Formation of ordered microphase-separated pattern during spin coating of ABC triblock copolymer

In this paper, the authors have systematically studied the microphase separation and crystallization during spin coating of an ABC triblock copolymer, polystyrene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO). The microphase separation of PS-b-P2VP-b-PEO and the crystallization of PEO blocks can be modulated by the types of the solvent and the substrate, the spinning speed, and the copolymer concentration. Ordered microphase-separated pattern, where PEO and P2VP blocks adsorbed to the substrate and PS blocks protrusions formed hexagonal dots above the P2VP domains, can only be obtained when PS-b-P2VP-b-PEO is dissolved in N,N-dimethylformamide and the films are spin coated onto the polar substrate, silicon wafers or mica. The mechanism of the formation of regular pattern by microphase separation is found to be mainly related to the inducement of the substrate (middle block P2VP wetting the polar substrate), the quick vanishment of the solvent during the early stage of the spin coating, and the slow evaporation of the remaining solvent during the subsequent stage. On the other hand, the probability of the crystallization of PEO blocks during spin coating decreases with the reduced film thickness. When the film thickness reaches a certain value (3.0 nm), the extensive crystallization of PEO is effectively prohibited and ordered microphase-separated pattern over large areas can be routinely prepared.

Triblock poly(lactic acid)-b-poly(ethylene glycol)-b-poly(lactic acid)/paclitaxel conjugates: Synthesis, micellization, and cytotoxicity

A triblock poly(lactic acid)-b-poly(ethylene glycol)-b-poly(lactic acid) (PLA-PEG-PLA)/paclitaxel (PTX) conjugate was synthesized by the reaction of carboxyl-terminated copolymer PLA-PEG-PLA with PTX in the presence of dicyclohexylcarbodiimide and dimethylaminopyridine. Carboxyl-terminated copolymer PLA-PEG-PLA was prepared by the reaction of the hydroxyl end groups in copolymer PLA-PEG-PLA with succinic anhydride. Its structure was confirmed by NMR and gel permeation chromatography. The PLA-PEG-PLA/PTX conjugates could self-assemble into micelles in aqueous solutions with a low critical micelle concentration. Dynamic light scattering and environmental scanning electron microscopy analyses of the PLA-PEG-PLA/PTX micelles revealed their spherical structure and size of 220 nm. The antitumor activity of the conjugate against woman Hela cancer cells, evaluated by the 3-(4,5-dimethylthiazol2-yl)-2,5-diphenyl tetrazolium bromide method, showed that the conjugates had an antitumor activity similar to that of pure PTX. The obtained PLA-PEG-PLA/PTX conjugates are expected to be used in clinical practice.

Supramolecular isomerism in zinc hydroxide coordination polymers with pyridine-2,4-dicarboxylic acid: Two polymorphs with centrosymmetric two-dimensional and acentric three-dimensional coordination networks

Reactions of Zn(BF4)(2) and pyridine-2,4-dicarboxylic acid (2,4-pydcH(2)) in the presence of 1,2-bis( 4-pyridyl) ethylene or 1,3-bis(4-pyridyl) propane under hydro(solvo) thermal conditions yielded two polymorphic metal-organic coordination polymers formulated as Zn-2(OH)(2)(2,4-pydc) (1 and 2). Polymorph 1 features a two-dimensional (2-D) layer-like structure that is constructed by 2,4-pydc ligands bridging between the Zn-OH-Zn double-chain units. Each single Zn-OH-Zn chain is composed of mu(2)-OH groups connecting trigonal bipyramidal and tetrahedral Zn centers. Polymorph 2 is a 3-D coordination polymer containing 2-D Zn-OH-Zn sheets that consist of mu(2)- and mu(3)-OH groups and trigonal bipyramidal Zn centers. The sheets are pillared by 2,4-pydc ligands to form an acentric structural architecture. 1 and 2 are rare examples that the two polymorphs exhibit a centrosymmetric 2-D coordination network and an acentric 3-D coordination network, respectively. The different structures lead to differences in photoluminescent properties and thermal stabilities for 1 and 2.

The combined catalytic action of solid acids with nickel for the transformation of polypropylene into carbon nanotubes by pyrolysis

The effects of both organically modified montmorillonite (OMMT) and Ni2O3 on the carbonization of polypropylene (PP) during pyrolysis were investigated. The results from TEM and Raman spectroscopy showed that the carbonized products of PP were mainly multiwalled carbon nanotubes (MWNTs). Surprisingly, a combination of OMMT and Ni2O3 led to high-yield formation of MWNTs. X-ray powder diffraction (XRD) and GC-MS were used to investigate the mechanism of this combination for the high-yield formation of MWNTs from PP. Bronsted acid sites were created in degraded OMMT layers by thermal decomposition of the modifiers. The resultant carbenium ions play an important role in the carbonization of PP and the formation of MWNTs. The degradation of PP was induced by the presence of carbenium ions to form predominantly products with lower carbon numbers that could be easily catalyzed by the nickel catalyst for the growth of MWNTs. Furthermore, carbenium ions are active intermediates that promote the growth of MWNTs from the degradation products with higher carbon numbers through hydride-transfer reactions. The XRD measurements showed that Ni2O3 was reduced into metallic nickel (Ni) in situ to afford the active sites for the growth of MWNTs.

