Rheological properties of multisticker associative polyelectrolytes in semidilute aqueous solutions

Multisticker associative polyelectrolytes of acrylamide (≈86 mol %) and sodium 2‐acrylamido‐2‐methylpropanesulfonate (≈12 mol %), hydrophobically modified with N,N‐dihexylacrylamide groups (≈2 mol %), were prepared with a micellar radical polymerization technique. This process led to multiblock polymers in which the length of the hydrophobic blocks could be controlled through variations in the surfactant‐to‐hydrophobe molar ratio, that is, the number of hydrophobes per micelle (N_H). The rheological behavior of aqueous solutions of polymers with the same molecular weight and the same composition but with two different hydrophobic block lengths (N_H = 7 or 3 monomer units per block) was investigated as a function of the polymer concentration with steady‐flow, creep, and oscillatory experiments. The critical concentration at the onset of the viscosity enhancement decreased as the length of the hydrophobic segments in the polymers increased. Also, an increase in the N_H value significantly enhanced the thickening ability of the polymers and affected the structure of the transient network. In the semidilute unentangled regime, the behavior of the polymer with long hydrophobic segments (N_H = 7) was studied in detail. The results were well explained by the sticky Rouse theory of associative polymer dynamics. Finally, the viscosity decreased with an increase in the temperature, mainly because of a lowering of the sample relaxation time. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1640–1655, 2004     

Investigating the effect of hydrophobic structural parameters on the thickening properties of HEUR associative copolymers

Hydrophobically modified ethoxylated urethanes (HEUR) associative copolymers are prepared through the hydrophobic modification of polyethylene glycol based polyurethanes. These types of thickeners are categorized as anionic associative thickeners. To investigate the effect of structure of the hydrophobic groups on the thickening properties, three different hydrophobic groups were selected. These groups were comprised of cetyl alcohol (16 carbons), dodecyl alcohol (12 carbons) and a cyclic group such as cyclo hexanol. These functional groups were substituted on the identical prepolymers made from H₁₂MDI and polyethylene glycol. Here, three different urethane associative polymers containing hydrophobic segments and different hydrophobic groups were synthesized. The viscoelastic characteristics of all the samples were determined using a cone and plate rheometer. The viscosities of the examined HEUR samples showed both Newtonian and non-Newtonian behaviours (shear thinning and thickening) for the explored shear rates window. The steady shear viscosity results were interpreted using the theories by Raspaud [Macromolecules 27 (1994) 2956] and Semenov [Macromolecules 28 (1995) 1066]. The Cox-Merz rule happened to be applicable to these systems for the various hydrophobic ends and concentrations at lower shear rates indicating typical associative polymer behaviour. The cyclic end groups did not show viscoelasticity for the frequencies window explored. The zero shear viscosity increased by almost two orders of magnitude from HEUR-cyc to HEUR-dod and by four orders of magnitude from HEUR-cyc to HEUR-cet. The intermediate shear thickening was only observed for the concentrated HEUR-cet samples.     

Insight into shear‐induced modification for improving processability of polymers: Effect of shear rate on the evolution of entanglement state

Many experimental results have revealed that the re‐entanglement kinetics of disentangled polymers is much slower than that predicted by tube theory. This retarded recovery of fully entangled state is of practical significance that shear‐induced modification may offer a way to improve processability for a polymer by reducing viscosity. This work tried to figure out the shear‐rate dependence variation of viscosity in the view of evolution of entanglement state through disentanglement and re‐entanglement, aiming to provide fundamental insights into application prospect of shear‐induced modification in preparing “in‐pellet” disentangled polymers prior to final processing. High‐density polyethylene was sheared on a parallel‐plate rotational rheometer with a linearly increased shear rate. Results showed that higher shear rate could induce further disentanglement, resulting in a lower viscosity with a reduction rate up to 93.7%, larger molecular weight between entanglements M_e , and longer re‐entanglement time. Additionally, less entanglement would give a larger lamellar thickness of sheared samples after nonisothermal crystallization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 598–606     

Influence of Surfactant and Charged Monomer Concentrations on Micro-Block Length of Associative Polymers by Micellar Polymerization

