Effect of binary block-selective solvents on self-assembly of ABA triblock copolymer in dilute solution

We have studied the self-assembly of the ABA triblock copolymer (P4VP-b-PS-b-P4VP) in dilute solution by using binary block-selective solvents, that is, water and methanol. The triblock copolymer was first dissolved in dioxane to form a homogeneous solution. Subsequently, a given volume of selective solvent was added slowly to the solution to induce self-assembly of the copolymer. It was found that the copolymer (P4VP(43)-b-PS366-b-P4VP(43)) tended to form spherical aggregate or bilayer structure when we used methanol or water as the single selective solvent, respectively.

The study of synthesis of poly(ethylene oxide)-b-poly(N,N-dimethylacrylamide) by atom transfer radical polymerization and self-assembly in selective solvents

Poly( ethylene oxide)-b-poly(N, N-dimethylacrylamide) (PEO-b-PDMA) was synthesized by successive atom transfer radical polymerization (ATRP) of N, N-dimethylacrylamide (DMA) monomer using PEO-Br macro initiators as initiator, CuBr and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazamacrocyclotetra decane (Me-6[14] aneN(4)) as catalyst and ligand. PEO-Br macroinitiator was synthesized by esterification of PEO with 2-bromoisobutyryl bromide. GPC and H-1 NMR studies show that the plot of ln([DMA](0)/[ DMA]) against the reaction time is linear, and the molecular weight of the resulting PDMA increased linearly with the conversion. Within 3 h, the polymerization can reach almost 60% of conversion. PEO-b-PDMA copolymer with low polydispersity index (M-w/M-n approximate to 1.1) is obtained. Self-assembly of PEO-b-PDMA in selective solvents is also studied. It could self-assemble into micelles in methanol/acetone (1/10, v/v) solution. TEM analyses of the PEO-b-PDMA micelles with narrow size distribution revealed that their size and shape depend much on the copolymer composition.

Syntheses and Self-Assembling Characteristics of Amphiphilic Star Diblock Copolymers

Uusien polymeeripohjaisten teknologioiden ja materiaalien myötä räätälöityjen polymeerien tarve on kasvanut. Viime vuosituhannen lopussa kehitetyt kontrolloidut polymerointimenetelmät ovat avanneet uusia mahdollisuuksia paitsi monimutkaisten polymeerien synteesiin, myös itsejärjestyvyyteen perustuvien funktionaalisten nanorakenteiden suunnitteluun ja valmistukseen. Nämä voivat jäljitellä luonnossa esiintyviä rakenteita, joita muodostavat esimerkiksi lipidit ja proteiinit. Itsejärjestyvät molekyylit ovat usein amfifiilisiä eli ne koostuvat hydrofiilisistä ja hydrofobisista osista ja polymeereissä nämä osat voivat olla omina lohkoinaan, jolloin puhutaan amfifiilisistä lohko- tai blokkikopolymeereistä. Riippuen järjestyneiden rakenteiden koostumuksesta ja muodosta, amfifiilisiä blokkikopolymeerejä on tutkittu tai jo käytetty nanoteknologiassa, elastomeereissä, voiteluaineissa, pinta-aktiivisina aineina, lääkkeenannostelussa, maaleissa, sekä elektroniikka-, kosmetiikka- ja elintarviketeollisuudessa. Tavallisimmin käytetyt amfifiiliset blokkikopolymeerit ovat olleet lineaarisia, mutta viime aikoina tutkimus on suuntautunut kohti monimutkaisempia rakenteita. Tällaisia ovat esimerkiksi tähtipolymeerit. Tähtimäisissä polymeereissä miselleille tyypillinen ydin-kuori-rakenne säilyy hyvin alhaisissakin polymeerikonsentraatioissa, koska polymeeriketjut ovat kiinni toisissaan yhdessä pisteessä. Siten ne ovat erityisen kiinnostavia tutkimuskohteita erilaisten hydrofobisten orgaanisten yhdisteiden sitomiseksi ja vapauttamiseksi. Tässä työssä on tarkasteltu amfifiilisten tähtipolymeerien itsejärjestymistä vesiliuoksissa sekä kokeellisesti ja tietokonesimulaatioin. Työ koostuu kahdesta osasta: tähtipolymeerien synteesistä makrosyklisillä initiaattoreilla ja amfifiilisten tähtimäisten blokkikopolymeerien ominaisuuksien tutkimisesta.

