VISCOSITY BEHAVIOR OF PS/TOLUENE SOLUTION IN DILUTE AND EXTREMELY DILUTE CONCENTRATION REGION

1.INTRODUCTIONAsearlyas1950sitwasfoundthatsolutionviscosityofasinglepolymerinextremelydiluteconcentrationregionusuallyrevealssomeabnormalities,i.e.,thereducedviscosityconcentration(hsp/c~c)curvesdeviatefromlinearrelationshippredictedasHugginsequationandshoweitheranupwardoradownwardturnasconcentrationisverylow[1].Evenifforthe[()-0.2()]identicalPMMA/toluenesolution,therearetwocontraryresults:onereportedthecurvebendsupward[2],whiletheotherfounditdownward[3].Inordertointerpretthisabnormalphe…     

Associated inter‐ and intrachain conformational transitions in polystyrene solutions

Understanding the conformational changes of polymeric chains in solutions is an essential and integral part of polymer physics. By increasing the concentration of polymer solutions from dilute to semidilute regime, the critical chain overlapping has been reported at the concentration termed as C*. In this study, the associated inter‐ and intrachain conformational transitions in polystyrene (PS) solutions are reported. By comparing the spectroscopic intensity ratio versus concentration for an intrachain PS system, a break point was observed in good solvent which coincided with the theoretically predicted C*. Moreover, the intrachain conformation showed no obvious change below C*, while significant collapse started to occur above C*. This result reveals a new insight in polymer physics, since traditionally the size of polymer chains is considered to decrease weakly regarding the concentration change in the semidilute regime. It is important to find such an abrupt intrachain conformational transition between the dilute and semidilute solutions and provide the first experimental observation that inter‐ and intrachain conformational transitions are correlated to one the other. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1373–1379     

Free energy and dimensions of macromolecules under confinement in layered assemblies

The changes in the free energy ΔA accompanying penetration of polymer solutions from bulk into slit-like cavities were determined by lattice simulations. In dilute solutions the thermodynamics of penetration is controlled mainly by the parameter ϵ_w specifying interaction between polymer and walls of repulsive or adsorptive cavities. However, the magnitude of |ΔA| is substantially reduced by increasing concentration ∅︁ in bulk solution. Furthermore, compression of chains by concentration in good solvents and adsorptive cavities was found to be larger in the slit then in the bulk. At intermediate confinement, a region of a minimum coil size was observed at all concentrations and attraction strengths, where molecules are squeezed along all three axes.     

VISCOSITY BEHAVIOR OF PS／TOLUENE SOLUTION IN DILUTE AND EXTREMELY DILUTE CONCENTRATION REGION

The influences of both the volume of PS/toluene solution in the Ubbelohde viscometer and the precision of the time measuring on the viscosity behavior in dilute and extremely dilute concentration region are investigated. It was found that the influence of the former can neglect, but that of the latter is so prominent that the data fluctuate bitterly and linearity of the curve of the reduced viscosity vs. concentration (ηsp/c-c) becomes too bad to obey the Huggins equation down to the extremely dilute region, despite the error of the flow times Δt≤0.2s, which is permitted by the conventional method of viscosity measurement. Through strict mathematical analyses, it was found that the error (E) of the reduced viscosity is in proportion and inverse propor tion to Δt and concentration c, respectively. So the less the concentration, the more the error is. Consequently, a lowest concentration limit cL corresponding to given experimental error may exist and it will be meaningless for further operation below CL because of the great fluctuation of the data. Therefore, it needs to seriously reconsider the application of the conventional method of Ubbelohde viscosity measurement in the extremely dilute polymer solution under traditional conditions because of the great influence of the experimental error.     