In the micellar polymerization to prepare associative polyelectrolyte, the influence of solution environment on hydrophobical micro-block length has been investigated. The results revealed that the aggregation number (N_agg) of surfactant micelles and micro-block length (N_H) of polymers closely related to electrolyte concentration in polymerization solution, and all of the surfactant and charged monomer concentration can change the free counterion concentration (C_aq) to affect N_agg and N_H. Therefore, the N_H with traditional calculation method which N_agg is looked as constant value was not accurate enough. Subsequently, we studied the attribution of N_H to rheological properties. The results indicated that the micro-block length can increase obviously the reversible network strength in solution to make a few contribution of thickening properties of associative polymer.     

Experimental investigation toward obtaining a new correlation for viscosity of WO3 and Al2O3 nanoparticles-loaded nanofluid within aqueous and non-aqueous basefluids

In this study, the effect of temperature and mass fraction of Al₂O₃ and WO₃ nanoparticles dispersed in deionized water and liquid paraffin was investigated on dynamic viscosity of nanofluid. The results of the TEM tests showed that the size of Al₂O₃ and WO₃ nanoparticles was ranged from 10 to 60 nm, and the results showed that nanoparticles were semi-spherical. Also the results of DLS and zeta potential tests, respectively, exhibited the uniform size and high stability of the nanoparticles in the basefluid environment. The findings showed that adding a certain amount of nanoparticles to water and liquid paraffin increases dynamic viscosity, and in the case of various shear rates, the viscosity is constant for the water-based nanofluids, which indicates the Newtonian behavior of the nanofluid. In addition, for those prepared by liquid paraffin as a basefluid, the viscosity does not remain constant at different shear rates and at low amount of shear rate the viscosity achieves higher value, indicating non-Newtonian behavior of liquid paraffin-based nanofluids. The results showed that by increasing the temperature in liquid paraffin-based nanofluid the uniformity and linearity of the viscosity curve at various shear rates could be observed, which represents an approach for Newtonian behavior of nanofluid at higher temperatures. These results also showed that with increasing the mass fraction of nanoparticles in water and liquid paraffin, the viscosity increases at different shear rates. Finally, the correlation presented in this study shows that for nanofluid viscosity as a function of nanoparticles load and temperature, the deviation of correlated data from experimental values is less than 10%.

     

Nanometrization of Lanthanide‐Based Coordination Polymers

Heteronuclear lanthanide‐based coordination polymers are microcrystalline powders, the luminescence properties of which can be precisely tuned by judicious choice of the rare‐earth ions. In this study, we demonstrate that such materials can also be obtained as stable solutions of nanoparticles in non‐toxic polyols. Bulk powders of the formula [Ln_2?2xLn′_2x(bdc)₃ ? 4 H₂O]_∞ (where H₂bdc denotes 1,4‐benzene‐dicarboxylic acid, 0≤x≤1, and Ln and Ln′ denote lanthanide ions of the series La to Tm plus Y) afford nanoparticles that have been characterized by dynamic light‐scattering (DLS) and transmission electron microscopy (TEM) measurements. Their luminescence properties are similar to those of the bulk materials. Stabilities versus time and versus dilution with another solvent have been studied. This study has revealed that it is possible to tune the size of the nanoparticles. This process offers a reliable means of synthesizing suspensions of nanoparticles with tunable luminescence properties and tunable size distributions in a green solvent (glycerol). The process is also extendable to other coordination polymers and other solvents (ethylene glycol, for example). It constitutes a new route for the facile solubilization of lanthanide‐based coordination polymers.     

