Effect of associating polymer on the viscosity behavior of suspensions consisting of particles with different surface properties

Associating polymers which consist of water-soluble long-chain molecules containing a small fraction of hydrophobic groups (hydrophobes) behave as flocculants in aqueous suspensions. The effects of associating polymers on the rheological behavior are studied for single suspensions of particles with hydrophilic and hydrophobic surfaces, and their mixtures. For particles with hydrophilic surfaces, the suspensions are highly flocculated by a bridging mechanism, because the water-soluble chains adsorb onto hydrophilic surfaces. On the other hand, the particles with hydrophobic surfaces cannot be dispersed in water without polymer and the additions of a small amount of polymer are required for preparation of homogeneous suspensions. The associating polymer acts as a dispersant at low concentrations. However, further additions of polymer lead to a drastic increase in viscosity. Since the hydrophobes on one end of molecules adsorb onto hydrophobic surfaces and other hydrophobes tending from the particles can form micelles, the particles are connected by linkage of interchain associations. By mixing two suspensions of particles with hydrophilic and hydrophobic surfaces, the viscosity is substantially reduced and the flow becomes nearly Newtonian. The associating polymer in complex suspensions acts as a binder between the hydrophilic and hydrophobic surfaces. The hetero-flocculation which leads to the formation of composite particles may be responsible for the viscosity reduction of complex suspensions.     

Size effect on the rheological behavior of nanoparticle suspensions in associating polymer solutions

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups and tend to create bonds between chains by reversible associating interactions. The effects of associating polymer on the steady-shear viscosity and dynamic viscoelasticity are studied for suspensions of silica nanoparticles with diameters of 8, 18, and 25 nm. The silica particles of 8 nm are entrapped in the transient network of associating polymer by reversible adsorption. The enhancement of network results in the high viscosity with a Newtonian flow profile in the limit of zero shear rate. In suspensions of 25 nm silica, the hydrophobes extending from the chains adsorbed onto different particles can form a micelle by association interactions. The multichain bridging gave rise to the shear-thinning flow and high storage modulus at low frequencies. The suspensions of 25 nm silica are characterized as flocculated systems. Because of intermediate curvature, the flexible bridges are formed between silica particles of 18 nm. When the flexible bridges are highly extended within the lifetime in shear fields, the suspensions show shear-thickening flow. The shear-thickening flow can be attributed to the elastic effect of flexible bridges.     

Viscosity behavior of silica suspensions flocculated by associating polymers

Associating polymers are hydrophilic long-chain molecules containing a small number of hydrophobic groups, and act as flocculants in aqueous suspensions. The effects of associating and nonassociating polymers on viscosity behavior are studied for silica suspensions. Since flocculation is induced by polymer bridging, the viscosity behavior is converted from Newtonian to shear-thinning profiles. The additions of surfactant cause an increase in viscosity for suspensions prepared with associating polymer, whereas the flow behavior of suspensions with nonassociating polymer is not significantly influenced. In adsorption of associating polymers onto silica particles, the chain may adopt a conformation with a water-soluble backbone attached to the particle surfaces. The hydrophobic groups extending from the chains adsorbed onto different particles can form a micelle by association with surfactant. Therefore, the bridging flocculation is enhanced by surfactant. The cooperative micellar formation between associating polymer and surfactant is responsible for viscosity increase in suspensions.     

THE EFFECT OF POLYMER ON THE CLOUD POINT OF A SERIES OF TRIBLOCK NONIONIC SURFACTANTS IN AQUEOUS SOLUTION

A series of triblock nonionic surfactants with different Propylene oxide and ethylene oxide chain lengths were synthesized. The triblock nonionic surfactants and poly(ethylene glycols) with different molecular weight were used, to find the effects of polymer chain length and size of the micelles on the cloud point of the surfactants. Two possible models are considered on the basis of cloud point changes of the solutions, to describe the polymer- surfactant interactions. One model suggests that flocculation depletion for the polymer chains exist between two regular micelles. This provides the driving force for the neighboring micelles to approach each other and destabilize the colloidal system. The flocculation effect is more important for polymers with a shorter chain block the approach of the micelles, since there is no typical polymer-surfactant association formed but just simple small molecule associations in which the steric and solvation effects of the polymer chains make the inter-micelles interactions repulsive. The other model considers that intra-chain micelles of polysoap are formed among the surfactant monomers and long polymer chains. The bridging attraction between two intra-chain micelles in such structures can enhance the collisions among the micelles, due to the exchange of amphiphilic monomers among the neighboring micelles.     