Light-scattering studies on polystyrenes in isorefractive poly(methyl methacrylate)–toluene “solvents”

The rms radii of gyration 〈S²〉^1/2 and second virial coefficients Γ₂ of five monodisperse polystyrenes (M × 10^?5 = 1.6, 2.8, 4.2, 6.6) were measured in isorefractive toluene–poly(methyl methacrylate) (M?_v = 4.0 × 10⁴, 1.6 × 10⁵, and 6.3 × 10⁵) “solvents.” For a given PMMA, the concentration at which the θ condition (defined by Γ₂ = 0) was reached was independent of PS molecular weight, but varied inversely with PMMA molecular weight (0.10, 0.056, and 0.023 g/mL, respectively). When this θ condition is reached by adding PMMA to toluene, the radii of gyration are decreased by only about 15%, much less than when it is reached by going to a poor, low-molecular-weight solvent. This reflects the exclusion of PMMA from the PS coils, the internal environment of which is essentially pure toluene.     

Modulating catalytic activity of polymer‐based cuAAC “click” reactions

The copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction is used to synthesize complex polymer architectures. In this work, we demonstrate the control of this reaction at 25 °C between polystyrene (PSTY) chains through modulating the catalytic activity by varying the combinations of copper source (i.e., Cu(I)Br or copper wire), ligand (PMDETA and/or triazole ligand), and solvent (toluene or DMF). The fastest rate of CuAAC was found using Cu(I)Br/PMDETA ligand in toluene, reaching near full conversion after 15 min at 25 °C. For the same catalysts system, DMF also gave fast rates of “click” (95% conversion in 25 min). Cu(0) wire in toluene gave a conversion of 98% after 600 min, a much higher rate than that observed for the same catalyst system used in DMF. When the PSTY had a chemically bound triazole ring close to the site of reaction, the rate of CuAAC in toluene increased significantly, 97% in 180 min at 25 °C, in agreement with our previously published results. This suggests that rapid rates can be obtained using copper wire and will have direct applications to the synthesis of compound where air, removal of copper, and reuse of the copper catalyst are required. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

部分水解聚丙烯酰胺柠檬酸铝体系临界交联浓度的研究

采用落球粘度计、核孔膜过滤、动态光散射 (DLS)和2 7Al NMR法 ,研究了高分子量、低浓度的部分水解聚丙烯酰胺 (HPAM)与柠檬酸铝 (AlCit)体系形成交联聚合物溶液 (LPS)的临界交联浓度 .研究结果表明 ,HPAM AlCit体系在聚合物浓度较低时 ,溶液中主要发生形成交联聚合物线团 (LPC)的交联反应 ,此时形成的是LPS ,聚合物浓度增加到某一临界值后 ,体系中形成线团后 ,存在线团间的交联 ,此时形成的是弱凝胶 .不同方法所测得的HPAM AlCit体系的临界交联浓度基本相同 ,对于粘均相对分子质量为 1 4× 10 7的HPAM ,在NaCl浓度为 2 0 0 0mg L ,交联比 2 0∶1时形成的交联体系 ,其临界交联浓度在 2 0 0～ 30 0mg L间 .     

Solvent diffusion in amorphous polymers: Polystyrene–solvent systems

The inverse gas chromatography (IGC) technique was used to obtain the partition and diffusion coefficients of solvents in polystyrene over a wide range of temperatures. Infinite dilution experiments were performed with three solvents: toluene, benzene, and hexane. Finite concentration data were measured for the polystyrene–toluene system at various concentrations from 110 to 180 °C. For the finite concentration region, the modified capillary column model used by Tihminlioglu and Danner (J Chromatogr A 1999, 845, 93–101) was used to calculate diffusion and thermodynamic data. Finite concentration thermodynamic data were also calculated with the retention theory approach and compared with the capillary column model. The experimental IGC results are in good agreement with data from other experimental techniques. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1965–1974, 2000     

Synthesis,characterization, and self‐assembly of ion‐bonded A2B rod‐coil copolymer with oligo(para‐phenyleneethynylene) as rod segment