New dendronized polymers from acrylate Behera amine and their ability to produce visco-elastic structured fluids when mixed with CTAT worm-like micelles

Two new water soluble dendronized polymers (PLn) from acrylate Behera amine monomer of different molecular weights were successfully synthesized. The polymers were characterized by FTIR, NMR, GPC and DLS. Both GPC and DLS results indicated that these PLn have a remarkable tendency to form aggregates in solution that lead to apparent molecular weights that are much higher than their theoretical values, as well as large diameters in solution. However, the addition of any PLn to water did not cause any increase in viscosity up to concentrations of 1000 ppm. The possible interactions of PLn with the cationic surfactant CTAT were explored by solution rheometry. A synergistic viscosity enhancement was found by adding small amounts of dendronized PLn polymers to a CTAT solution composed of entangled worm-like micelles. The highest association tendency with CTAT was found for PL1 at the maximum polymer concentration before phase separation (i.e., 100 ppm). The solution viscosity at low-shear rates could be increased by an order of magnitude upon addition of 100 ppm of PL1 to a 20mM CTAT solution. For this mixture, the fluid obtained was highly structured and exhibited only shear thinning behavior from the smallest shear rates employed. These PL1/CTAT mixtures exhibited an improved elastic character (as determined by dynamic rheometry) that translated in a much longer value of the cross-over relaxation time and a pronounced thixotropic behavior which are indicative of a strong intermolecular interaction. In the case of the polymer with a higher theoretical molecular weight, PL2, its association with CTAT leads to an extraordinary doubling of solution viscosity with just 0.25 ppm polymer addition to a 20mM CTAT solution. However, such synergistic viscosity enhancement saturated at rather low concentrations (25 ppm) indicating an apparent lower solubility as compared to PL1, a fact that may be related to its higher molecular weight.     

Hydrophobically modified polyelectrolytes I. Dilute solution properties of fluorocarbon-containing poly (acrylic acid)

Dilute solution viscosity of fluorocarbon‐containing hydrophobically modified poly (acrylic add) was measured in aqueous solutions of various NaCl concentrations. The intrinsic viscosity ([η]) and Huggins coefficient (k_H) were evaluated using Huggins equations. It is found that, at low Nacl concentration, the modified polymers exhibit values of intrinsic viscosity ([η]) and Huggins coefficient (k_H) similar to those of unmodified polymers. For both of the modified and unmodified polymers, the intrinsic viscosity decreases with increase of NaCl concentration, while the Huggins coefficient increases upon addition of NaCl. But the variation of [η] and k_H is more significant for the modified polymers, which reflects the enhanced intra‐ and intermolecular hydrophobic association at higher Nacl concentration.     

Interactions between surfactant-coated surfaces in hydrocarbon liquids containing functionalized polymer dispersant

The forces and viscosity between calcium benzene sulfonate surfactant-coated mica surfaces in various hydrocarbon liquids containing a polyamine-functionalized hydrocarbon polymer (M _W≈8000) have been measured using the surface forces apparatus technique. The polymer is found to adsorb to the substrate surfaces by displacing the surfactant layer, and to produce forces that are monotonically repulsive. The forces have a maximum range of 50–100 nm (>3R _H), indicating that tails play a particularly important role in the interaction of this relatively low molecular weight polymer. The forces become steeply repulsive below about 10 nm (∼0.6R _H), at which point a “hard-wall” repulsion comes in that can sustain pressures greater than 100 atm. Thin-film viscosity measurements indicate that the far-field positions of the slipping planes Δ_H depend on the shear rate, showing that significant shear thinning/thickening effects occur within the outermost tail regions of the adsorbed layers during shear. The position of the slipping plane, or hydrodynamic layer thickness Δ_H, varies from 0.6R _H to 2R _H away from each surface (mica and surfactant-coated mica surfaces). Beyond the hydrodynamic layer the far-field fluid viscosity is the same as that of the bulk polymer solution. At separations below D = 2Δ_H the viscosity increases as each polymer layer is compressed. The static forces exhibited various time- and history-dependent effects, which further indicate that a number of different relaxation/equilibration processes are operating simultaneously in this complex multicomponent system. The results reveal that the interactions of tails of functionally adsorbed polymers play a more important role than previously thought. This is especially true in this study where the adsorbed polymers are of low molecular weight and where the tails may represent the largest fraction of interacting segments. Received: 22 September 1998 Accepted: 11 January 1999     

Synthesis and characterization of hydrophobically modified polyacrylamides and some observations on rheological properties

