Surfactant induced mesomorphic behaviour of flexible polymers

Conditions for micro phase separated structures based on flexible polymers associated with surfactants have been investigated. Reasonably strong attractive interactions are required to oppose macro phase separation between polymer and surfactant. In order to obtain micro phase separation, additionally a sufficiently strong polar-nonpolar repulsion has to be present. Poly(4-vinyl pyridine), poly(2-vinyl pyridine) and polyamide 6 have been used as model polymers in this work. Associations based on protonation, metal coordination and hydrogen bonding are presented and shown to yield micro phase separation under suitable conditions. In the charged systems, the polar-nonpolar repulsion easily becomes large enough to render micro phase separated structures. In hydrogen bonded (i.e. noncharged) systems a more delicate balance can be achieved in which case an order-disorder transition takes place from a homogeneous state, exhibiting nonetheless a distinct SAXS peak due to characteristic block copolymer-like fluctuations, to a micro phase separated ordered state.</p

MESOMORPHIC STATE OF POLY(VINYLPYRIDINE)-DODECYLBENZENESULFONIC ACID COMPLEXES IN BULK AND IN XYLENE SOLUTION

Theoretically, lyotropic behavior of flexible polymers can be induced by associating the polymers with a large amount of long-tail surfactants leading to bottle-brush type conformations in suitable solvents. To address this and related questions, complexes of poly(2-vinylpyridine) (P2VP) and poly(4-vinylpyridine) (P4VP) with p-dodecylbenzenesulfonic acid (DBSA), characterized by FT-IR, were investigated in the bulk and in xylene, i.e., a good solvent for the alkyl side chains. At a 1:1 molar ratio of vinylpyridine monomer and DBS, the polymers are shown by FT-IR to be almost completely protonated. In the bulk, the complexes form mesomorphic layer structures which have been characterized by polarized optical microscopy and by both wide- and small-angle X-ray scattering. In the xylene solutions, birefringence indicating liquid crystallinity is observed for concentrations of the fully protonated P4VP-(DBSA)(1.0) complex of ca. 50% (w/w) and higher. In contrast, for P2VP(DBSA)(1.0), this is only observed at complex concentrations of ca. 70% (w/w) and higher. The mesomorphic behavior of P4VP(DBSA)(1.0) in xylene was further demonstrated by SAXS

On the feasibility of a nuclear exciton laser

Nuclear excitons known from M\"ossbauer spectroscopy describe coherent excitations of a large number of nuclei -- analogous to Dicke states (or Dicke super-radiance) in quantum optics. In this paper, we study the possibility of constructing a laser based on these coherent excitations. In contrast to the free electron laser (in its usual design), such a device would be based on stimulated emission and thus might offer certain advantages, e.g., regarding energy-momentum accuracy. Unfortunately, inserting realistic parameters, the window of operability is probably not open (yet) to present-day technology -- but our design should be feasible in the UV regime, for example.Comment: 7 pages RevTeX, 4 figure

Intermediate segregation type chain length dependence of the long period of lamellar microdomain structures of supramolecular comb-coil diblocks

A characteristic intermediate segregation type chain length dependence of the long period D of the lamellar microdomain structure of a class of comb-coil supramolecules is reported. The supramolecular comb-coil diblock copolymers studied consist of a polystyrene (PS) “coil” block and a “comb” block of poly(4-vinylpyridine) (P4VP) either hydrogen bonded to pentadecyl phenol (PDP) (i.e., P4VP(PDP)-b-PS) or first protonated with methanesulfonic acid (MSA) and then hydrogen bonded to PDP (i.e., P4VP(MSA)(PDP)-b-PS). In both cases we find a scaling D ~ Ntotδ, δ ≈ 0.8, where Ntot denotes the total number of monomers of the P4VP-b-PS backbone. In the case of diblock copolymers this would correspond to a characteristic intermediate segregation regime behavior. Pure PS-b-P4VP, on the other hand, shows the expected strong segregation behavior D ~ Ntotδ, δ ≈ 0.7.

Self-Assembly of Supramolecular Triblock Copolymer Complexes

Four different poly(tert-butoxystyrene)-b-polystyrene-b-poly(4-vinylpyridine) (PtBOS-b-PS-b-P4VP) linear triblock copolymers, with the P4VP weight fraction varying from 0.08 to 0.39, were synthesized via sequential anionic polymerization. The values of the unknown interaction parameters between styrene and tert-butoxystyrene and between tert-butoxystyrene and 4-vinylpyridine were determined from random copolymer blend miscibility studies and found to satisfy 0.031<χS,tBOS<0.034 and 0.39<χ4VP,tBOS<0.43, the latter being slightly larger than the known 0.30<χS,4VP≤0.35 value range. All triblock copolymers synthesized adopted a P4VP/PS core/shell cylindrical self-assembled morphology. From these four triblock copolymers supramolecular complexes were prepared by hydrogen bonding a stoichiometric amount of pentadecylphenol (PDP) to the P4VP blocks. Three of these complexes formed a triple lamellar ordered state with additional short length scale ordering inside the P4VP(PDP) layers. The self-assembled state of the supramolecular complex based on the triblock copolymer with the largest fraction of P4VP consisted of alternating layers of PtBOS and P4VP(PDP) layers with PS cylinders inside the latter layers. The difference in morphology between the triblock copolymers and the supramolecular complexes is due to two effects: (i) a change in effective composition and, (ii) a reduction in interfacial tension between the PS and P4VP containing domains. The small angle X-ray scattering patterns of the supramolecules systems are very temperature sensitive. A striking feature is the disappearance of the first order scattering peak of the triple lamellar state in certain temperature intervals, while the higher order peaks (including the third order) remain. This is argued to be due to the thermal sensitivity of the hydrogen bonding and thus directly related to the very nature of these systems.

Self-assembly in solution of a reversible comb-shaped supramolecular polymer

We report a single step synthesis of a polyisobutene with a bis-urea moiety in the middle of the chain. In low polarity solvents, this polymer self-assembles by hydrogen bonding to form a combshaped polymer with a central hydrogen bonded backbone and polyisobutene arms. The comb backbone can be reversibly broken, and consequently, its length can be tuned by changing the solvent, the concentration or the temperature. Moreover, we have proved that the bulkiness of the side-chains have a strong influence on both the self-assembly pattern and the length of the backbone. Finally, the density of arms can be reduced, by simply mixing with a low molar mass bis-urea