International audienceA new polymer blend formed by poly(3-hexylthiophene)-poly(4-vinylpyridine) (P3HT-P4VP) block copolymers and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is reported. The P4VP and PCBM are mixed together by weak supramolecular interactions, and the resulting materials exhibit microphase separated morphologies of electron-donor and electron-acceptor rich domains. The properties of the blend, used in photovoltaic devices as active layers, are also discussed

We describe the synthesis, the morphology, and self-assembly behavior of semiconducting poly-(4-vinylpyridine-b-diethylhexyloxy-p-phenylenevinylene) (P4VP-b-PPV) rod-coil block copolymer systems. Three different block copolymers with 55%, 80%, and 88% coil volume fraction were synthesized by convergent anionic polymerization in THF using lithium R-methylstyrene as initiator. The morphology of the block copolymers was studied by transmission electron microscopy, small-angle X-ray scattering, and small-angle neutron scattering as a function of the volume fraction of the rod block as well as different annealing conditions. The microphaseseparated morphologies in these block copolymers vary from lamellar, to hexagonal, and spherical, when the volume fraction of the rod is progressively reduced. By combining the lattice parameter measured by scattering techniques with the volume fraction of rod domains obtained by nuclear magnetic resonance, it was shown that the block copolymers in the lamellar structure are organized in a smectic C double layer, while in the hexagonal phase they self-organize in a homeotropic arrangement, with the rod blocks forming the dispersed phase. Furthermore, while self-assembly of rod-coil block copolymers in columnar hexagonal phase prevents close rod packing, for the lamellar phase evidence of this configuration among rods is shown by wide-angle X-ray scattering. As a consequence, the morphology and long-range order in the lamellar phase are the result of simultaneous inter-rods liquid crystalline interactions and the tendency to microphase segregation of rod and coil. As a result, depending on temperature, the lamellar phase can exist both with rods oriented in a smectic configuration and with randomly packed rods. We show that annealing the lamellar phase below its order-disorder transition temperature, T ODT , but above the maximum affordable temperature for inter-rods liquid crystalline interactions, called smectic-in-lamellar to lamellar order-disorder transition temperature, T SL (with T SL < T ODT ), leads to highly improved long-range lamellar order, which is then preserved when the system is cooled below T SL , at which temperature rod close packing is fully recovered.

The morphology arising from the self-assembly of π-conjugated poly(diethylhexyloxy-pphenylenevinylene) rod homopolymers (PPV) and poly(diethylhexyloxy-p-phenylenevinylene)-polystyrene (PPV-PS) rod-coil block copolymers is described. Two PPV-PS block copolymers, one with low rod volume fraction (∼17%) and the other with high volume fraction (∼50%), were synthesized by convergent anionic polymerization and atom transfer radical polymerization, respectively. In the first case, given the low volume fraction of the rod block, the pure asymmetrical rod-coil block copolymer formed an isotropic homogeneous phase. However, ordered clusters of alternating PS and PPV domains with characteristic length of the order of several micrometers appeared when PPV rod homopolymers were blended to the PS-PPV diblock. Furthermore, the long-range order of the clusters as well as their volume fraction could be greatly increased when the symmetric rod-coil PPV-PS was blended to PPV homopolymer. Tomographic reconstruction from transmission electron micrographs allowed demonstrating that the clusters were organized in lamellar phase with well-defined width for both the intercalated PS and PPV domains, while wide-angle X-ray scattering showed that within the PPV domains the PPV blocks and PPV homopolymer rods were closely packed. The study of the spacing widths of the PPV and PS domains showed that clusters are organized in a smectic C configuration with large tilt angles of the rods (54°) and stretching of the coil blocks which is typical of weakly segregated block copolymers organized in a lamellar phase. The stability of the rod-to-rod interaction peak at high temperatures (190°C), well beyond the order-disorder transition temperature of the clusters (130°C), suggests that the (i) aggregation of the rods is mediated by π-π interactions and (ii) the clusters are thermodynamically stable structures. The energetic driving force toward the formation of these clusters is discussed in the last part of this work.