Polypropylene as a carbon source for the synthesis of multi-walled carbon nanotubes via catalytic combustion

Multi-walled carbon nanotubes (MWCNTs) were efficiently synthesized by catalytic combustion of polypropylene (PP) using nickel compounds (such as Ni2O3, NiO, Ni(OH)(2) and NiCO3 (.) 2Ni(OH)(2)) as catalysts in the presence of organic-modified montmorillonite (OMMT) at 630-830 degrees C. Morphologies of the sample undergoing different combustion times were observed to investigate actual process producing MWCNTs by this method. The obtained MWCNTs were characterized by X-ray diffraction (XRD), transmission electron microscope and Raman spectroscopy. The yield of MWCNTs was affected by the composition of PP mixtures with OMMT and nickel compounds and the combustion temperature. The proton acidic sites from the degraded OMMT layers due to the Hoffman reaction of the modifiers at high temperature played an important role in the catalytic degradation of PP to supply carbon sources that are easy to be catalyzed by nickel catalyst for the growth of MWCNTs. The XRD measurements demonstrated that the nickel compounds were in situ reduced into the Ni(0) state with the aid of hydrogen gas and/or hydrocarbons in the degradation products of PP, and the Ni(O) was really the active site for the growth of MWCNTs. The combination of nickel compounds with OMMT was a key factor to efficiently synthesize MWCNTs via catalytic combustion of PP.

Effect of swelling response of the support particles on ethylene polymerization

Macroporous and modified macroporous poly(styrene-co-methyl methacrylate-co-divinylbenzene) particles (m-PS and mm-PS) supported Cp2ZrCl2 were prepared and applied to ethylene polymerization using methylaluminoxane (MAO) as cocatalyst. The influences of the swelling response of the support particles on the catalyst loading capabilities of the supports as well as on the activities of the supported catalysts were studied. It was shown that the Zr loadings of the supports and the activities of the supported catalysts increased with the swelling extent of the support particles. The m-PS or mm-PS supported catalysts exhibited very high activities when the support particles were well swollen, whereas those catalysts devoid of swelling treatment gave much lower activities. Investigation on the distribution of the supports in the polyethylene by TEM indicated that the swelling of the support particles allowed the fragmentation of the catalyst particles. In contrast, the fragmentation of the support particles with poor swelling was hindered during ethylene polymerization.

Effect of copolymerized ethylene unit on the crystallization behavior of poly(propylene-co-ethylene)s

The crystallization behavior of two kinds of commercial poly(propylene-co-ethylene)s (PPE1, PPE2) with similar average molecular weight and molecular weight distribution, isotacticity and copolymerized ethylene unit content and their fractions was investigated by differential scanning calorimetry (DSC), transmission electron microscopy (TEM) and polarized optical microscopy (POM) techniques. The results indicate that the PPE1 isothermally crystallized films possess thicker and less cross-hatched lamellar structure than those of the PPE2. As for the fractionated samples, the thin films of low temperature (less than or equal to 90 degreesC) fractions (PPE1-80, PPE2-80) of both PPE1 and PPE2 exhibit similar crystallization behavior, while for the high temperature ( greater than or equal to 95 degreesC) fractions (PPE1-108, PPE2-108), the crystalline morphology has marked differences. Compared with PPE2-108, the PPE1-108 isothermally crystallized thin films possess thicker lamellae and less crosshatched lamellar structure, while for the fibrous crystal number, the former is less than that of the latter. The main reason to create the crystallization behavior differences between the two PPEs and their fractions is due to the effect of molecular chain structure, i.e. the different distribution of copolymerized ethylene unit in polypropylene chains.

Crystallization kinetics in shearing-induced oriented and stretched poly(ethylene oxide)

Isothermal crystallization kinetics in the melting of poly(ethylene oxide) (PEO) were investigated as a function of the shear rate and crystallization temperature by optical microscopy. The radial growth rates of the spherulites are described by a kinetics equation including shearing and relaxation combined effects and the free energy for the formation of a secondary crystal nucleus. The free-energy difference between the liquid and crystalline phases increased slightly with rising shearing rates. The experimental findings showed that the influence of the relaxation of PEO, which is related to the shear-induced orientation and stretch in a PEO melt, on the rate of crystallization predominated over the influence of the shearing. This indicated that the relaxation of PEO should be more important so that the growth rates increase with shearing, but it was nearly independent of the shear rate within the measured experimental range.

Mechanical and thermal properties of glass bead-filled nylon-6

The mechanical and thermal properties of glass bead-filled nylon-6 were studied by dynamic mechanical analysis (DMA), tensile testing, Izod impact, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) tests. DMA results showed that the incorporation of glass beads could lead to a substantial increase of the glass-transition temperature (T-g) of the blend, indicating that there existed strong interaction between glass beads and the nylon-6 matrix. Results of further calculation revealed that the average interaction between glass beads and the nylon-6 matrix deceased with increasing glass bead content as a result of the coalescence of glass beads. This conclusion was supported by SEM observations. Impact testing revealed that the notch Izod impact strength of nylon-6/glass bead blends substantially decreased with increasing glass bead content. Moreover, static tensile measurements implied that the Young's modulus of the nylon-6/glass bead blends increased considerably, whereas the tensile strength clearly decreased with increasing glass bead content.