Supramolecular A₂B rod‐coil copolymer, composed of two polystyrene (PSt) arms and one oligo(para‐phenyleneethynylene) (OPE) arm linked via ionic bond, has been designed and successfully synthesized. First, a trifunctional initiator, methyl 1,3‐bis(bromomethyl)benzonate, was prepared and used to initiate the polymerization of styrene under atom transfer radical polymerization (ATRP) condition to provide polystyrene (PSt) carrying monoester group at the middle of polymer chain. Then, the ester group was transferred into tertiary amino group to give amino‐functionalized PSt, (PSt)₂? N(CH₃)₂. Subsequently, the ion‐bonded rod‐coil copolymer, (PSt)₂? OPE, was obtained by the reaction of (PSt)₂? N(CH₃)₂ with carboxy‐terminated OPE (OPE? COOH). The resulting copolymer was characterized by nuclear magnetic resonance (NMR), Fourier transformer infrared (FTIR), and gel permeation chromatography (GPC) techniques. Vesicles and spherical micelles were generated from this supramolecular rod‐coil copolymer through the manipulation of the initial polymer concentration in toluene. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7667–7676, 2008     

Formation of nanofibers in Poly(9,9‐dioctylfluorene) toluene solutions during aging

We report the formation of β‐phase nanofibers of poly(9,9‐dioctylfluorene) (PF8) in aged toluene solution at low temperature and link their photophysical properties and rheological behaviors with the solution structures. By cooling the PF8 toluene solution and subsequently aging, the PF8 chains develop into nanofiber morphology and the effects of aging time, temperature, and solution concentration on the nanofiber formation are investigated. The formation and development process of PF8 β‐phase in aged solution captured by TEM has not been reported in previous studies. Further increasing the solution concentration leads to the gelation of PF8 after aging at low temperature. It is interesting to show that a scaling law correlating specific viscosity with the polymer concentration and intrinsic viscosity originally proposed for flexible polymer solutions also exists for this semiflexible PF8 polymer solution. This study may offer an effective way to improve the understanding of the formation mechanism of PF8 β‐phase and facilitate the ongoing exploration of using such nanofiber networks in electronic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 633–639     

A “plug and play” polymer through biocomplementary hydrogen bonding

This article describes a DNA‐like polymer that exhibits the ability to self‐assemble through hydrogen bonding. We synthesized poly[1‐(4‐vinylbenzyl)thymine] (PVBT) and 9‐hexadecyladenine (A‐C16) through an atom transfer radical polymerization (ATRP) and alkylation, respectively. Biocomplementary PVBT/A‐C16 hierarchical supramolecular complexes formed in dilute DMSO solution through nucleobase recognition, that is, hydrogen bonding interactions between the thymine (T) groups of PVBT and the adenine (A) group of A‐C16; evidence for this molecular recognition was also gained from dynamic light scattering studies. ¹H NMR titration studies in CDCl₃ showed that T–A complexes formed rapidly on the NMR time scale with high association constants (up to 534 M^?1). Moreover, FTIR spectroscopic, differential scanning calorimetry, wide‐angle X‐ray diffraction, and small‐angle X‐ray scattering analyses provided further details into the nature of the self‐assembly of these systems. In the bulk state, these complexes self‐assemble into well‐ordered lamellar structures; the changing d‐spacing distance (ranging from 4.98 to 2.32 nm) at different A‐C16 loadings reveals that the molecular structures of the PVBT/A‐C16 complexes are readily tailored. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6416–6424, 2008     

一种疏水缔合水溶性聚合物的合成及其溶液性能

粘度;抗盐性;表面活性剂;一种疏水缔合水溶性聚合物的合成及其溶液性能     

Synthesis of thermally responsive cylindrical molecular brushes via a combination of nitroxide-mediated radical polymerization and “grafting onto” strategy

