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1.
Stephanie Hoeppener Frank Wiesbrock Richard Hoogenboom Hanneke M. L. Thijs Ulrich S. Schubert 《Macromolecular rapid communications》2006,27(6):405-411
Summary: The influence of surface morphologies on the properties of materials is of essential importance and is therefore a widely discussed topic. In the present contribution, the properties of a set of diblock copoly(2‐oxazoline)s are analyzed in terms of their individual morphologies, which have been investigated with tapping‐mode SFM. This collection of diblock copolymers consists of 12 diblock copolymers and four corresponding homopolymers, representing a complete 16‐membered library of (co‐) poly(2‐oxazoline)s, composed of four differently substituted 2‐oxazoline monomers. For the investigated set of compounds, a correlation between the morphologies of the spin‐coated films and their surface energies could be determined.
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Moon Suk Kim Kwang Su Seo Gilson Khang Hai Bang Lee 《Macromolecular rapid communications》2005,26(8):643-648
Summary: The polymerization of ε‐caprolactone (CL) in the presence of HCl · Et2O by an activated monomer mechanism was performed to synthesize diblock or triblock copolymers composed of poly(ethylene glycol) (PEG) and poly(ε‐caprolactone) (PCL). The obtained PCLs had molecular weights close to the theoretical values calculated from the CL to PEG molar ratios and exibited monomodal GPC curves. We successfully prepared PEG and PCL block copolymers by a metal‐free method.
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Akihiro Yokoyama Tomohiro Masukawa Yuka Yamazaki Tsutomu Yokozawa 《Macromolecular rapid communications》2009,30(1):24-28
Well‐defined diblock condensation copolymers composed of an aromatic polyamide and an aromatic polyether have been synthesized by means of successive chain‐growth condensation polymerizations. Polymerization of a polyamide monomer with an orthogonally difunctional initiator is accompanied with side reactions. On the other hand, polymerization with a monofunctional initiator afforded well‐defined polyamide, which has been converted into a macroinitiator by introduction of a terminal 4‐fluorobenzophenone unit. Well‐defined diblock copolymers are obtained by polymerization of a polyether monomer in the presence of this macroinitiator.
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Xingqing Xiao Yongmin Huang Jian Feng Honglai Liu Ying Hu 《Macromolecular theory and simulations》2011,20(2):124-132
The microstructure of a diblock copolymer dispersed in nanorod arrays grafted on a plate are investigated via annealing MC simulation. The confinement in nanorod arrays provides a complex confined space which leads to complicated microphase separation structures. Different morphologies of top and bottom of the film in the nanorod arrays are observed by varying the inducing height of nanorod and its grafting density in the bottom. Due to a short inducing range by the nanorods, the top structures are therefore mainly dominated by the competition between the absolute height of off‐induced layer on the top and the nature of block copolymer itself; while the bottom structures are affected by the symmetry of block copolymer and the gap among rods.
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Ian W. Hamley Ben M. D. O'Driscoll Gudrun Lotze Claire Moulton Jürgen Allgaier Henrich Frielinghaus 《Macromolecular rapid communications》2009,30(24):2141-2146
The phase diagram of a series of poly(1,2‐octylene oxide)–poly(ethylene oxide) (POO–PEO) diblock copolymers is determined by small‐angle X‐ray scattering. The Flory–Huggins interaction parameter was measured by small‐angle neutron scattering. The phase diagram is highly asymmetric due to large conformational asymmetry that results from the hexyl side chains in the POO block. Non‐lamellar phases (hexagonal and gyroid) are observed near fPEO = 0.5, and the lamellar phase is observed for fPEO ≥ 0.5.
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Morgan Tizzotti Aurelia Charlot Etienne Fleury Martina Stenzel Julien Bernard 《Macromolecular rapid communications》2010,31(20):1751-1772
This review covers the literature concerning the modification of polysaccharides through controlled radical polymerizations (NMP, ATRP and RAFT). The different routes to well‐defined polysaccharide‐based macromolecules (block and graft copolymers) and graft‐functionalized polysaccharide surfaces as well as the applications of these polysaccharide‐based hybrids are extensively discussed.
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Zi‐Tong Liu Yan‐Mei He Bao‐Lin Li Ji Liu Qing‐Hua Fan 《Macromolecular rapid communications》2007,28(23):2249-2255
A new kind of chiral‐dendronized binaphthyl‐containing polyfluorene derivatives has been synthesized through “click chemistry” efficiently. The resulting copolymers exhibited desirable properties, such as excellent solubility, good thermal stability, and considerably high molecular weights. The photophysical properties of the copolymers were investigated in details, and the results indicated that the combination of chiral binaphthyl unit and bulky dendron could effectively suppress intermolecular packing and aggregation. In addition, the investigation of circular dichroism behavior of these chiral‐dendronized copolymers showed a strong Cotton effect at long wavelength (373–379 nm), indicating that the chirality of the binaphthyl units was transferred to the whole polyfluorene backbone.
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Andreas John Peter Friedel Doris Pospiech Dieter Jehnichen Christoph Kunert 《Macromolecular theory and simulations》2004,13(8):702-710
Summary: A modified random phase approximation method with a cumulant expansion for the semi‐flexible structure factor of diblock copolymers was exercised to describe the phase separation behavior of semi‐flexible and polydisperse diblock copolymers. Scattering curves and spinodal diagrams were calculated applying monomer specific input parameters. The influence of polydispersity was included applying basic concepts of mathematical statistics utilizing several probability density distributions in the case of the two single blocks. In contrast to semi‐flexibility, the main effect of polydispersity was found to shift the spinodal up, thus to enlarge the range of existence of the homogeneous phase.
