The Synthesis of Poly(ethylene oxide)-Block-Polybutylacrylate

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Poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene)oxide triblock copolymers at the water/air interface and in foam films

The behavior of commercial poly(ethylene oxide)(PEO)–poly(propylene oxide)(PPO)–PEO triblock copolymers at the water/air interface and in microscopic foam films is studied. In aqueous solution these amphiphilic nonionic substances exhibit a surfactant-like aggregation and adsorption behavior. Even below the critical micelle concentration (cmc) the surface concentration is so high that the PEO chains are squeezed and protrude into the solution in order to accommodate to the situation at the interface. As evidenced by measurements of the ellipticity of light reflected from the free surface of the solution a PEO brush is created at the fluid interface. The microscopic foam film is used as a tool for investigating the normal interaction between two PEO brushes facing each other. Stable foam films are obtained at concentrations below the cmc and steric repulsion predominates (in 0.1 M NaCl). A brush-to-brush contact is established only at higher capillary pressures and the disjoining pressure isotherm follows de Gennes' scaling prediction. At lower pressure a softer steric repulsion occurs. It is governed by the bulk copolymer concentration and hence is fundamentally different from the brush-to-brush repellency. On the whole PEO–PPO–PEO copolymers behave as nonionic surfactants, but the large size of their molecules exemplifies the excluded-volume features. Received: 13 July 1999/Accepted: 27 July 1999     

Pyrolysis kinetics of ethylene–propylene (EPM) and ethylene–propylene–diene (EPDM)

The thermal degradation kinetics of several ethylene–propylene copolymers (EPM) and ethylene–propylene–diene terpolymers (EPDM), with different chemical compositions, have been studied by means of the combined kinetic analysis. Until now, attempts to establish the kinetic model for the process have been unsuccessful and previous reports suggest that a model other than a conventional nth order might be responsible. Here, a random scission kinetic model, based on the breakage and evaporation of cleavaged fragments, is found to describe the degradation of all compositions studied. The suitability of the kinetic parameters resulting from the analysis has been asserted by successfully reconstructing the experimental curves. Additionally, it has been shown that the activation energy for the pyrolysis of the EPM copolymers decreases by increasing the propylene content. An explanation for this behavior is given. A low dependence of the EPDM chemical composition on the activation energy for the pyrolysis has been reported, although the thermal stability is influenced by the composition of the diene used.     

Selective assembly of cyclodextrins on poly(ethylene oxide)–poly(propylene oxide) block copolymers

This paper presents a computational study on the formation of a molecular necklace formed by specific threading of cyclodextrins (CDs) on block copolymers. Structural as well as energetic principles for the selective complexation of - and -cyclodextrin with poly(ethylene oxide)–poly(propylene oxide) block copolymers (PEO–PPO) are elucidated considering a diblock copolymer of equimolecular composition (PEO)4–(PPO)4 as guest. A non-statistical distribution of CDs, i.e. -CDs primarily located on the PEO chain and -CDs on PPO blocks of the polymer, is based on a variety of structural features and energetic preferences considering both potential as well as solvation energies. This selectivity becomes already obvious considering 1:1 complexes between PEO and PPO monomers and the two CDs, but is increasingly evident when calculating higher order ensembles. Besides the host–guest interaction, docking between CDs themselves is an important, also non-statistical, prerequisite for the self-assembly of highly ordered tubes. The formation of intermolecular hydrogen bonds between adjacent CDs in a tubular aggregate gives an important contribution to the overall stability of the molecular necklace. The net effect, based on the preferential interaction between host and guest as well as between the host molecules themselves, results in the formation of a stable, highly ordered macromolecular, multicomponent aggregate.     

Synthesis and Characterization of C60-Containing Poly（ethylene oxide）

C60-Containing poly(ethylene oxide) (PEO) was synthesized by a new method.Molecular structural characterization for the polymers was presented by ^1H-NMR, infrared and UV-Vis spectra.     

Enthalpy of mixing in the propylene oxide–dimethylformamide and propylene oxide–ethylene glycol systems

Heat of mixing of propylene oxide with N,N-dimethylformamide and ethylene glycol has been determined by means of microcalorimetry. Theoretically suggested choice of the aprotic solvent as a selective separating agent for the propylene oxide–methanol binary mixture has been experimentally justified.     

Synthesis and Reactivity of α-Bromo-4-(difluoromethylthio)acetophenone

A synthesis is reported for -bromo-4-difluoromethylthioacetophenone and the conditions for the condensation of this compound with 2-aminothiazole, 2-amino-5-chloropyridine, 2-amino-4,5-dihydro-3H-pyrrole, benzimidazoline-2-thione, oxadiazoline-2-thione, and thiourea were studied. S- and N-substituted azaheterocycles containing the 4-(difluoromethylthio)phenyl fragment were synthesized and characterized.     

