Triblock copolymers of BAB type were synthesized by ATRP with a poly(acrylic acid) central block and random copolymer end blocks containing both acrylic acid (AA) and hydrophobic n-butyl acrylate (nBA) units with varied composition of the B-blocks. Visco-elastic properties of these amphiphilic polymers were investigated by oscillatory shear measurements as a function of composition, concentration, temperature and pH. Whatever the composition for each polymer the terminal relaxation time and thus the viscosity increased sharply with decreasing degree of ionization of the AA units (α) and at low values self-supporting hydrogels were formed. However, the α- (respectively pH-) dependence of the terminal relaxation time as well as the critical range of α (respectively pH) where a transition between visco-elastic solutions and self-supporting hydrogels occurs strongly depend on the composition of the B-block.

We report some new and interesting observations on the abrupt and large shear-induced thickening of aqueous solutions of hydrophobically modified poly(N,N′-dimethylacrylamide-co-acrylic acid). High molecular weight copolymer was prepared by free radical copolymerization of N,N′-dimethylacrylamide [DMA] and acrylic acid [AA] and was subsequently modified to different extents using a hydrophobic compound, namely, 3-pentadecylcyclohexylamine [3-PDCA], which is derived from a renewable resource material, cashew nutshell liquid [CNSL]. The structural elucidation of the base copolymer and the hydrophobically modified copolymers was performed by 1H and 13C NMR spectroscopy. The zero shear viscosities [η0] of the hydrophobically modified polymers were lower than that of the precursor poly(N,N′-dimethylacrylamide-co-acrylic acid) until some critical polymer concentration, which increased with increase in hydrophobic modification. Above the critical concentrations, the η0 of the hydrophobically modified copolymers surpassed that of the precursor at the same concentration. At moderate shear rates some of these hydrophobically modified copolymers exhibited an abrupt shear-induced thickening in which the viscosity of the samples increased severalfold. We show here from creep experiments that thickening occurs only when the shear rate reaches a critical value, γ̇crit, and that the thickened samples can be trapped in different metastable states by controlling the applied stress. Interestingly, the shear thickened samples showed further thickening upon decreasing the applied stress. Eventually, the metastable samples revert to their equilibrium states at characteristic time that depends on (small) probe stress.

While aqueous solutions of several amphiphilic thermo-reversible polymers show gelation upon heating, there are fewer examples of polymer solutions that exhibit gelation when cooled. This paper reports an interesting phenomenon of abrupt thermoreversible gelation of aqueous solutions of a hydrophobically modified polymer upon cooling. A high molecular weight precursor copolymer (PCP, M w z 5 Â 10 6 g mol À1 ) of N,N-dimethylacrylamide (70 mol%) and acrylic acid (30 mol%) was modified by reacting 10 mol% of the acrylic acid groups with n-dodecyl amine to form a hydrophobically modified copolymer (HMCP). The composition of the copolymer was ascertained using NMR spectroscopy.Cooling the solution of PCP at a controlled rate resulted in a gradual increase in its low shear viscosity as dictated by the flow activation energy. In contrast, cooling the solution of HMCP under identical conditions resulted in an abrupt and large non-Arrhenius increase in viscosity at a specific transition temperature, which decreased with decrease in polymer concentration. Fluorescence measurements and dynamic light scattering data showed that abrupt gelation happened upon cooling, when polymer coils percolate accompanied with concomitant transition in chain conformation from compact micellar coils formed by intra-chain hydrophobic associations to swollen polymer coils connected by inter-chain hydrophobic interactions.

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Summary: Hydrophobically modified poly(acrylic acid) was synthesized using 3‐pentadecylcyclohexylamine (3‐PDCA), which was in turn synthesized from 3‐pentadecylphenol, one of the components of cashew‐nut shell liquid (CNSL), a renewable resource material. 1H NMR spectra confirmed the incorporation of 3‐PDCA onto PAA and a series of HMPs with three different molar concentrations, viz ≅ 3, 5 and 7 mol‐% of 3‐PDCA, were synthesized. An increase in viscosity with increasing hydrophobic content was observed by rheological measurements. The critical association concentrations were determined using an Ubbelohde viscometer and a controlled stress rheometer. The stability of HMPs towards temperature and shear was studied. Rheological measurements showed that there was a steady increase in viscosity with increase in hydrophobe content due to the formation of reversible networks. These polymers exhibited gel‐like behavior at low concentrations (≥2 wt.‐%) with an apparent yield stress (ca. 10 Pa) and showed shear thinning properties (non‐Newtonian). However, below a critical concentration, c [η], they showed Newtonian behavior.

A simple method for synthesis of methylene dioximes by reaction of ketoximes with dichloromethane in the presence of aqueous sodium hydroxide solution using poly (ethylene glycol)-400 (PEG-400) as a phase transfer catalyst is described.

Hydrophobically modified poly(vinyl alcohol) (HMPVA) polymers were synthesized by potassium t‐butoxide‐catalyzed reaction of PVA with methyl 3,4,5‐tris(n‐octyloxy) benzoate (MGC8)/3,4,5‐tris(n‐dodecyloxy) benzoate (MGC12) and 1,3‐propane sultone. The concentration of 1,3‐propane sultone was kept constant at 10 mol % and that of MGC8 (2, 3, and 4 mol %)/MGC12 (2 and 3 mol %) was varied to obtain HMPVAs with different hydrophobic contents. The incorporation of MGC8/MGC12 and 1,3‐propane sultone onto HMPVA was confirmed by NMR spectroscopy. Rheological properties of aqueous solutions also confirmed the presence of hydrophobic and charged functional groups on HMPVAs. In the semidilute regime, the specific viscosity of HMPVAs followed concentration scaling that is typical of polyelectrolytes. At higher concentrations, the HMPVA solutions with 3 and 4 mol % of MGC8 exhibited large increase in specific viscosity. Oscillatory experiments on these solutions exhibited gel‐like behavior at polymer concentrations of 40–50 g/L. Confocal microscopy images of HMPVA with 4 mol % of MGC8 clearly indicated the existence of microgels. The tendency of formation of microgels further increased with increasing chain length of the hydrophobe, that is, with MGC12. These samples exhibited rheological behavior that is typical of soft solids and was therefore probed by the strain‐rate frequency superposition technique reported recently in the literature. HMPVAs with improved rheological properties show potential applications as thickeners in cosmetic creams, lotions and as drug carriers in pharmaceutical formulations. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1054–1063, 2010

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