Study of controllable aggregation morphology of ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property

We have studied, both experimentally and theoretically, the aggregation morphology of the ABA amphiphilic triblock copolymer in dilute solution by changing the solvent property. Experimental results showed that the micellar morphology changed from spheres to rods and then to vesicles by changing the common solvent from N-N-dimethylformamide (DMF) to dioxane and then to tetrahydrofuran (THF). These controllable aggregates were also obtained by Monte Carlo simulation. The simulative results showed that the solvent property is a key factor that determines the copolymer aggregation morphology. The morphology changed from spheres to rods and then to vesicles by increasing the solvent solubility, corresponding to the change of stretched of the copolymer chains in the micellar cores. This result is in good agreement with the experimental one. Moreover, the simulative results revealed that the end-to-end distant of the ABA triblock copolymer in the vesicle was larger than that in the spheres and rods, indicating that the copolymer chains were more stretched in vesicles than in the spheres and rods. Furthermore, we gave the distribution of the fraction of the chain number with the end-to-end distance. The results indicated that the amount of folded chains is almost the same as that of stretched chains in the vesicle. Although most chains were folded, stretched chains could be found in the rod and sphere micelles.

Motion of integrated CdS nanoparticles by phase separation of block copolymer brushes

A new method of reversibly moving US nanoparticles in the perpendicular direction was developed on the basis of the phase separation of block copolymer brushes. Polystyrene-b-(poly(methyl methaerylate)-co-poly(cadmium dimethacrylate)) (PS-b-(PMMA-co-PCdMA)) brushes were grafted from the silicon wafer by surface-initiated atom transfer radical polymerization (ATRP). By exposing the polymer brushes to H2S gas, PS-b-(PMNlA-co-PCdNlA) brushes were converted to polystyrene-b-(poly(methyl methacrylate) -co-poly(methacrylic acid)(CdS)) (PS-b-(PMMA-co-PMAA(CdS))) brushes, in which US nanoparticles were chemically bonded by the carboxylic groups of PMAA segment. Alternating treatment of the PS-b-(PMMA-co-PMAA(CdS)) brushes by selective solvents for the outer block (a mixed solvent of acetone and ethanol) and the inner PS block (toluene) induced perpendicular phase separation of polymer brushes, which resulted in the reversible lifting and lowering of US nanoparticles in the perpendicular direction. The extent of movement can be adjusted by the relative thickness of two blocks of the polymer brushes.

Solvent-induced microphase separation in diblock copolymer thin films with reversibly switchable morphology

We have studied the surface morphology of symmetric poly(styrene)-block-poly(methyl methacrylate) diblock copolymer thin films after solvent vapor treatment selective for poly(methyl methacrylate). Highly ordered nanoscale depressions or striped morphologies are obtained by varying the solvent annealing time. The resulting nanostructured films turn out to be sensitive to the surrounding medium, that is, their morphologies and surface properties can be reversibly switchable upon exposure to different block-selective solvents.

Patterned self-adaptive polymer brushes by "grafting to" approach and microcontact printing

Patterned self-adaptive PS/P2VP mixed polymer brushes were prepared by "grafting to" approach combining with microcontact printing (muCP). The properties of the patterned surface were investigated by lateral force microscopy (LFM), XPS and water condensation figures. In the domains with grafted P2VP, the PS/P2VP mixed brushes demonstrated reversible switching behavior upon exposure to selective solvents for different components. The chemical composition of the top layer as well as the surface wettability can be well tuned due to the perpendicular phase segregation in the mixed brushes. While in the domains without grafted P2VP, the grafted PS did not have the capability of switching. The development and erasing of the pattern is reversible under different solvent treatment.

Inverted to normal phase transition in solution-cast polystyrene-poly(methyl methacrylate) block copolymer thin films

We have investigated the inverted phase formation and the transition from inverted to normal phase for a cylinder-forming polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer in solution-cast films with thickness about 300 nm during the process of the solution concentrating by slow solvent evaporation. The cast solvent is 1, 1,2,2-tetrachloroethane (Tetra-CE), a good solvent for both blocks but having preferential affinity for the minority PMMA block. During such solution concentrating process, the phase behavior was examined by freeze-drying the samples at different evaporation time, corresponding to at different block copolymer concentrations, phi. As phi increases from similar to 0.1 % (nu/nu), the phase structure evolved from the disordered sphere phase (DS), consisting of random arranged spheres with the majority PS block as I core and the minority PMMA block as a corona, to ordered inverted phases including inverted spheres (IS), inverted cylinders (IC), and inverted hexagonally perforated lamellae (IHPL) with the minority PMMA block comprising the continuum phase, and then to the lamellar (LAM) phase with alternate layers of the two blocks, and finally to the normal cylinder (NC) phase with the majority PS block comprising the continuum phase. The solvent nature and the copolymer solution concentration are shown to be mainly responsible for the inverted phase formation and the phase transition process.