Synthesis and Reactivity of (β-Amino-α-acylalkenyl)phenyliodonium Salts

During the last few years alkenyl(phenyl)iodonium salts have risen from mere chemical curiosities to valuable synthetic intermediates. [1] Because of an excellent leaving group ability of a phenyliodonyl moiety, alkenyl(phenyl) iodonium salts undergo nucleophilic vinyl substitutions under mild conditions, thus providing a useful route for the synthesis of various kinds of olefins. Recently, some of functionalized alkenyl iodonium salts have been prepared. [2]     

Enantiospecific Synthesis of (–)-Cuspareine and (–)-Galipinine

An enantiospecific route to the synthesis of tetrahydroquinoline alkaloids (–)-cuspareine and (–)-galipinine is reported. Coupling of an iodide derivative of D-serine with aromatic dithianes and Pd-catalyzed intramolecular C–N coupling are the key steps in the synthesis.     

Synthesis and Reactivity of β-Carboline-Hydantoin Systems

The synthesis of 2,5-disubstituted 1,3-dioxo-6H-1,2,3,5,11,11a-hexahydroimidazo[1, 5-b]-β-3a-y and the reduction of carbolines 3m-r with different amounts of lithium aluminium hydride is described.     

Synthesis and Characterization of Triblock Terpolymers with three Potentially Crystallisable Blocks: Polyethylene-b-poly(ethylene oxide)-b-poly(ε-caprolactone)

A first attempt was made to produce novel ABC triblock terpolymers with three potentially crystallisable blocks: polyethylene (PE), poly(ethylene oxide) (PEO), and poly(ε-caprolactone) (PCL). Polybutadiene-b-poly(ethylene oxide) diblock copolymers were synthesized by living anionic polymerization. Then, a non-catalyzed thermal polymerization of ε-caprolactone from the hydroxyl end group of the PB-b-PEO diblock precursors was performed. Finally, hydrogenation by Wilkinson catalyst produced PE-b-PEO-b-PCL triblock terpolymers. Side reactions were detected that lead to the formation of undesired PCL-b-PEO diblock copolymers, however, these impurities were successfully removed by purification. A range of triblock terpolymers with PCL and PEO minor components were prepared. Topological restrictions on the PEO middle block prevented this block from crystallizing while the complex crystallization behavior of the PE and PCL blocks was documented by DSC and WAXS measurements.     

Microwave-Assisted Synthesis of Poly(ε-caprolactone)-block-poly(ethylene glycol) and Poly(lactide)-block-poly(ethylene glycol)

Summary: This study reported the preparation and characterization of PCL-b-mPEG (poly(ε-caprolactone)-block-poly(ethylene glycol)) and PLL-b-mPEG (poly(L-lactide)-block-poly(ethylene glycol)) diblock copolymers by microwave heating and comparison of resulted products the ones with prepared by conventional heating. Diblock copolymers were synthesized successfully by the microwave-assisted ROP in the presence of stannous octoate (SnOct₂) as catalyst under nitrogen atmosphere in different monomer ratios. Structural and functional characterization of copolymers were performed by FTIR, ¹H-NMR and DSC. Molecular weight values were determined by GPC and also calculated from ¹H-NMR. According to the results, microwave irradiation allowed to obtain polymers with very narrow size distribution in very short reaction time. Similar polymers prepared by conventional heating were also synthesized for comparison. Molecular weight and conversion of polymers were increased by irradiation time. This change was continued until a certain time point after which no more increase was observed. It was concluded that microwave irradiation is a succesful method to obtain these diblock copolymers in very short reaction time and with a similar conversion obtained by conventional method.     

Poly(ethylene oxide)–poly(ethylene imine) block copolymers as templates and catalysts for the in situ formation of monodisperse silica nanospheres

Block copolymers based on poly(ethylene oxide) (PEO) and poly(ethylene imine) (PEI) are efficient catalysts/templates for the formation of uniform silica nanoparticles. Addition of tetraethylorthosilicate to a solution of PEO–PEI or PEI–PEO–PEI block copolymers results in the formation of silica particles with a diameter of ca. 30 nm and narrow size distribution. The particles precipitated with the diblock copolymers can be redispersed in water after isolation as individual nanoparticles. Evidently, block copolymers based on PEO and PEI serve as excellent templates for the biomimetic and “soft” synthesis of silica nanoparticles.