Abstract. We report on the self-assembly behaviour of two homologue series of rod-coil block copolymers in which, the rod, a π-conjugated polymer, is maintained fixed in size and chemical structure, while the coil is allowed to vary both in molecular weight and chemical nature. This allows maintaining constant the liquid crystalline interactions, expressed by Maier-Saupe interactions, ω, while varying the tendency towards microphase separation, expressed by the product between the Flory-Huggins parameter and the total polymerization degree, χN . Therefore, the systems presented here allow testing directly some of the theoretical predictions for the self-assembly of rod-coil block copolymers in a weakly segregated regime. The two rod-coil block copolymer systems investigated were poly(DEH-p-phenylenevinylene-b-styrene), whose self-assembly takes place in the very weakly segregated regime, and poly(DEH-p-phenylenevinylene-b4vinylpyridine), for which the self-assembly behaviour occurs under increased tendency towards microphase separation, hereby referred to as moderately segregated regime. Experimental results for both systems are compared with predictions based on Landau expansion theories.PACS. 61.46.-w Nanoscale materials -61.30.Vx Polymer liquid crystals -64.60.Cn Order-disorder transformations; statistical mechanics of model systems

Free radical polymerization in microfluidic devices modeled with the help of numerical simulations is discussed. The simulation method used allows the simultaneous solvation of partial differential equations resulting from the hydrodynamics, thermal and mass transfer (convection, diffusion and chemical reaction). Three microfluidic devices are modeled, two interdigital multilamination micromixers respectively with a large and short focusing section, and a simple T-junction followed by a microtube reactor together considered as a bilamination micromixer with a large focusing section. The simulations show that in spite of the heat released by the polymerization reaction, the thermal transfer in such microfluidic devices is high enough to ensure isothermal conditions. Moreover, for low radial Peclet number, microfluidic devices with a large focusing section can achieve better control over the polymerization than a laboratory scale reactor as the polydispersity index obtained is very close to the theoretical limiting value. As the characteristic dimension of the microfluidic device increases, i.e. for high radial Peclet number, the reactive medium cannot be fully homogenized by the diffusion transport before leaving the system resulting in a high polydispersity index and a loss in the control of the polymerization.

This paper investigates the modeling of styrene free radical polymerization in two different types of microreactor. A multiphysics model which simultaneously takes into account the hydrodynamics, thermal and mass transfer (convection, diffusion and chemical reaction) is proposed. The set of partial differential equations resulting from the model is solved with the help of the finite elements method either in a 2D or a 3D approach. The different modeled microreactors are on one hand an interdigital multilamination microreactor with a large focusing section, and on the other hand a simple T-junction followed by a straight tube with three different radii. The results are expressed in terms of reactor temperature, polydispersity index, number-average degree of polymerization and monomer conversion for different values of the chemical species diffusion coefficient. It was found that the 2D approach gives the same results as the 3D approach but allows to dramatically reduce the computing time. Despite the heat released by the polymerization reaction, it was found that the thermal transfer in such microfluidic devices is high enough to ensure isothermal conditions. Concerning the polydispersity index, the range of diffusion coefficients over which the polydispersity index can be maintained close to the theoretical value for ideal conditions increases as the tube reactor radius decreases. The interdigital multilamination microreactor was found to act as a tubular reactor of 0.78 mm ID but with a shorter length. This underlines that the use of microfluidic devices can lead to a better control of polymerization reactions.

Summary: Two different approaches to obtain electron donor-acceptor interfaces via self-assembly of block copolymer systems are discussed, where the donor domains are formed by a p-conjugated rod-like polymer and the acceptor domains result from a coiled polymer modified by C 60 fullerenes. In the first strategy, C 60 is chemically grafted onto the coil polymer, typically a statistical copolymer of styrene and chloromethyl styrene. This has as major effect the increase in molecular weight and volume fraction of the coil block, which can markedly perturb the self-assembled block copolymer final morphologies and eventually suppress any microseparated nanostructure in favour of fully isotropic homogeneous phases. We discuss how the presence of free homopolymer rods in the system can help recovering a microphase separated morphology suitable for photovoltaic applications. In the second approach we discuss the poly(diethylhexyl-p-phenylenevinylene-b-4-vinylpyridine) (PPV-P4VP) rod-coil block copolymer system and we argue how supramolecular interactions among P4VP and free C 60 can be exploited to blend rod-coil block copolymers and C 60 preserving the original lamellar phase.

Atom transfer radical polymerization (ATRP) was used as a versatile route to well-defined poly(diethylhexyl-p-phenylenevinylene-b-styrene) (PPV-b-PS) semiconducting block copolymers. For this purpose, original conjugated macroinitiators were synthesized from DEH-PPV and further used for the copolymerization reaction. The microphase-separated morphologies obtained with the semiconducting PPV-b-PS block copolymer fulfill the basic structural requirements required to build efficient organic photovoltaic devices.