Loosely grafted amphiphilic molecular brushes consisting of a hydrophobic polystyrene backbone and hydrophilic poly(ethylene glycol) monomethyl ether (MPEG) side chains, PS-MPEG, were synthesized by a novel two step method. In the first step, well-defined linear poly(p-chloromethylstyrene) PCMS with the degree of polymerization DP ≈ 200 and polydispersity index, M_w/M_n = 1.4 was prepared by bulk nitroxide (TEMPO)-mediated radical polymerization (NMP). In the second step, pendant p-chloromethyl units were coupled with activated chains of poly(ethylene glycol) monomethyl ether (MPEG) during the course of the Williamson etherification reaction. Using MPEG with M_n = 1100 g/mol over 50% repeating units on PCMS underwent nucleophilic substitution yielding a densely grafted brush with theoretical molecular weight M_n,th ≈ 123,000 g/mol. The molecular brush PS-MPEG assumed conformation of a stiff cylinder in both dilute toluene (non-selective good solvent for PS backbone and MPEG grafts) and water (selective for MPEG grafts) solutions as determined by small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS). The contour length L = 570 Å and L = 694 Å obtained by fitting the scattering data using model of Sharp-Bloomfield, Pedersen-Schurtenberger and Kholodenko worm revealed dimensions corresponding to theoretically estimated size of a single molecular brush. It was found that PS-MPEG molecular brush in dilute aqueous solutions exhibited lower critical solution temperature (LCST) in the physiological range.     

Pyrene functional poly(vinyl alcohol) by “click” chemistry

Side‐chain pyrene functional poly(vinyl alcohol) (PVA) was synthesized by using “click chemistry” strategy. First, partial tosylation of PVA with p‐toluene sulfonyl chloride were performed. The resulting PVA‐Ts polymer was then quantitatively converted into poly(vinyl alcohol)‐azide (PVA‐N₃) in the presence of NaN₃/DMF at 60 °C. Propargyl pyrene was prepared independently as a photoactive click component. Finally, azido functionalized PVA was coupled to propargyl pyrene with high efficiency by click chemistry. Incorporation of pyrene functionality in the resulting polymer was confirmed by spectral analysis. It is also shown that pyrene functionalized PVA (PVA‐Py) exhibited characteristic fluorescence properties and improved solubility in highly polar solvents such as water, DMSO, and DMF as well as less polar solvent such as THF compared with pristine PVA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1317–1326, 2009     

羧酸型接枝共聚物的合成及其络合物做化学阀

用大单体技术合成了带规整聚苯乙烯支链的聚丙烯酸接枝共聚物 .研究了各种聚合条件包括温度、时间、单体浓度、大单体分子量及大单体与小单体的投料比等对接枝效率、共聚物分子量的影响 .纯化的共聚物表现出良好的乳化性质及高吸水率 ,在稀溶液中的行为如同聚电解质 .此接枝共聚物与含规整聚氧乙烯支链的聚丙烯酸乙酯络合生成的大分子间络合物膜呈现化学阀的作用 ,水通过它的渗透速率能通过调节pH加以可逆地控制 .     

On the resistance to the interpenetration between macromolecular coils of different segment densities

Using viscometry techniques on polymer fractions, we determine the critical concentrationc ^* (separating the dilute and semi dilute solutions). The same measurements have been conducted with mixtures of these fractions (mixtures 1:1 by weight of fractions differing in molecular mass and chemical nature, or fractions differing only in molecular mass). The determined values of critical concentrationc ^* of the mixtures are higher than the values calculated based on the critical concentrations of the corresponding fractions. This deviation from the additivity rule is attributed to the resistance in the interpenetration (delay to the attainment of the homogeneous state) between macromolecular coils of different chemical nature or of the same chemical nature but of different molecular mass. Higher values of the reduced viscosities of the mixture of the fractions, compared to the values calculated using the reduced viscosities of the corresponding fractions, are observed above the critical concentrationc ^*. In this concentration region the interaction parameter between two different polymers is calculated.     