Hydrophobically modified polyacrylamide (PAM) polymers were synthesized by means of an aqueous micellar copolymerization, the di-alkyl substituted acrylamides di-n-propylacrylamide (DPAM) and di-n-octylacrylamide (DOAM) being used as hydrophobic comonomers. The number of hydrophobic blocks was varied using three different comonomer contents (f=1, 3 and 5 wt.%). The length of hydrophobic blocks, i.e. the number of hydrophobes per micelle, N_H, was controlled by the sodium dodecyl sulphate surfactant concentration. The effect of the type of hydrophobic comonomer and the number and length of hydrophobic units on the composition of the copolymer and its solubility and rheological properties were studied. The results indicate that the average copolymer composition is independent of the degree of conversion and surfactant concentration. Solubility and rheological measurements lead to a number of conclusions. First, DPAM is a weak hydrophobic monomer, all DPAM/AM (AM=acrylamide) copolymers being water soluble. Second, there is no strong hydrophobic interaction between DPAM units, in particular for low polymer concentration and N_H, and thus no strong associative thickening behaviour. Third, DOAM is a strong hydrophobic comonomer. Incorporation of a small amount of DOAM into PAM causes a dramatic enhancement in viscosity due to hydrophobic interactions. The properties of the copolymers are strongly dependent on the N_H values, most DOAM/AM copolymers being insoluble in water.     

Rheology of chlorosulphonated polyethylene solutions

The viscosity behaviour of chlorosulphonated polyethylene was studied as a function of shear rate, concentration and temperature in three aromatic solvents viz. benzene, toluene and xylene. The Carreau model was used to correlate the data. The time constant t₁ arising from the Carreau model was compared with the Bueche time constant λ_H; there appears to be good agreement between them especially at lower temperatures and higher concentrations. A unified curve based on plots of η/η_O vs γλ_H correlated the data successfully. The temperaure dependence of the zero shear viscosity was studied. The apparent activation energy for viscous flow was linearly related to the polymer concentration.     

Gas transport properties of poly(ether‐b‐amide) segmented block copolymers

The permeation properties of H₂, N₂, and CO₂ were determined at 35 °C and pressures up to 15 atm in phase‐separated polyether‐b‐polyamide segmented block copolymers. These polymers contain poly(ethylene oxide) [PEO] or poly(tetramethylene oxide) [PTMEO] as the rubbery polyether phase and nylon‐6 [PA6] or nylon‐12 [PA12] as the hard polyamide phase. Extremely high values of polar (or quadrupolar)/nonpolar gas selectivities, coupled with high CO₂ permeability coefficients, were observed. CO₂/H₂ selectivities as high as 9.8 and CO₂/N₂ selectivities as high as 56 were obtained in polymers with CO₂ permeability coefficients of approximately 220 × 10⁻¹⁰ cm³(STP) cm/(cm² s cmHg). As the amount of polyether increases, permeability increases. Gas permeability is higher in polymers with less polar constituents, PTMEO and PA12, than in those containing the more polar PEO and PA6 units. CO₂/N₂ and CO₂/H₂ selectivities are higher in polymers with higher concentrations of polar groups. These high selectivity values derive from large solubility selectivities in favor of CO₂. Because CO₂ is larger than H₂ and has, therefore, a lower diffusion coefficient than H₂, the weak size‐sieving ability of the rubbery polyether phase, which is the locus of most of the gas permeation, also contributes to high CO₂/H₂ selectivity. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2051–2062, 2000     

Salt influence in the polymer-surfactant interaction in solution. A fluorescence probe investigation of the EHEC/SDS/ water system

