Thermoresponsive behavior of water-salt solutions of a graft copolymer with a main polyimide chain and side poly(<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylamino-2-ethyl methacrylate) side chains

The water-salt solutions of the graft copolymer bearing a polyimide main chain and poly(N,N-dimethylamino-2-ethyl methacrylate) side chains (M = 4.7 × 10⁵, the density of grafting with side chains z = 0.44) are studied by static and dynamic light scattering and turbidimetry. The solutions are investigated in a tenfold range of NaCl concentrations (from 0.015 to 0.15 mol/L) at the polymer concentration from 0.002 to 0.015 g/cm³ and pH from 8 to 12. The temperature dependences of the intensity of scattered light, optical transmission, hydrodynamic radius of scattering objects, and their concentrations in solutions are derived. The temperatures of phase separation onset T ₁ and end T ₂ are determined. It is shown that an increase in the salt content in solution leads to reduction in the polymer solubility and in temperatures T ₁ and T ₂. The watersalt solutions retain all the regularities of phase-separation temperature variation observed for aqueous solutions with change in the concentration of solution and pH of a medium: the values of T ₁ and T ₂ increase upon dilution and growth of acidity.     

Enumeration of labeled outerplanar bicyclic and tricyclic graphs

The class of outerplanar graphs is used for testing the average complexity of algorithms on graphs. A random labeled outerplanar graph can be generated by a polynomial algorithm based on the results of an enumeration of such graphs. By a bicyclic (tricyclic) graph we mean a connected graph with cyclomatic number 2 (respectively, 3). We find explicit formulas for the number of labeled connected outerplanar bicyclic and tricyclic graphs with n vertices and also obtain asymptotics for the number of these graphs for large n. Moreover, we obtain explicit formulas for the number of labeled outerplanar bicyclic and tricyclic n-vertex blocks and deduce the corresponding asymptotics for large n.     

Solution behavior of polyimide‐graft‐polystyrene copolymers in selective solvents

A polyimide‐graft‐polystyrene (PI‐g‐PS) copolymer with a polyimide backbone and polystyrene side chains was synthesized by the “grafting from” method using styrene polymerization on a polyimide multicenter macroinitiator via ATRP mechanism. The side chain grafting density z = 0.86 of PI‐g‐PS is rather high for graft‐copolymers synthesized by the ATRP method. Molecular characteristics and solution behavior of PI‐g‐PS were studied in selective solvents using light scattering and viscometry methods. In all solvents, the backbone tends to avoid contact with a poor solvent. To describe the conformation and hydrodynamic properties of PI‐g‐PS macromolecules in thermodynamically good solvents for side chains and PI‐g‐PS, the wormlike spherocylinder model is used. Macromolecules of the studied graft‐copolymer are characterized by high equilibrium rigidities (Kuhn segment length >20 nm). In Θ‐conditions, PI‐g‐PS macromolecules may be modeled by a rigid prolate ellipsoid of revolution with a low asymmetry form and a collapsed backbone as the ellipsoid core. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1539–1546     

Interpolymer complexes of poly(N-vinylpyrrolidone) with copolyimide-grafted side chains of poly(methacrylic acid)

The process of formation and structural organization of interpolymer complexes formed by macromolecules of poly(N-vinylpyrrolidone) and poly(methacrylic acid) chains grafted onto polyimide in solution is investigated via the method of polarized luminescence. A luminescent label of anthracene structure is covalently bound to both polymers. Relaxation times characterizing intramolecular mobility of each of the components in their interpolymer complex are measured in relation to the composition of the system.     

Conformations of molecular brushes based on polyimide and poly(methyl methacrylate) in selective solvents: Experiment and computer simulation

The effect of solvent quality with respect to main and side chains on the conformations of molecular brushes is investigated by the methods of molecular hydrodynamics and optics as well as by computer simulation. Copolymers with a polyimide backbone and poly(methyl methacrylate) side chains are studied in solvents featuring strongly different thermodynamic qualities (chloroform, ethyl acetate, and 3-heptanone). The studied samples have close total molecular masses and backbone lengths but differ in grafting densities and lengths of side chains: a brush with densely grafted and relatively short side chains versus a brush with loosely grafted but very long side chains. For both types of brushes, similar changes in hydrodynamic behavior with improvement in the solvent quality are found experimentally. Computer simulation shows that these changes have different origins. In the former case, macromolecules are elongated, and their volumes grow simultaneously, while in the latter case, the shape of the macromolecules remains close to spherical and the changes in hydrodynamic parameters are mainly due to an increase in the volume of macromolecules.     

Synthesis and investigation of the solution behavior of graft block copolymers of polyimide and poly(methyl methacrylate)

Graft copolymers with a polyimide backbone and poly(methyl methacrylate) side chains are investigated in dilute chloroform and ethyl acetate solutions via the methods of molecular hydrodynamics and optics. Copolymer samples are prepared through the “grafting from” method via atom-transfer radical polymerization with a multicenter polyimide macroinitiator. In solutions of copolymers with low degrees of functionalization Z (40%), supermolecular structures are formed as a result of interactions between the polyimide backbones. In samples with Z → 100%, the backbone is well screened by side chains; therefore, molecular solutions are formed in both solvents. The hydrodynamic and conformational behavior of samples with high functionalization degrees changes after the transition from ethyl acetate to chloroform owing to the different thermodynamic qualities of the solvents with respect to the copolymer components. In both solvents, the backbone tends to avoid contact with a poor solvent. This effect is more pronounced in the case of ethyl acetate. Macromolecules of the studied graft copolymers are characterized by high equilibrium rigidities (>40 nm) that are 10 times higher than the corresponding characteristics of aromatic polyimides.