of AFFFF

Summary: The number (N) and size distribution of particles (PSD) of a styrene emulsion polymerization above the CMC were studied by means of asymmetric flow‐field flow fractionation (AF⁴). Bimodal PSDs were obtained, suggesting that coagulation of the primary particles is not as extensive as would be expected, according to the coagulative mechanism. AF⁴ allowed it to be demonstrated that N is constant during interval II, and that the resolution limit of other particle sizing techniques can lead to erroneous mechanistic inferences, from the evolution of N.

Particle size distribution measured at low conversion for the emulsion polymerization of styrene, obtained by AF⁴ and DLS. The initial surfactant (S₀), initiator (I₀) and monomer (M₀) concentrations are indicated in the figure.     

Micellization Phenomena in Semicrystalline Block Copolymers: Reflexive and Critical Views on the Formation of Cylindrical Micelles

Investigations on the self‐assembly of block copolymers in solution have in some way a less well‐studied history than the study of their phase separation in the solid state, and many aspects are yet not completely understood. Here we focus on the behavior of a specific class of copolymers, namely semicrystalline block copolymers, capable of forming cylindrical aggregates in a solvent selective for the non‐crystalline, complementary block. A common model of micellization is proposed, in principle applicable to most of these copolymeric systems.

     

The Aggregation Work and Shape of Molecular Aggregates upon the Transition from Spherical to Globular and Cylindrical Micelles

The transition from spherical to globular and cylindrical equilibrium modifications of micelles in solutions of nonionic surfactants is numerically studied within the framework of the droplet model of molecular aggregates. Two branches of the curve of micelle aggregation work are plotted as a function of aggregation numbers. One of these curves corresponds to the globular micelles; the other, to spherocylindrical micelles. At aggregation numbers corresponding to the limiting spherical packing, both the globules and spherocylinders are transformed into the limiting sphere. It is shown that the ratio between the branches depends on the dimensionless parameter characterizing the ratio of electrostatic and surface contributions to the aggregation work. It is elucidated that, at certain values of this parameter and surfactant monomer concentration in solution, in addition to the maximum in the region of submicellar aggregates for spherical micelles, the second maximum arises on the curve of aggregation work as a function of aggregation numbers in the region of transition to spherocylindrical micelles. The appearance of an additional maximum is shown to be caused by the sum of surface, electrostatic, and concentration contributions to the aggregation work and is not directly related to the conformational contribution to the aggregation work.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 3, 2005, pp. 363–376.Original Russian Text Copyright © 2005 by Kshevetskiy, Shchekin.     

Effect of Interfacial Alcohol Concentrations on Oil Solubilization by Sodium Dodecyl Sulfate Micelles

Alcohol partitioning and its effect on oil solubilization in Winsor Type I microemulsion systems was investigated. The microemulsion systems consisted of sodium dodecyl sulfate (SDS), pentanol, isopropanol (IPA), and dodecane, with either deionized water or an aqueous solution of 50 mM CaCl(2). Alcohol partitioning between aqueous, oil, and interfacial phases of the microemulsion was described using a pseudophase model in which the alcohol was assumed to self-associate in the oil phase. Partitioning in these miroemulsions was consistent with pentanol self-association in the oil phase. IPA did not self-associate but co-associated with pentanol in the oil phase. IPA concentrations as high as 20 g/kg of water had no effect on pentanol partitioning. The partition coefficient for pentanol between aqueous and interfacial phases was about 220 on a mole fraction basis. However, pentanol saturated the interfacial phase at a mole ratio of 3 : 1 pentanol to SDS. Addition of pentanol beyond that sufficient to saturate the interface resulted in large amounts of pentanol partitioning into the oil, reaching concentrations in excess of 25 g dL(-1) of oil phase. Dodecane solubilization increased linearly with pentanol mole fraction in the interface up to the 3 : 1 pentanol-to-SDS saturation level. The fact that dodecane solubilization was unaffected by pentanol at concentrations beyond those necessary for interfacial saturation suggests that pentanol behaves as a cosurfactant and not a cosolvent in these microemulsion systems. Copyright 2000 Academic Press.     