Demixing in athermal mixtures of colloids and excluded-volume polymers from density functional theory

We study the structure and interfacial properties of model athermal mixtures of colloids and excluded volume polymers. The colloid particles are modeled as hard spheres whereas the polymer coils are modeled as chains formed from tangentially bonded hard spheres. Within the framework of the nonlocal density functional theory we study the influence of the chain length on the surface tension and the interfacial width. We find that the interfacial tension of the colloid-interacting polymer mixtures increases with the chain length and is significantly smaller than that of the ideal polymers. For certain parameters we find oscillations on the colloid-rich parts of the density profiles of both colloids and polymers with the oscillation period of the order of the colloid diameter. The interfacial width is few colloid diameters wide and also increases with the chain length. We find the interfacial width for the end segments to be larger than that for the middle segments and this effect is more pronounced for longer chains.     

获得环境响应聚合物胶束和空心球的途径

概述了本研究组近年来发展的几种制备环境敏感的聚合物纳米胶束和空心球的新方法,包括通过聚合物间的氢键相互作用构建“非共价键合胶束”的自组装方法,将聚合物自组装与单体的原位聚合相结合的方法以及利用接枝共聚物中的主链和支链间的络合作用诱导胶束化和胶束与空心球的可逆转化等.讨论了这些聚合物纳米微球和空心球对温度、pH及离子强度等的响应特性.     

Phase behavior of cationic hydroxyethyl cellulose-sodium dodecyl sulfate mixtures: effects of molecular weight and ethylene oxide side chain length of polymers

Novel cationic hydroxyethyl cellulose (HEC) polymers with different molecular weights (1.1 x 10(5) to 1.7 x 10(6) g/mol) and ethylene oxide (EO) side chain lengths (1.5-2.9 EO units) were mixed with sodium dodecyl sulfate (SDS) in aqueous solutions. The phase diagrams of cationic HEC-SDS complexes were determined in the dilute polymer concentration regime (< 0.5 wt %) with gradual addition of SDS molecules. The viscosity and structures of the complexes during the phase evolution were studied using rheometry and dynamic light scattering. The gradual addition of SDS first induced interchain associations with the bound SDS aggregates serving as cross-linkers to form an open network structure, producing a very broad size distribution and high viscosities of the complex solutions, and then condensed the network and induced a structure reorganization, resulting in globular aggregates with narrow size distributions. The growth of these globular aggregates in size eventually led to macroscopic sedimentation near charge neutralization. Further addition of SDS randomly broke the sedimentary aggregates into small particles and SDS micelles with low solution viscosities. The effects of molecular weight and EO side chain length of polymers on the phase boundary, viscosity, and structure of cationic HEC-SDS complexes were discussed.     

Thermoresponsive amphiphilic symmetrical triblock copolymers with a hydrophilic middle block made of poly(N-isopropylacrylamide): synthesis, self-organization, and hydrogel formation

Several series of symmetrical triblock copolymers were synthesized by the reversible addition fragmentation chain transfer method. They consist of a long block of poly(N-isopropylacrylamide) as hydrophilic, thermoresponsive middle block, which is end-capped by two small strongly hydrophobic blocks made from five different vinyl polymers. The association of the amphiphilic polymers was studied in dilute and concentrated aqueous solution. The polymer micelles found at low concentrations form hydrogels at high concentrations, typically above 30–35 wt.%. Hydrogel formation and the thermosensitive rheological behavior were studied exemplarily for copolymers with hydrophobic blocks of polystyrene, poly(2-ethylhexyl acrylate), and poly(n-octadecyl acrylate). All systems exhibited a cloud point around 30 °C. Heating beyond the cloud point initially favors hydrogel formation but continued heating results in macroscopic phase separation. The rheological behavior suggests that the copolymers associate into flower-like micelles, with only a small share of polymers that bridge the micelles and act as physical cross-linkers, even at high concentrations.     