Synthesis and characterization of poly(ethylene glycol) based β-cyclodextrin polymers

A series of novel water soluble β-cyclodextrin (βCD) polymers has been synthesized from functionalized poly(ethylene glycol) (PEG). The chemical composition of the polymers has been characterized by ¹H NMR and the βCD content is found to be between 48 and 33% (w/w). The molecular weight has been determined by Size Exclusion Chromatography (SEC) and depends on the ratio between βCD and PEG, varying from 2.1 × 10⁴ to 8.6 × 10⁴ g mol^?1. The physico chemical properties have been characterized by differential scanning calorimetry (DSC), viscometry and isothermal titration calorimetry (ITC). ITC shows that the polymers have association constants comparable to βCD with different guest molecules, indicating a good accessibility of the CDs.     

Synthesis,Structure and Reactivity of Lanthanocene Complexes

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Effect of bovine serum albumin on the micellization of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) block copolymers in aqueous solutions by fluorescence spectroscopy

Effect of bovine serum albumin (BSA) on the temperature-dependent association behavior of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) block copolymers was investigated using pyrene fluorescence spectroscopy. The critical micellization temperature (CMT) of pluronics in aqueous solution was increased by the addition of BSA. A closed association model was used to obtain the standard free energies (△G0), enthalpies (△H 0), and entropies (△S 0) of micellization. The standard enthalpy and entropy of micellization for pluronic polymers in water were decreased with an increase of the BSA content. The more PPO component in the pluronic polymer, the higher the changed values of micellization enthalpy and entropy. The hydrophobic part of the pluronics, PPO, was responsible for the interaction between pluronics and BSA. Hydrophobic interaction between PPO and BSA was correlated to the alternation of the PPO-PPO interaction by the addition of BSA, which would shift the CMT toward higher temperature and alter the thermodynamic parameters of micellization for pluronics in aqueous solutions.     

Dielectric polarization of cross-linked poly(ethylene oxide)—phenomenology

Results of dielectric relaxation studies will be discussed. It turns out that competition of electric and structural relaxation coins permittivity and as a result conductivity mechanism at low temperature. It dominates long-ranging relaxation in the molten state. In the opposite limit of temperature, cross-linked poly(ethylene oxide) (PEO) with low mesh size can be transferred into super-cooled liquid state. Then, PEO behaves like a hydrogen-bonded liquid since crystallization is strongly suppressed. As a result, one observes slow Debye-like relaxation at low temperature. Beyond the low-frequency region, there appears an extended region between crossings of impedance components, where Z′ ≈ Z″ at acceptable approximation. It is coined by damped oscillation under action of the electric field. These effects lessen with increasing mesh size of the sample as clearly shown by M″(ω) spectra. The dipole moment of the PEO samples in molten state decreases only slightly with increasing mesh size.     

Study on Synthesis of Star‐Shaped Poly(ethylene oxide) by Atom Transfer Radical Polymerization

Star‐shaped poly(ethylene oxide) (PEO) was prepared by atom transfer radical polymerization (ATRP) with a 2‐bromoisobutyryl PEO ester as a macroinitiator. Divinylbenzene (DVB) and ethylene glycol dimethacrylate were employed as the coupling reagents. Several factors pertinent to star polymer formation are: type of coupling reagents and solvents, feed ratio of DVB to the macroinitiator, and reaction time. These were studied and used to optimize the star formation process. The optimum yield of star polymer was ca. 90–98%.     

Mechanocaloric properties of poly(dimethylsiloxane) and ethylene–propylene rubbers

We measured the temperature change in strips of poly(dimethylsiloxane) (PDMS) and ethylene–propylene rubbers that occurred as they were stretched and allowed to shrink by a factor of 3.5–4.5, along with the tensile force that effected the deformation. Main results obtained are as follows: (1) the temperature change is fully reversible in E–P rubber and slightly but definitely irreversible in PDMS rubber. The temperature rise in the latter on stretching is larger than the fall on shrinking by ca. 20 %. (2) The reversible part of heat that evolves from or is absorbed by PDMS rubber is smaller than, but close to, the mechanical energy expended. For E–P rubber, the heat generated greatly exceeds the expended mechanical energy. (3) The entropy of extension as a function of extension is reproduced well by Wang and Guth calculation for PDMS rubber, but not for E–P rubber.     

Formation of the phase structure of polymer systems of ethylene copolymers–[3-(2-aminoethylamino)propyl]trimethoxysilane

Solubility of components is investigated in a wide range of temperatures and formulations in systems of ethylene copolymers–[3-(2-aminoethylamino)propyl]trimethoxysilane. Phase diagrams are constructed. Temperature and concentration ranges of variation of solubility are revealed, and the structure of modified copolymers is studied.