On the evolution of the rate of polymerization,number and size distribution of particles in styrene emulsion polymerization above CMC

This work is an extension of a communication reported by two of the authors [Carro and Herrera‐Ordoñez, Macromol Rapid Commun 2006, 27, 274], where bimodal particle size distributions (PSD), obtained by asymmetric flow‐field flow fractionation (AFFF, AF⁴), were taken as evidence of certain degree of stability of primary particles. Now, emulsion polymerizations of styrene were performed under conditions employed before by other researchers, intending to examine if the behavior observed is general. The number of particles (N) and PSD were studied by means of dynamic light scattering and AF⁴. By the later, bimodal PSDs were detected in all cases, where the population corresponding to primary particles (diameter <20 nm) depends on reaction conditions. Regarding N, AF⁴ results show that it is constant during interval II, in contrast to DLS results. Primary particle coagulation was evidenced as minimums in N evolution and the rate of polymerization curves, monitored by calorimetry and gravimetry, which are enhanced when higher particle number is generated and/or the ionic strength is increased. These results suggest that particle coagulation is not as extensive as it would be expected according to the coagulative theory. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3152–3160, 2010     

Hierarchical Assembly of Peptoid‐Based Cylindrical Micelles Exhibiting Efficient Resonance Energy Transfer in Aqueous Solution

Herein we show that by appending bulky β‐cyclodextrin (CD) groups onto sheet‐forming peptoids, we obtain cylindrical micelles that further assembly into membranes and intertwined ribbons on substrates in aqueous solution, depending on the choice of solution and substrate conditions. In situ atomic force microscopy (AFM) shows that micelle assembly occurs in two steps, starting with “precursor” particles that transform into worm‐like micelles, which extend and coalesce to form the higher order structures with a rate and a degree of cooperativity dependent on pH and Ca²⁺ concentration. After co‐assembly with hydrophobic 4‐(2‐hydroxyethylamino)‐7‐nitro‐2,1,3‐benzoxadiazole (NBD) donors that occupy the hydrophobic core, followed by exposure to hydrophilic Rhodamine B as acceptors that insert into cyclodextrin, the micelles exhibit highly efficient Förster resonance energy transfer efficiency in aqueous solution, thereby mimicking natural light harvesting systems.     

Conductive,Monodisperse Polyaniline Nanofibers of Controlled Length Using Well‐Defined Cylindrical Block Copolymer Micelles as Templates

Stable colloidal dispersions of polyaniline (PAni) nanofibers with controlled lengths from about 200 nm–1.1 μm and narrow length distributions (L_w/L_n<1.04; L_w=weight average micelle length, L_n=number average micelle length) were prepared through the template‐directed synthesis of PAni using monodisperse, solution‐self‐assembled, cylindrical, block copolymer micelles as nanoscale templates. These micelles were prepared through a crystallization‐driven living self‐assembly method from a poly(ferrocenyldimethylsilane)‐b‐poly(2‐vinylpyridine) block copolymer (PFS₂₅‐b‐P2VP₄₂₅). This material was initially self‐assembled in iPrOH to form cylindrical micelles with a crystalline PFS core and a P2VP corona and lengths of up to several micrometers. Sonication of this sample then yielded short cylinders with average lengths of 90 nm and a broad length distribution (L_w/L_n=1.32). Cylindrical micelles of PFS₂₅‐b‐P2VP₄₂₅ with controlled lengths and narrow length distributions (L_w/L_n<1.04) were subsequently prepared using thermal treatment at specific temperatures between 83.5 and 92.0 °C using a 1D self‐seeding process. These samples were then employed in the template‐directed synthesis of PAni nanofibers through a two‐step procedure, where the micellar template was initially stabilised by deposition of an oligoaniline coating followed by addition of a polymeric acid dopant, resulting in PAni nanofibers in the emeraldine salt (ES) state. The ES–PAni nanofibers were shown to be conductive by scanning conductance microscopy, whereas the precursor PFS₂₅‐b‐P2VP₄₂₅ micelle templates were found to be dielectric in character.     

Controllable One-Step Assembly of Uniform Liquid Crystalline Block Copolymer Cylindrical Micelles by a Tailored Nucleation-Growth Process and Their Application as Tougheners

The fabrication of uniform cylindrical nanoobjects from soft materials has attracted tremendous research attention from both fundamental research and practical application points of view but has also posed outstanding challenges in terms of their preparation. Herein, we report a one-step method to assemble cylindrical micelles (CMs) with highly controllable lengths from a single liquid crystalline block copolymer by an in situ nucleation-growth strategy. By adjusting the assembly conditions, the lengths of the CMs are controlled from hundreds of nanometers to micrometers. Several influencing factors are systematically investigated to comprehensively understand the process. Particularly, the solvent quality is found determinative in either enhancing or suppressing the nucleation process to produce shorter and longer CMs, respectively. Taking advantage of this strategy, the lengths of CMs can be nicely controlled over a wide concentration range of four orders of magnitude. Lastly, CMs are produced on decent scales and applied as additives to dramatically toughen glassy plastic matrix, revealing an unprecedented length-dependent toughening effect.     