A polymer composite film with reversible responsive behaviors

A responsive polymer composite film was generated by the use of reversibly switchable Surface morphology of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) films in response to different block selective solvents on the rough isotactic poly(propylene) (i-PP) substrate. The Maximum difference of the water contact angle of the composite films increased from 22.6 degrees of PS-b-PMMA films on the smooth substrate to 42.6 degrees when they were treated by PS and PMMA selective solvents, respectively. The mechanisms of the responsive extent enhanced and the superhydrophobicity of the composite films were discussed in detail.

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

Linear block copolymers of L–lactide and 2–dimethylaminoethyl methacrylate : synthesis and properties

Part of the research described in this thesis is conducted in collaboration with Centre d' étude et de Recherche sur les Macromolécules (CERM), Université de Liège, Sart-Tilman, Belgium

Nanopartikel durch Strukturfixierung mizellarer Assoziate aus amphiphilen, endgruppenfunktionalisierten Diblockcopolymeren

Nanopartikel durch Strukturfixierung mizellarer Assoziate aus amphiphilen, endgruppenfunktionalisierten Diblockcopolymeren Zwei unterschiedliche Diblockcopolymersysteme mit Molmassen unterhalb von Mw = 10 000 g/mol wurden über anionische Polymerisation synthetisiert. Ein hetero-telecheles a,w-Poly(dimethylsiloxan)-b-Poly(ethylenoxid) (PDMS-PEO) Diblockcopolymer wurde mit einer Methacrylatendgruppe am PDMS und entweder einer Benzyl-, Hydroxy- oder Carboxylatendgruppe am PEO funktionalisiert. Ein Poly(butadien)-b-Poly(ethylenoxid) (PB-PEO) Diblockcopolymer wurde am PEO ebenfalls entweder mit einer Benzyl-, Hydroxy- oder Carboxylatendgruppe funktionalisiert. In selektiven Lösungsmitteln wie Wasser oder Methanol bilden beide Diblockcopolymersysteme supramolekulare Strukturen mit sphärischer, zylindrischer oder toroider Geometrie aus, die mit statischer und dynamischer Lichtstreuung in Lösung und mit Rasterkraftmikroskopie (AFM) und Transmissionselektronenmikroskopie (TEM) auf der Oberfläche untersucht wurden. Durch Zusatz eines Vernetzers und Initiators wurden die selbstassoziierenden Mizellen des PDMS-PEO Diblockcopolymers permanent durch radikalische Polymerisation mit UV-Licht fixiert. Mizellen des PB-PEO Diblockcopolymers wurden über Bestrahlung mit gamma-Strahlen permanent fixiert. Die Untersuchung der resultierenden Nanopartikel beider Diblockcopolymersysteme mit AFM und TEM zeigte, daß diese sogar in nicht selektiven Lösungsmitteln wie Tetrahydrofuran formstabil bleiben.

Remarkable isomer-selective gelation of aromatic solvents by a polymorph of a urea-linked bile acid-amino acid conjugate

We report an unusual, isomer-selective gelation of aromatic solvents by a polymorph of a urea-linked bile acid-amino acid conjugate. The gelator showed selectivity towards gelation of 1,2-disubstituted aromatic solvents.

Selective Homonuclear Decoupling in H-1 NMR: Application to Visualization of Enantiomers in Chiral Aligning Medium and Simplified Analyses of Spectra in Isotropic Solutions

The proton NMR spectral complexity arising due to severe overlap of peaks hampers their analyses in diverse situations, even by the application of two-dimensional experiments. The selective or complete removal of the couplings and retention of only the chemical shift interactions in indirect dimension aids in the simplification of the spectrum to a large extent with little investment of the instrument time. The present study provides precise enantiodiscrimination employing more anisotropic NMR parameters in the chiral liquid crystalline medium and differentiates the overlapped peaks of many organic molecules and peptides dissolved in isotropic solvents.