核-壳结构微球的制备进展

综述了近年来核-壳结构微球制备方面的研究进展,介绍了高分子胶束交联、模板逐层组装、模板微球表面原位引发聚合、动态溶胀法、种子聚合法以及溶胶-凝胶法等主要制备方法,并对各种方法所涉及的核-壳微球形成机理进行了必要阐述.     

New approaches to stimuli-responsive polymeric micelles and hollow spheres

This article briefly describes some new approaches to stimuli-sensitive polymeric micelles and hollow spheres, which were developed in the authors’ laboratory in recent years. (1) Self-assembly of component polymers to non-covalently connected micelles (NCCM) driven by specific interactions. For example, in water, PCL and PAA formed core-shell nanospheres due to interpolymer hydrogen bonding. After crosslinking the PAA shell and removing the PCL core, “nanocages” made of PAA network were obtained. This hollow structure shows perfect reversible size-pH dependence. (2) Simultaneous in-situ polymerization of monomers and self-assembly of the polymers. In this approach, PNIPAM network was formed by radical polymerization covering PCL particles. Hollow spheres of PNIPAM network were then obtained by biodegradation of the PCL core. Both the core-shell spheres and hollow spheres show reversible size dependence on temperature change because of the phase transition of PNIPAM around 32°C. (3) Complexation-induced micellization and transition between the micelles and hollow spheres. Graft copolymers of hydroxylethyl cellulose (HEC) and PAA were prepared by free radical polymerization. The copolymers showed pH dependent micellization, i.e., micelles formed when pH of the graft copolymer solution decreased to around 3. The micellar structure could be locked by crosslinking the PAA grafts. The resultant cross-linked micelles undergo pH-dependent transition between the micelles and hollow spheres, which accompanies a remarkable particle size change. Both the micellization and the structure transition were found to be reversible and associated with H-bonding complexation between the main chain and grafts. __________ Translated from Acta Polymerica Sinica, 2005, 650(5) (in Chinese)     

Effects of added surfactants on thermoreversible gelation of associating polymer solutions

The influence of added surfactants on physical properties of associating polymer solutions was examined by a new statistical‐mechanical theory of associating polymer solutions with multiple junctions and by computer simulation. The sol–gel transition line, the spinodal line, and the number of elastically effective chains in the mixed networks were calculated as functions of the concentration of added surfactants. All of them exhibited nonmonotonic behavior as a result of the following two competing mechanisms. One was the formation of new mixed micelles by binding surfactants onto the polymer associative groups. These micelles serve as crosslink junctions and promote gelation. The other was the replacement of polymer associative groups in the already formed network junctions by added surfactants. Such replacement lowers connectivity of junctions and destroys networks. The critical micelle concentration was also calculated. The results are compared with the reported experimental data on poly(ethylene oxide)‐based associating polymers and hydrophobically modified cellulose derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 733–751, 2004     

Immobilization of RAFT agents on silica nanoparticles utilizing an alternative functional group and subsequent surface‐initiated RAFT polymerization

Silica–polystyrene core‐shell particles were successfully prepared by surface‐mediated reversible addition fragmentation chain transfer (RAFT) polymerization of styrene monomer from the surfaces of the silica‐supported RAFT agents. Initially, macro‐RAFT agents were synthesized by RAFT polymerization of γ‐methacryloxypropyltrimethoxysilane (MPS) in the presence of chain transfer agents (CTAs). Immobilization of CTAs onto the silica surfaces was then performed by reacting silica with macro‐RAFT agents via a silane coupling. Grafting of polymer onto silica forms core‐shell nanostructures and shows a sharp contrast between silica core and polymer shell in the phase composition. The thickness of grafted‐polymer shell and the diameter of core‐shell particles increase with the increasing ratio of monomer to silica. A control experiment was carried out by conventional free radical emulsion copolymerization of MPS‐grafted silica and styrene under comparable conditions. The resulting data provide further insight into the chemical composition of grafted‐polymers that are grown from the silica surface through RAFT process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 467–484, 2009     

