M. P. Kurlykin

Behavior of thermosensitive graft copolymer with aromatic polyester backbone and poly-2-ethyl-2-oxazoline side chains in aqueous solutions

ABSTRACT Thermoresponsive graft copolymers with alkylene-aromatic polyester main chain and poly-2-ethyl-2-oxazoline side chains were synthesized. Two copolymer samples which differed in grafting density (0.5 and 0.7) were studied using dynamic and static light scattering and turbidimetry in aqueous solutions at concentration 0.0053u2009gu2009cm−3. Hydrodynamic radii of scattering objects and their contribution to light scattering were obtained as a function of temperature in a wide temperature interval. Temperatures of phase separation were found out. Effect of grafting density on the copolymer behavior in aqueous solutions upon heating was determined. In particular, the phase separation temperature reduces with the decreasing grafting density.

Multicenter polyester initiators for the synthesis of graft copolymers with oligo(2-ethyl-2-oxazoline) side chains

Multicenter alkylene-aromatic polyester initiators for the cationic polymerization of oxazolines are synthesized via the high-temperature polycondensation of 2-[4-(2-Br-ethyl)]phenylsulfonyl hydroquinone with 4,4- (alkanoyldioxydibenzoyl)dichlorides. The Kuhn segment values, liquid-crystalline properties, and molecularmass characteristics of the macroinitiators are determined. It is shown that the obtained polyesters may be used as initiators for the cationic polymerization of 2-ethyl-2-oxazoline. The graft copolymers form aqueous micellar solutions with a narrow particle-size distribution and possess a lower critical solution temperature.

Synthesis of comb-shaped polymers via controlled cationic polymerization of oxazolines with polyester-type macroinitiator

On the basis of macroinitiators of polyester type, hybrid comb-shaped polymers with poly-2-isopropyl-2-oxazoline side fragments are prepared via ring-opening cationic polymerization. A method for estimating the length of polyoxazoline side chains and their grafting density is proposed. It is shown that, at the given ratio of the length of backbone and side chains, which depends on the chemical structure of the initiator, the graft copolymers are capable of formation of micellar aqueous solutions with a lower critical solution temperature.

Behavior of aqueous solutions of polymer star with block copolymer poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) arms

ABSTRACT Eight-arm star-shaped poly(2-alkyl-2-oxazoline) (Mu2009≈u200921,000u2009gu2009·u2009mol−1) was studied by turbidimetry and light scattering in aqueous solutions within concentration ranging from 0.00038 to 0.0276u2009gu2009·u2009cm−3. The arms were the block copolymers of poly(2-isopropyl-2-oxazoline) (PiPrOx) and poly(2-ethyl-2-oxazoline) (PEtOx). Calix[8]arene core was connected with poly(2-isopropyl-2-oxazoline). The behavior of investigated polymer differed from that of thermosensitive stars with poly(2-alkyl-2-oxazoline) homopolymer arms. At low temperatures, the aggregates were formed due to interaction of hydrophobic cores. The phase separation temperatures T1 and T2 of studied star were higher than those for star-shaped poly(2-isopropyl-2-oxazoline) and lower than for poly(2-ethyl-2-oxazoline). T1 and T2 increased with dilution.

Photophysical and conformation properties of luminescent-labeled star poly-2-isopropyl-2-oxazolines based on octa-tert-butylcalix[8]arene in solution

The synthesis of luminescent-labeled copolymers of octa-tert-butylcalix[8]arene with 8 poly-2-isopropyl-2-oxazoline arms is carried out. Each macromolecule involves one luminescent label of the anthracene structure located at the end of one of the arms. The luminescent properties of the copolymers in water and methanol are studied. It is shown that, in aqueous solutions, the formation of intermolecular aggregates with a hydrophobic core and a hydrophilic shell results in a new photophysical process of migration of electron excitation energy accompanied by a decrease in the solution luminescence polarization. The interaction of oxazoline arms with poly(methacrylic acid) via the mechanism of interpolymer complex formation implies a weakening of the efficiency of energy migration.

Influence of a hydrophobic core on thermoresponsive behavior of dendrimer-based star-shaped poly(2-isopropyl-2-oxazoline) in aqueous solutions

The behavior of eight-arm, star-shaped poly(2-isopropyl-2-oxazoline) (PiPrOx8) with a hydrophobic dendrimer core was studied in aqueous solutions by light scattering and turbidimetry methods. In order to reveal the influence of the star-shaped structure, model linear PiPrOxs were investigated for comparison. The experiments were carried out within a 100-fold concentration interval at temperatures from 15 to 63xa0°C. Dendrimer core interaction lead to the formation of different types of aggregates at low temperatures as compared to star-shaped PiPrOx with different cores. The temperatures of the phase separation interval were determined and analyzed depending on concentration. It was shown that macromolecule shrinkage and aggregation occur below the phase separation onset which results from the specific chemical nature of macromolecules and their hydrophilic-hydrophobic balance.

Behavior of Aqueous Solutions of Thermosensitive Starlike Polyalkyloxazolines with Different Arm Structures

The behavior of aqueous solutions of starlike polyalkyloxazolines with a calix[8]arene core is investigated by light scattering and turbidimetry. Polyethyloxazoline, the gradient copolymer of ethyloxazoline and isopropyloxazoline, and the block copolymers of polyethyloxazoline and polyisopropyloxazoline are used as arms. Using the methods of molecular hydrodynamics and optics, it is shown that the arms of the studied stars are strongly folded in organic solvents. It is found that the structure of arms affects the processes of self-organization and aggregation of their macromolecules in aqueous solutions. At room temperature, the dimensions of aggregates and their fraction in solutions depend on the position of ethyloxazoline and isopropyloxazoline units with respect to the calixarene core. Introducing ethyloxazoline units into macromolecules is accompanied by an increase in both the phase-separation temperature and the width of this interval relative to the corresponding characteristics of the star with polyisopropyloxazoline arms. For stars with copolymer arms, the temperatures of the end of phase transition differ insignificantly. Differences in the behavior of the studied arms are due to the fact that the dehydration temperature for polyethyloxazoline is noticeably higher than that for polyisopropyloxazoline.

Behavior of a Thermosensitive Star-Shaped Polymer with Polyethyloxazoline-block-Polyisopropyloxazoline Copolymer Arms

The aqueous solutions of the star-shaped eight-arm polymer in which arms consist of the block copolymer of poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) and a more hydrophilic poly(2- ethyl-2-oxazoline) is attached to the calix[8]arene core are studied by light scattering and turbidimetry. For the sake of comparison, the linear block copolymer modeling arms of the star-shaped polymer is examined. The temperature and concentration dependences of light scattering intensity and optical transmission, the hydrodynamic radii of particles occurring in solutions, and their fraction in solution are determined. At room temperature, solutions of the linear copolymer are molecularly dispersed because of a high hydrophilicity of blocks and aggregates are formed in solutions of the star-shaped polymer as a result of interaction between hydrophobic calix[8]arene cores. As the temperature grows, the dehydration of poly(2-isopropyl-2-oxazoline) units initially occurs and entails both the compaction and aggregation of star-shaped molecules. At higher temperatures, the dehydration of poly(2-ethyl-2-oxazoline) leading to phase separation begins. The temperature of phase separation grows upon dilution. A high intramolecular density of the star-shaped polymer is responsible for a marked deceleration of self-organization processes. This effect is especially pronounced in the vicinity of the phase-separation temperature.