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A series of well‐defined rod‐coil PAA‐b‐DPS block copolymers, containing Fréchet‐type dendronized polystyrene (DPS) with different generation as a rod‐like hydrophobic block and poly(acrylic acid) (PAA) as a hydrophilic coil were synthesized. The procedure included the following steps: the precursor PMA‐b‐DPS copolymer was prepared through ATRP of Fréchet‐type dendritic styrene macromonomer bearing the first to the third generation (G1–G3), respectively, initiated by poly(methyl acrylate) (PMA‐Br). Then, by converting PMA into PAA by subsequent hydrolysis, the targeted amphiphilic copolymers were obtained. Moreover, by using the rod‐coil amphiphiles as building blocks, large compound micelles and vesicles were formed in a binary solvent mixture of DMF/H2O. Morphological changes in self‐assembly showed dependence on the length of the dendronized block.
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Sandra Demel Christian Slugovc Franz Stelzer Katalin Fodor‐Csorba Giancarlo Galli 《Macromolecular rapid communications》2003,24(10):636-641
Perfectly alternating copolymers can be synthesised by reacting diacrylates with terminal dienes using alternating diene metathesis polycondensation (ALTMET). This novel method is very versatile and allows preparation of diverse structures of polymers, including main‐chain liquid crystalline polymers.
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Caixia Cheng Ye Tian Yanqiao Shi Rupei Tang Fu Xi 《Macromolecular rapid communications》2005,26(15):1266-1272
Summary: Fabrication of honeycomb‐patterned films from amphiphilic dendronized block copolymer (PEO113‐b‐PDMA82) by ‘on‐solid surface spreading’ and ‘on‐water spreading’ method is reported. Highly ordered honeycomb films with quasi‐horizontally paralleled double‐layered structure can be fabricated by the on‐solid surface spreading method. This work raises the possibility that such structures can be formed in amphiphilic dendronized block copolymers and extends the family of source materials.
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Summary: Dissipative particle dynamics simulations are performed on the distribution of binary nanoparticle mixtures in lamellar diblock copolymers. The results show that the self‐assembly of nanoparticle mixtures in polymer matrix is a cooperative assembly that is affected by various factors, providing molecular‐level information for the rational design of new polymer nanocomposites with tailored properties.
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Li Lin Zeng Yan Junsi Gu Yuanyuan Zhang Ze Feng Yanlei Yu 《Macromolecular rapid communications》2009,30(13):1089-1093
A novel amphiphilic diblock copolymer composed of a hydrophilic poly(ethylene oxide) and a hydrophobic polymethacrylate with photochromic azopyridine moieties in the side groups was synthesized by atom transfer radical polymerization. The copolymeric vesicles showed photoinduced circular process including fusion, damage and defect formation, disruption, disintegration and rearrangement in H2O/THF during the irradiation of UV light. The process of photoresponsive cycle can be inhibited at any moment by visible light.
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A new versatile synthesis strategy for macromonomers has been developed that uses the living ring‐opening metathesis polymerization (ROMP) with commercial Grubbs first generation ruthenium initiators. Homopolymers as well as diblock copolymers were end‐functionalized with norbornene derivatives to serve as macromonomers. The graft copolymerization of the macromonomers was also carried out employing ROMP. Well‐defined and highly functional graft copolymers are accessible by this new synthetic route.
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The formation of superlattices in blends of a series of asymmetric BSV triblock terpolymers and symmetric SV or VC diblock copolymers is investigated with S being polystyrene, B being poly(1,2‐butadiene), V being poly(2‐vinylpyridine), and C being poly(cyclohexyl methacrylate). All of these triblock terpolymers and diblock copolymers by themselves self‐assemble into lamellae. Apart from various core shell morphologies, in these blends some new unexpected superstructures were obtained.
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Anna Tsimelzon David Deamer Rebecca Braslau 《Macromolecular rapid communications》2005,26(23):1872-1877
Summary: An initiator for nitroxide mediated ‘living’ free radical polymerization was prepared with a fluorescent tag attached to the initiating alkyl radical terminus. This was used to synthesize amphiphilic poly(acrylic acid)‐block‐polystyrene diblock copolymers, which self assembled in a tetrahydrofuran/buffer solution to form structures that are visible by fluorescence.
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Hongge Tan Qinggong Song Shuang Yang Dadong Yan An‐Chang Shi 《Macromolecular theory and simulations》2008,17(1):45-51
In this paper, we study the morphology of diblock copolymers with the body‐centered‐cubic (bcc) phase confined between two flat surfaces. Employing the Landau–Brazovskii mean field theory and the single mode approximation, we obtain three amplitude parameters as functions of temperature, surface field strength, and film thickness. Because of the effect of confinement size and the surface inducement, the morphology of confined diblock copolymers is different from the bulk structure. By controlling confinement size and surface field strength, lamella, undulated lamella, cylinder, and distorted cylinder can be observed in the bcc bulk phase of diblock copolymers. Also, we construct a “phase diagram” of confinement‐induced structures at different surface field strengths. We compare the present theoretical results with the other relevant theoretical results. The predictions about these interesting confinement‐induced structures should be observable in the experiments under suitable conditions.