Copolymerization of Tri-n-butyltin Acrylate and Tri-n-butyltin Methacrylate Monomers with Vinyl Monomers Containing Functional Groups

A new approach to obtaining thermoset organotin polymers, which permits control of crosslinking site distribution and, through it, a better control of properties of organotin antifouling polymers, is reported. Tri-n-butyltin acrylate and tri-n-butyltin methacrylate monomers were prepared and copolymerized, by the solution polymerization method with the use of free-radical initiators, with several vinyl monomers containing either an epoxy or a hydroxyl functional group. The reactivity ratios were determined for six pairs of monomers by using the analytical YBR method to solve the differential form of the copolymer equation. For copolymerization of tri-n-butyltin acrylate (M₁) with glycidyl acrylate (M₂), these reactivity ratios were n = 0.295 ± 0.053, r₂ = 1.409 ± 0.103; with glycidyl methacrylate (M₂) they were r₁ = 0.344 ± 0.201, r₂ = 4.290 ± 0.273; and with N-methylolacrylamide (M₂) they were r₁ = 0.977 ± 0.087, r₂ = 1.258 ± 0.038. Similarly, for the copolymerization of tri-n-butyltin methacrylate (Mi) with glycidyl aery late (M₂) these reactivity ratios were r₁ = 1.356 ± 0.157, r₂ = 0.367 ± 0.086; with glycidyl methacrylate (M₂) they were r₁ = 0.754 ± 0.128, r₂ = 0.794 ± 0.135; and with N-methylolacrylamide (M₂) they were r₁ ?4.230 ± 0.658, r₂ = 0.381 ± 0.074. Even though the magnitude of error in determination of reactivity ratios was small, it was not found possible to assign consistent Q,e values to either of the organotin monomers for all of its copolymerizations. Therefore, Q,e values were obtained by averaging all Q,e values found for the particular monomer, and these were Q = 0.852, e = 0.197 for the tri-n-butyltin methacrylate monomer; and Q = 0.235, e = 0.401 for the tri-n-butyltin acrylate monomer. Since the reactivity ratios indicate the distribution of the units of a particular monomer in the polymer chain, the measured values are discussed in relation to the selection of a suitable copolymer which, when cross-linked with appropriate crosslinking agents through functional groups, would give thermoset organotin coatings with an optimal balance of mechanical and antifouling properties.     

三官能度甲基丙烯酰氧基单体的合成与性能研究

用甲基丙烯酰氯分别与二乙醇胺和三乙醇胺反应合成了两种三官能度甲基丙烯酰氧基单体.以实时红外光谱(RT-IR)法研究了两种单体的光聚合动力学性质,考察了不同单体、不同引发剂和引发剂浓度、不同光强对聚合性能的影响,并采用动态力学分析仪(DMA)测试了光固化后材料的力学性能.结果表明,随着引发剂浓度的增大,单体转化率、最大反应速率都增大,随着光强的增大,单体转化率、最大反应速率都降低.与二苯甲酮(BP)相比,2-羟基-2-甲基-1-苯基丙酮(1173)对两种单体具有较好的引发效果.两种单体加入三缩四乙二醇双甲基丙烯酸酯(SR209)中后,对体系光固化后的产物力学性能有不同影响.     

Safety and Quality Aspects of Acrylic Monomers

Summary : Acrylic monomers are important intermediates for the chemical industry. Especially acrylic acid (AA) is the basis for various reactions, such as polymerizations and esterifications and is, therefore, responsible for high product diversity. Spontaneous polymerization is a safety problem during the transportation and storage of acrylic monomers. In the production process, polymerization leads to blockages in the apparatus. For the prevention of these issues, special stabilizer systems are used such as hydroquinone monomethyl ether (MeHQ)/oxygen and phenothiazine (PTZ). The reactions of these stabilizer systems are not well understood at the moment. Therefore a lot of expertise and experience are necessary to guarantee safe handling. In this paper some methods for the investigation of stability related reaction kinetics are presented. A better comprehension of the mechanism of the polymerization inhibition is generated by the kinetic simulation with these data.