Semiflexible grafted polymers in poor solvents: toroidal, archway, and tower micelles

We study a system of grafted semiflexible polymers in a poor solvent which form toroidal or rodlike conformations in the bulk. However, because of the physical constraint of surface grafting, macrophase separation is inhibited and a number of different polymer aggregates (or micelles) form which can be related to the chains' stiffness and their affinity for each other. In contrast to the fully flexible Gaussian case, we observe a number of novel micelle structures, including tower micelles, archway micelles, and spider micelles. We also attempt to develop a phase diagram for the occurrence of these structures with respect to the variables of chain length, chain stiffness, and polymer grafting density.     

Rheological behavior of silica suspensions in aqueous solutions of associating polymer

Associating polymers are hydrophilic long-chain molecules containing a small amount of hydrophobic groups. The aqueous solutions show viscoelastic responses above some critical concentrations because a three-dimensional structure is formed by association of hydrophobic groups. When the associating polymers are added to silica suspensions at low concentrations, the flocculation is induced by bridging mechanisms, and the flow of suspensions become shear-thinning. For suspensions prepared with polymer solutions in which the associating network is developed, the viscosity decreases, shows a minimum, and then increases with increasing particle concentration. The viscosity decrease may arise from the breakdown of associating network due to adsorption of polymer chains onto the silica surfaces. As the particle concentration is increased, the polymer concentration in solution is decreased, and finally, all polymer chains are adsorbed on the surfaces. Beyond this point, the partial coverage of particle surfaces takes place and strong interactions are generated between particles by polymer bridging. Since the stable suspensions are converted to highly flocculated systems, the viscosity is increased and the flow becomes shear-thinning. The concentration effect of silica particles on the viscosity behavior of suspensions can be explained by a combination of viscosity decrease in solution due to polymer adsorption and viscosity increase due to flocculation.     

Interactions between colloidal particles in polymer solutions: A density functional theory study

We present a density functional theory study of colloidal interactions in a concentrated polymer solution. The colloids are modeled as hard spheres and polymers are modeled as freely jointed tangent hard sphere chains. Our theoretical results for the polymer-mediated mean force between two dilute colloids are compared with recent simulation data for this model. Theory is shown to be in good agreement with simulation. We compute the colloid-colloid potential of mean force and the second virial coefficient, and analyze the behavior of these quantities as a function of the polymer solution density, the polymer chain length, and the colloid/polymer bead size ratio.     

聚苯乙烯-b-聚丙烯酸模板剂成核段长度对聚苯胺尺寸及性能的影响

以两亲性嵌段共聚物为模板是构筑导电聚合物纳米结构并对其形貌尺寸进行调控的有效方法之一。 嵌段共聚物成核段长度的变化对其胶束化行为有显著影响,进而也会改变受限于其胶束形貌的导电聚合物的形貌尺寸。 形貌尺寸的变化必然导致导电聚合物电化学性能变化。 本文欲通过嵌段共聚物模板诱导实现对聚苯胺(PANI)形貌尺寸的调控并使其电化学性能得到优化,采用可逆加成-断裂链转移自由基聚合(RAFT)法成功合成了嵌段共聚物聚苯乙烯-b-聚丙烯酸PS_x-b-PAA₇₀(x=38、64、101)并以其胶束为“模板”制备了窄相对分子质量分布的PANI。 在成核段(PS)长度较短时,模板诱导形成的棒状PANI颗粒,直径为100~200 nm。当 x=101时PANI呈现空间网状结构,其放电比容量高于其它样品,在电流密度为1 A/g时,其放电比容量可达386.71 F/g。     