Zirconocene catalyst well spaced inside modified montmorillonite for ethylene polymerization: role of pretreatment and modification of montmorillonite in tailoring polymer properties

Zirconocene catalyst was heterogenized inside an organosilane-modified montmorillonite (MMT) pretreated by calcination and acidization, for supported catalyst systems with well-spaced alpha-olefin polymerization active centers. The varied pretreatment and modification conditions of montmorillonite are efficient for supported zirconocene catalysts in control of polyethylene microstructures, in particular, molecular weight distribution. In contrast to other supported catalyst systems, Cp2ZrCl2/modified montmorillonite(MMT-7)-supported catalysts with a distinct interlayer structure catalyzed ethylene homopolymerization and copolymerization with I-octene activated by methylaluminoxane (MAO), resulting in polymers with a bimodal molecular weight distribution (MWD).

An infrared study on Langmuir-Blodgett films of octadecylammonium octadecanoate: FWHM and the vibrational coupling

The monolayer of the mixture of octadecanoic acid and octadecylamine with molar ratio 1: 1 has been investigated at the air-water interface. It was found that the monolayer shows a rather stable state at the surface pressure of 30 mN/m and this monolayer can be transferred onto a CaF2 plate by Langmuir-Blodgett (LB) technique. The infrared spectra of LB films indicated that octadecyl ammonium octadecanoate is formed by an intermolecular proton exchange between adjacent carboxylic and aminic groups (COO- and NH3+). In three-layer LB film, the CH2 scissoring mode of the long hydrocarbon chains of octadecyl ammonium octadecanoate shows a broad band feature at about 1468 cm(-1) while this vibrational mode of three-layer LB film of the mixture (1: 1) of deuterated stearic acid and octadecylamine (octadecylammonium octadecanoate-d35, C18H37NH3+C17D35COO-) only shows a narrow band. The broad feature of the CH2 scissoring mode in octadecylammonium octadecanoate probably originates from the coupling between the chain of stearic acid and that of octadecylamine while this kind of coupling could be completely removed in octadecylammonium octadecanoate-d35.

Conductive property of multiwall carbon nanotubes-PEO-salt nanocomposite film

By adding a small amount of multiwall carbon nanotubes (MWNTs) to polyethylene oxide (PEO) and a salt system, a new type of nanocomposite film was constructed. At ambient temperature, the conductivity of the PEO-salt-0.5 wt % MWNTs was nearly three orders of magnitude higher than that of the PEO-salt system. The conductive property of the nanocomposite film was characterized by ac impedance and the differential scanning calorimetry technique.

Thermal and dynamic mechanical properties of PES/PPS blends

Blends of poly(ether-sulfone) (PES) and poly(phenylene sulfide) (PPS) with various compositions were prepared using an internal mixer at 290degreesC and 50 rpm for 10 min. The thermal and dynamic mechanical properties of PES/PPS blends have been investigated by means of DSC and DMA. The blends showed two glass transition temperatures corresponding to PPS-rich and PES-rich phases. Both of them decreased obviously for the blends with PES matrix. On the other hand, T-g of PPS and PES phase decreased a little when PPS is the continuous phase. In the blends quenched from molten state the cold crystallization temperature of PPS was detected in the blends of PES/PPS with mass ratio 50/50 and 60/40. The melting point, crystallization temperature and the crystallinity of blended PPS were nearly unaffected when the mass ratio of PES was less than 60%, however, when the amount of PES is over 60% in the blends, the crystallization of PPS chains was hindered. The thermal and the dynamic mechanical properties of the PPS/PES blends were mainly controlled by the continued phase.

New titanium complexes with two beta-enaminoketonato chelate ligands: Syntheses, structures, and olefin polymerization activities

New titanium complexes with two nonsymmetric bidentate beta-enaminoketonato (N,O) ligands (4a-e), [(Ph)NC(R-2)C(H)C(R-1)O](2)TiCl2, have been synthesized. X-ray crystal structure reveals that complex 4a has a C-2-symmetric conformation with a distorted octahedral geometry around the titanium center. With modified methylaluminoxane (MMAO) as a cocatalyst, complexes 4a-e are active catalysts for ethylene polymerization at room temperature, producing high molecular weight polyethylenes bearing linear structures. The 4a,b/MMAO catalyst systems exhibit the characteristics of a quasi-living polymerization of ethylene, producing polyethylenes with narrow molecular weight distributions. Moreover, the 4a-d/MMAO catalyst systems are also capable of promoting the quasi-living copolymerization of ethylene with norbornene at room temperature, yielding high molecular weight alternating copolymers with narrow molecular weight distributions. The quasi-living nature of the catalysts allows the synthesis of new A-B polyethylene-block-poly(ethylene-conorbornene) diblock copolymer.