 The effect of small amounts of salt on the interaction between two fractions of ethyl(hydroxy)ethyl cellulose, EHEC, and sodium dodecyl sulfate, SDS, has been investigated by means of steady-state fluorescence measurements. The two polymer fractions display different properties in hydrophobicity expressed as different cloud points. The results are discussed in relation to hydrodynamic (viscosity) and thermodynamic (equilibrium dialysis) properties. The micropolarity as sensed by the probe pyrene shows that the polymers begin to interact with SDS at a lower concentration in the presence of salt. The average aggregation numbers of polymer-bound clusters, N _p, were obtained by fluorescence-quenching data in combination with equilibrium dialysis experiments. N _p was found to increase in the presence of salt for the EHEC fraction with a high cloud point (CP). The polymer with a low CP displays higher N _p in the presence of salt at low SDS concentrations, but exhibit lower N _p at higher SDS concentrations than in the salt-free system. The microviscosity index as determined by intramolecular excimer formation of 1, 3-di(1-pyrenyl)propane (P3P) is highest for the lowest N _p and there is a corre-lation with N _p in the presence as well as absence of salt for both EHEC fractions. It is found that when the same fractional amount of SDS is bound to the polymers, 10–20% of the value of saturation, the increase in macroviscosity occurs and the microviscosity shows high rigidity. Received: 3 March 1997 Accepted: 23 May 1997     

Plasma polymerization of some organic compounds and properties of the polymers

Plasma polymerizations (under 13.5-MHz radiofrequency inductively coupled glow discharge) of some organic compounds are investigated by their properties (elemental analysis, surface energy, and infrared spectra) and their relations to the concentrations of free radicals in the polymers as detected by electron spin resonance (ESR) spectroscopy. Monomers that have been investigated are hexamethyldisiloxane, tetrafluoroethylene, acetylene, acetylene/N₂, acetylene/H₂O, acetylene/N₂/H₂O, allene, allene/N₂, allene/H₂O, allene/N₂/H₂O, ethylene, ethylene/N₂, ethylene oxide, propylamine, allylamine, propionitrile, and acrylonitrile. Plasma-polymerized polymers generally contain oxygen, even if the starting monomers do not contain oxygen. This oxygen incorporation is related to the free-radical concentration in the polymer. Molecular nitrogen copolymerizes with other organic monomers such as acetylene, allene, and ethylene, and their properties are very similar to those of plasma-polymerized polymers from nitrogen-containing compounds such as amines and nitriles. The addition of water to the monomer mixture reduces in a dramatic manner the concentration of free radicals in the polymer and consequently the oxygen-incorporation after the polymer is exposed to air. The concentrations of free radicals (by ESR) are directly correlated to the change of the properties of plasma-polymerized polymers with time of exposure to the atmosphere. These changes are primarily the introduction of carbonyl (and possibly hydroxyl) groups. The addition of water to the plasma introduces these groups during the polymerization.     

Rheological Modeling of Dispersion System of Nano/Microsized Polymer Particles Considering Swelling Behavior

Rheological behavior of dispersion system containing nano/microsized cross-linked polymer particle was studied considering particle hydration and swelling. Viscosity of the dispersion system depends on swelling kinetics of polymer particles. Under shear flow, dispersion of swollen polymer particles is shear thinning. According to experimental results, kinetics of particle swelling and hydration was described well by second-order kinetic equation. Relational expression between equilibrium particle size and influencing factors of swelling such as salt concentration and temperature was presented. Assume that swollen polymer particles are uniform and have a simple core-shell structure, interacting through a repulsive steric potential. The rheological modeling of such dispersion system at low shear rate was presented using the concept of effective volume fraction, which depends on swelling kinetics and interparticle potential. Cross model was introduced to describe shear-thinning behavior. The viscosity equation allows correlation of experimental data of relative viscosity versus shear rate or hydration time; accounting for effect of temperature and salt concentration on viscosity. Predictions of the model have a good agreement with experimental results.     

Pathways in the Nucleophilic Substitution Reactions of Halogenocyclophosphazenes and Subtle Aspects of the Mechanism of Formation of Bicyclic Phosphazenes

Abstract

Both associative [S_N2(P)] and dissociative [S_N1(P) and E₁CB] mechanisms have been established for the amination reactions of haloenocyclophosphazenes from synthetic and kinetic studies. Several intricate details concerning the formation of bicyclic phosphazenes have been unravelled.     