pH-controlled, polymer-mediated assembly of polymer micelle nanoparticles

We describe pH-controlled, polymer-mediated assembly of polymer micelles in aqueous media based on reversible complexation between the micelles of pyrene-labeled poly(epsilon-caprolactone)-b-poly(carboxylic acid) copolymers and proton-accepting water-soluble polymers such as poly(ethylene glycol) (PEG), poly(2-ethyl-2-oxazoline) (PEtOz), and poly(1-vinylpyrrolidone) (PVP). The key factor determining assembly phenomena was identified as the modulation of hydrogen-bonding interaction between ionizable anionic micellar shells and the proton-accepting polymers by the pH control. As pH decreased from 7.4 to 2.0, the mixture of the polymer micelles and polymers underwent assembly and formed solid hybrids at specific pH values. The micelles assembled in the hybrid could be reversibly dispersed as micelles above specific pH ranges. The assembly/disassembly behavior as well as phase transitions of the micelle/proton-accepting polymer could be precisely controlled by adjusting pH. This assembling behavior depended on the rationally designed parameters such as the chemical structure and length of micellar shell-forming poly(carboxylic acid)s and the class of proton-accepting polymers.     

Structure and size of spontaneously formed aggregates in Aerosol OT/PEG mixtures: effects of polymer size and composition

Dynamic light scattering and Cryo-TEM measurements have allowed us to obtain the size and structure of spontaneous aggregates formed by mixtures of Aerosol OT, AOT, and ethylene glycol polymers of different molecular mass. The results presented in this work show that small unilamellar vesicles predominate in pure Aerosol OT solutions and in dilute polymer solutions mixed with AOT. In the latter case, elongated micelles coexist with unilamellar vesicles. When polymer concentration increases above a certain concentration, the small vesicles disappear and the size of the elongated micelles decreases to a radius compatible with spherical micelles. For PEG concentrations above the overlapping ones, spherical micelles coexist with very large aggregates probably formed by large rod like micelles or by superstructures of elongated micelles embedded in a polymer network. This behavior is consistent with theoretical models based in molecular mean-field theory [M. Rovira-Bru, D.H. Thompson, I. Szleifer, Biophys. J. 83 (2002) 2419]. The properties of the different types of aggregates are obtained by fluorescence spectroscopy and electrophoretic mobility measurements.     

Effect of polymer size and chain length on depletion interactions between two colloids

A density functional theory based on the weighted density has been developed to investigate the depletion interactions between two colloids immersed in a bath of the binary polymer mixtures, where the colloids are modeled as hard spheres and the polymers as freely jointed tangent hard-sphere chain mixtures. The theoretical calculations for the depletion forces between two colloids induced by the polymer are in good agreement with the computer simulations. The effects of polymer packing fraction, degree of polymerization, polymer/polymer size ratio, colloid/polymer size ratio on the depletion interactions, and colloid-colloid second virial coefficient B2 due to polymer-mediated interactions have been studied. With increasing the polymer packing fraction, the depletion interaction becomes more long ranged and the attractive interaction near the colloid becomes deeper. The effect of degree polymerization shows that the long chain gives a more stable dispersion for colloids rather than the short chain. The strong effective colloid-colloid attraction appears for the large colloid/polymer and polymer/polymer size ratio. The location of maximum repulsion Rmax is found to appear Rmax approximately sigmac+Rg2 for the low polymer packing fraction and this is shifted to smaller separation Rmax approximately sigmac+sigmap2 with increasing the polymer packing fraction, where sigmap2 and Rg2 are the small-particle diameter and the radius of gyration of the polymer with the small-particle diameter, respectively.     

Structure-defined c60/polymer colloids supramolecular nanocomposites in water

We report a new supramolecular method for the synthesis of well-defined pristine C 60/polymer colloid nanocomposites in water. The colloids include polymer micelles and emulsion particles. To a polymer colloid solution in water or alcohol, we introduced C 60 solution in a solvent that is miscible with water or alcohol. After the two solutions mixed, polymer colloids and C 60 spontaneously assembled into stable colloidal nanocomposites. After a dialysis process, a nanocomposite dispersion in pure water was obtained. As characterized by DLS and (Cryo-)TEM, the nanocomposites have a core-shell structure with C 60 aggregated on the surface of emulsion particles or micellar cores. The resulting nanocomposites have many potential applications such as biomedicals and photovoltaics.