Poly(2‐hydroxyethyl methacrylate‐co‐N,O‐dimethacryloylhydroxylamine) particles by dispersion polymerization

Poly(2‐hydroxyethyl methacrylate‐co‐N,O‐dimethacryloylhydroxylamine) particles were prepared by dispersion polymerization in toluene/2‐methylpropan‐1‐ol medium using cellulose acetate butyrate and dibenzoyl peroxide (BPO) as a steric stabilizer and initiator, respectively. The particle size was reduced with decreasing solvency of the reaction medium (more nuclei were generated) because the critical chain length of the precipitated oligomers decreased with an increasing toluene content, which is a poorer solvent for the polymer than 2‐methylpropan‐1‐ol. There is an optimum initiator concentration (2 wt % BPO relative to monomers) for producing low‐polydispersity particles under given conditions. Additionally, discrete spherical particles were obtained at a low monomer concentration and/or higher polymerization temperature. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1625–1632, 2002     

Colloidal dispersions of octadecyl grafted silica spheres in toluene: a global analysis of small angle neutron scattering contrast variation and concentration dependence measurements

In this paper we report measurements of the form factor and the structure factor of a sterically stabilized colloidal dispersion consisting of silica spheres coated with octadecane in toluene by small angle neutron scattering (SANS). The phase diagram of this system shows the liquid-liquid coexistence line and also a jamming transition at higher concentrations, where the jamming line intersects the coexistence line roughly at the critical point. We have performed SANS experiments at a temperature well above the transition temperature and at various volume fractions phi, spanning from the very dilute regime (phi=0.2%) to the critical concentration (phi=16%) and the highly viscous regime (phi=39.2%). Except for the very dilute regime, we observe a structure factor S(q) in all other cases. We fitted our data over the whole concentration regime using a global fitting routine with a core-shell model for the form factor P(q), taking into account the structure factor, which we describe with the Robertus model for an adhesive polydisperse core-shell particle. At a volume fraction of phi=5% a SANS contrast variation experiment has been performed. From that the product of the volume of the shell and the amount of solvent within the corona of our core-shell particle could be determined. At the most probable shell thickness of 2.3 nm a solvent content of about 50% within the corona was found. Moreover we could conclude that the core is not interpenetrated by solvent molecules. From the contrast variation experiment followed that the structure factor at zero average contrast exhibits a strong q dependence, which is an effect of an inhomogeneous particle in combination with a size distribution.     

“One‐step” Preparation of Thiol‐Ene Clickable PEG‐Based Thermoresponsive Hyperbranched Copolymer for In Situ Crosslinking Hybrid Hydrogel

A well‐defined poly(ethylene glycol) based hyperbranched thermoresponsive copolymer with high content of acrylate vinyl groups was synthesized via a “one‐pot and one‐step” deactivation enhanced atom transfer radical polymerization approach, which provided an injectable and in situ crosslinkable system via Michael‐type thiol‐ene reaction with a thiol‐modified hyaluronan biopolymer. The hyperbranched structure, molecular weight, and percentage of vinyl content of the copolymer were characterized by gel permeation chromatography and ¹H NMR. The lower critical solution temperature of this copolymer is close to body temperature, which can result in a rapid thermal gelation at 37 °C. The scanning electron microscopy analysis of crosslinked hydrogel showed the network formation with porous structure, and 3D cell culture study demonstrated the good cell viability after the cells were embedded inside the hydrogel. This injectable and in situ crosslinking hybrid hydrogel system offers great promise as a new class of hybrid biomaterials for tissue engineering.     

A highly sensitive “test paper” for Hg2+ ions based on polyurethane membrane

Heavy metals have caused a lot of serious problems to human beings. A reusable, highly sensitive metal sensor based on polyurethane membrane, which can detect and remove Hg²⁺ ions, was prepared and tested in this work. A sensor with hydroxyl (?OH) group was grafted to polyurethane, and the heavy metal sensitive membrane was synthesized accordingly. Upon addition of Hg²⁺ ion solution to the as‐prepared membrane, the color change occurred instantly. Moreover, different colors appeared with different concentration of the Hg²⁺ ions, which could make the membrane be employed as a heavy metal “test paper”. In addition, the membrane sensor could be recycled after the interaction with Hg²⁺ ions by treating the used membrane with dilute ethylenediaminetetraacetic acid 2Na solution. This efficient and easily prepared membrane‐based sensor has a promising application in environmental science. Copyright © 2013 John Wiley & Sons, Ltd.