L. V. Vinogradova

Molecular and hydrodynamic characteristics of star-shaped polystyrenes with one or two fullerene (C60) molecules as a branching center

The molecular properties of regular star-shaped polystyrenes with different numbers of arms (6, 12, and 22) and different structures of the branching center (one or two covalently bonded fullerene C60 molecules) are studied by static light scattering; translational diffusion; and viscometry in toluene, THF, and chloroform. The lengths of the arms for the studied polymer stars are found to be the same. (The molecular mass of the arm is 8.1 × 103.) The molecular mass and hydrodynamic sizes of macromolecules are estimated. It is shown that the conformational and hydrodynamic characteristics of polymer stars remain practically unchanged on passage from THF to chloroform. Compared to the linear analog, star-shaped fullerene-containing PSs are characterized by a higher density of the molecular coil. The shape of their macromolecules differs insignificantly from spherical, in consistence with theoretical predictions for polymer stars with relatively short arms.

Gas-separating properties of membranes based on star-shaped fullerene (C60)-containing polystyrenes

Based on regular star-shaped PSs differing in the structure of the branching center (one or two covalently bound fullerene C60 molecules) and in the number of branchings (6 and 12), homogeneous gas-separation membranes have been produced. The transport behavior of the membranes with respect to several gases, such as H2, He2, N2, CO, CO2, and CH4, has been studied by mass spectrometry. It has been found that the membranes prepared from six-arm PSs are characterized by a smaller density of macromolecular packing than the membranes obtained from 12-arm PCs and, consequently, they possess higher gas permeability. The starshaped PSs demonstrate a higher selectivity factor for separation of the O2/N2 gas pair compared to the corresponding characteristics of the linear PSs. The analysis of gas-separation characteristics by means of the Reitlinger-Robeson diagrams demonstrates that the transport behavior of star-shaped PSs qualitatively surpasses similar parameters of the known polymers in the separation of the CO/N2 gas pair.

Structural features of star-shaped fullerene (C60)-containing polystyrenes: Neutron scattering experiments

Structural features of star-shaped polyprotostyrene and polydeuterostyrene containing fullerene C60 as a branching center have been studied by small-angle neutron scattering in benzene solutions. The results are compared with the corresponding characteristics of linear PSs, the molecular mass of which is equal to the molecular mass of one star arm in star-shaped macromolecules. The molecular masses of star-shaped polymers are estimated, and their branching center is shown to be hexafunctional. At relatively low concentrations of starshaped polymers in solutions, one can observe excluded volume effects, which are related by the presence of regions with higher densities at the center of a macromolecule. Using the Fourier transform of the scattering cross section, three-dimensional correlation functions are obtained, and the regular structure of stars is proved. Conclusions about the local correlations of units within one star arm and averaged correlations between units of neighboring arms within a given star are derived. An analysis of three-dimensional correlations shows that the centers of mass of all star arms are directed along orthogonal axes passing through the C60 branching center of a star-shaped macromolecule.

Structure and supramolecular structures of star-shaped fullerene-containing heteroarm polymers in deuterotoluene

Self-organization of star-shaped polymers containing six PS arms and six polar polymer arms on a common C60 branching center is studied by means of small-angle neutron scattering in deuterotoluene. The results are compared with the corresponding characteristics of six-arm star-shaped fullerene-containing PSs. It is shown that the incorporation of additional polar arms into a six-arm macromolecule leads to its compression due to an increase in the degree of coiling of polar chains in the nonpolar solvent. In solution, heteroarm stars give rise to supramolecular structures in the form of clusters whose dimensions and density depend on the nature of the polar arms. Stars containing PS and poly(2-vinylpyridine) arms are weakly associated, and the mean number of particles in an associate is ∼1.3. Hybrid polymers containing PS and poly(tert-butyl methacrylate) arms demonstrate capability for mutual penetration that favors the appearance of large structures that have a diameter of ∼50 nm and that include up to 12 macromolecules. Hybrid stars containing PS and diblock copolymer (poly(2-vinylpyridine)-poly(tert-butyl methacrylate)) arms exhibit moderate self-organization that manifests itself in the formation of chain associates built from four macromolecules.

Mass-spectrometric investigation of the thermal stability of polymethyl methacrylate in the presence of C60 fullerene

The thermal degradation of polymethyl methacrylate, synthesized by the method of free-radical polymerization, in a mixture with C60 fullerene has been investigated by mass-spectrometric thermal analysis. C60 suppresses the first two, low-temperature, stages in the thermal degradation of polymethyl methacrylate and thereby increases its thermal stability.

NSE-study of fullerene-containing polymers

Abstract Stars of Poly(styrene) chains grafted to C60 have been studied by SANS and NSE below glass transition (TG∼94∘C). In stars the arms are not condensed at fullerene surface, spreading away from C60-core. The interaction between fullerene core and polymer chains slows down the β-relaxation in arms at T=−20 to +70 ∘ C

Effect of C60 on the thermal stability of polyethylene glycol grafted to it

The thermal degradation of regular polymer networks, cross-linked by C60 molecules along the end groups of polyethylene glycol, has been investigated by mass-spectrometric thermal analysis for the example of polyethylene glycol grafted to fullerene C60. The character of the thermal degradation of the networks is substantially different from that of free polyethylene glycol and other polymer systems investigated earlier. The grafting to C60 increases the thermal stability of polyethylene glycol.

Internal organization and conformational characteristics of star-shaped polystyrene with fullerene C60 as a branching center in deuterotoluene

The internal organization of star-shaped polystyrene macromolecules containing fullerene C60 as a branching center is studied via small-angle neutron scattering in deuterotoluene. Analysis of the experimental data according to the Debye-Benoit approximation and the Fourier transformation of the momentum transfer dependences of scattering cross sections for the linear PS precursor and stars is used to determine their molecular masses (9 × 103 and 5 × 104) and gyration radii (∼2.7 and ∼5.5 nm), the gyration radius of the arm (∼3.4 nm), and the average functionality of the star (5.7). The behavior of scattering cross sections for the fullerene-containing polymer on the whole is described by the law of scattering for stars with Gaussian arms (the Benoit model). However, at the local level (within one chain segment), the fullerene center exerts a specific effect on the conformation of arms. As a result, their statistical flexibility decreases and eventually the size of the star increases by ∼30%. This finding conflicts with the Daoud-Cotton theory.

Segmental dynamics in stars of poly(ethylene oxide) chains grafted to fullerene

Abstract We have studied the structure and dynamics of star-shaped poly(ethylene-oxide) (PEO), grafted to fullerene, in D2O-solutions as compared to linear polymer. The neutron scattering gives the radius of stars having a value close to the end-to-end distance of their PEO arms. The spin-echo measurements revealed a strong damping of segmental diffusion in stars showing stretched relaxation behavior.

Anomalies of Glass Transition: Manifestation in fullerene core polystyrene stars

Segmental dynamics around Tg in the 4- and 6-arm fullerene (C60) core star-like polystyrenes with different preset arm lengths was studied by DSC as compared to that in the linear PS and PS/C60 blend. The ‘anomalies’ in glass transition behavior were found for the stars including both suppression and facilitation of segmental motion, and pronounced dynamic heterogeneity within a transition range. The results are interpreted in terms of breakdown of intermolecular cooperativity of segmental motions and PS-C60 interactions.