Synthesis and characterization of functionalized amphiphilic polymers for utilization as surfactants

Eight novel PEG-based amphiphilic block copolymers having self-assembling properties has been reported in the present study. The polymers have been synthesized by reacting Poly(ethylene glycols) (PEGs) of different molecular weights viz. 600, 1000, 1500 and 2000 and dimethyl-5-hydroxyisophthalate in presence of concentrated H₂SO₄ as catalyst in solventless condition at 80–90°C and further alkylating the resulting polymers by attaching octyl and hexadecanyl chains to phenolic hydroxyl group. The resulting functionalized amphiphilic polymers have been characterized by ¹H and ¹³C-NMR spectroscopy. These polymers, when dissolved in water, aggregate to form micelles, giving sizes ranging from 13.00 to 87.24 nm as determined by Dynamic Light Scattering (DLS) instrument. The molecular weights have been also calculated from the DLS and are in the range 3.5×10⁴ to 1.8×10⁶ KDa (Kilo Daltons). Critical Micelle Concentrations (CMC) of the synthesized polymers was determined using electrical conductivity meter with values in the range of 105 to 138 mg L^?1 (milligrams per litre).     

Organometallic polymers. XV. Synthesis and characterization of some ferrocene-containing oxysilane polymers from bis(dimethylamino)silanes

Three bis(dimethylamino)silane monomers have been polymerized with 1,1'-bis-(hydroxymethyl)ferrocene to give ferrocene-containing polyoxysilanes I and II. They were bis(dimethylamino)dimethylsilane (III), bis(dimethylamino)diphenylsilane (IV), and 1,4-bis(N,N-dimethylaminodimethylsilyl)benzene (V). Mixing of the diol and III or IV at O°C followed by heating resulted in polymerization to higher molecular weights than when the monomers were initially mixed at higher temperatures. At higher temperatures the formation of monomeric cyclic products seriously competed with polymerization, and the five atom bridged derivative, 3-sila-2,4-dioxa-3,3diphenyl[5]ferrocenophane (VI) was isolated in good yield. The use of silane V, where cyclization is not expected to compete, led to higher polymer yields and molecular weights. The polymers were low melting and I (R = C₆H₅) could be cast into films and weak fibers were drawn from its melt. The polymers were sensitive to hydrolytic decomposition; those containing Si-CH₃ linkages were completely hydrolyzed in refluxing THF-H₂O (10:1) in 1 hr. The polymers were characterized by viscosity studies, gel-permeation chromatography, and infrared and NMR spectroscopy.     

Synthesis and characterization of new ointment-like poly(ortho esters)

Ointment-like poly(ortho esters) were synthesized for the first time from the reaction of 3,9-bis(methylene)-2,4,8,10-tetraoxaspiro[5. 5] undecane with poly(ethylene glycol)-400, N,N-bis(2-hydroxyethyl)-n-hexadecylamine and N,N-bis(2-hydroxyethyl) palmitamide, respectively. The obtained polymers were characterized by 1H NMR spectra, 13C NMR spectra, elemental analyses, light scattering, and measurements of intrinsic viscosity. The influence of catalyst on the intrinsic viscosity of polymers was investigated. The 9-[(1,3-dihydroxy-2-propoxy) methyl] guanine controlled release profiles of hydrophobic ointment-like polymers such as polymer P_II in vitro were also discussed.     

Kinetic Studies on Interaction of Platinum(II) Complexes with an ‘S’ Containing Ligand in Aqueous Medium

The kinetics of the substitution reactions of [Pt(dach)(H₂O)₂]²⁺ and [Pt(en)(H₂O)₂]²⁺ (where ‘dach’ and ‘en’ are cis-1,2-diaminocyclohexane and ethylenediamine, respectively) with excess N,N′-diethylthiourea have been studied in aqueous solution by UV–Vis spectrophotometry. The effect of different N–N spectator ligands on the reactivity of platinum(II) complexes was investigated by studying the water lability of the reactant complexes. The kinetic study has been substantiated by product isolation, IR, NMR and ESI-MS spectral analysis and DFT calculations. The reactions follow normal square-planar substitution mainly in an associative way. Rate parameters have been evaluated under different conditions. The substitution rates of the complexes studied can be tuned through the nature of the N–N chelates, which is important in the development of new active compounds for cancer therapy.