Combining cationic ring‐opening polymerization and click chemistry for the design of functionalized polyurethanes

A straightforward strategy for the synthesis and functionalization of polyurethanes (PUs) via the use of alkyne‐functionalized polytetrahydrofuran (PTHF) diols is described. The alkyne groups have been introduced into the PTHF chains by the cationic ring‐opening copolymerization of tetrahydrofuran and glycidyl propargyl ether. These PTHF prepolymers were combined with 1,4‐butanediol and hexamethylene diisocyanate for the synthesis of linear PUs with latent functionalization sites. The polyether segments of the PUs have then been coupled with several types of functionalized azides by the copper‐catalyzed azide‐alkyne “click” chemistry, for example with phosphonium containing azides for their antibacterial properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Møller Energy-Momentum Distribution of Higher Dimensional Vaidya Space-Time

In this paper, we intend to clarify the energy-momentum problem of higher dimensional Vaidya space-time in the general theory of relativity. In this connection, Møller energy and momentum for the higher dimensional Vaidya space-time are evaluated in the frame of general relativity. We have obtained that the Møller energy distribution of higher dimensional Vaidya space-time is equal to zero, while the Møller momentum distribution of higher dimensional Vaidya space-time is not equal to zero.     

Copolymerization with the feeding of one of the comonomers: Cationic activated monomer copolymerization of ε‐caprolactone with ethylene oxide

The cationic copolymerization of ε‐caprolactone with ethylene oxide (EO) under the conditions of activated monomer polymerization, that is, with a low‐molecular‐weight diol as an initiator and BF₃ etherate as a catalyst, was studied. To ensure the uniform composition of the resulting copolymers (telechelic oligodiols), the copolymerization was conducted with incremental feeding of the EO comonomer, which was more reactive in the cationic process. ¹H NMR analysis of samples isolated at different stages of the copolymerization indicated that the average composition of the copolymer was indeed nearly constant over the course of the copolymerization. Matrix‐assisted laser desorption/ionization time‐of‐flight spectra of the products revealed, however, that for the same degree of polymerization, macromolecules containing different numbers of EO units were present. The observed distribution was compared with the distribution simulated under the assumption that the probability of incorporating a given unit depended only on the feed composition (nearly constant during the copolymerization). With this assumption, a good agreement between the observed and simulated spectra was obtained. This indicated that, even when the optimum conditions for the formation of a uniform copolymer were created, the individual macromolecules differed in composition because of the statistical character of the copolymerization. The results of differential scanning calorimetry analysis were compatible with such a conclusion; two melting peaks appeared on differential scanning calorimetry curves when a sample was heated immediately after fast cooling, and this may indicate the presence of different types of crystallites. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3788–3796, 2005     

Star polymers by ATRP of styrene and acrylates employing multifunctional initiators

Multifunctional initiators for atom transfer radical polymerization (ATRP) are prepared by converting ditrimethylolpropane with four hydroxyl groups, dipentaerythritol with six hydroxyl groups, and poly(3‐ethyl‐3‐hydroxymethyl‐oxetane) with ～11 hydroxyl groups to the corresponding 2‐bromoisobutyrates or 2‐bromopropionates as obtained by reaction with acid bromides. Star polystyrene (PS) is produced by using these macroinitiators and neat styrene in a controlled manner by ATRP at 110 °C, employing the catalytic system CuBr and bipyridine. M_n up to 51,000 associated with narrow molecular weight distributions (PDI < 1.1) are obtained with conversions up to 32%. Hydrolysis of the star‐PS leads to linear chains having the expected M_n values. The star‐PS polymers based on dipentaerythritol degrade thermally in nitrogen in a two‐step process in which the first low‐temperature step involves scission of the ester linkages and the second step corresponds to the normal PS degradation. Star poly(methyl acrylates) with various cores are likewise prepared in a controlled manner by ATRP of methyl acrylate in bulk and in solution at 60–80 °C with the 1,1,4,7,7‐pentamethyldiethylene triamine ligand. Under these conditions, higher conversions were possible still maintaining low PDI signaling controlled star growth. Multiarm stars of poly(n‐butyl acrylate) and poly(n‐hexyl acrylate) with controlled characteristics have also been prepared. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3748–3759, 2005     

On approximations of the de Rham complex and their cohomology

For a commutative algebra R, its de Rham cohomology is an important invariant of R. In the paper, an infinite chain of de Rham-like complexes is introduced where the first member of the chain is the de Rham complex. The complexes are called approximations of the de Rham complex. Their cohomologies are found for polynomial rings and algebras of power series over a field of characteristic zero.     

Influence of the PVOH molar mass on the morphology and functional properties of EVOH/PVOH films prepared by melt blending

The influences of the molar mass (low, medium, and high) and content of poly(vinyl alcohol) (PVOH) dispersed by melt-blending in an ethylene vinyl alcohol (EVOH) copolymer on the morphology, microstructure, thermal, mechanical, and oxygen barrier properties were investigated. Multilayer films with external low-density polyethylene layers and inner EVOH/PVOH blend layer and respective monolayer films were elaborated and characterized. EVOH/PVOH blends exhibited a good compatibility because of the initial presence of PVOH segments in EVOH. The detailed quantitative analysis of the morphology performed for all blends showed that the finest dispersion was obtained with the PVOH with the lowest molar mass. The properties of the films as a function of the PVOH content and its molar mass were determined herein. Significant improvement of barrier properties was obtained at moderated water activities (up to a_w = 0.6) by using the PVOH with the lowest molar mass. Compared to the neat EVOH material, the oxygen permeability coefficients decreased by a factor 2 by adding 15 vol% PVOH while the thermal and mechanical properties remained similar.     

Dyson orbitals for ionization from the ground and electronically excited states within equation-of-motion coupled-cluster formalism: theory, implementation, and examples

Implementation of Dyson orbitals for coupled-cluster and equation-of-motion coupled-cluster wave functions with single and double substitutions is described and demonstrated by examples. Both ionizations from the ground and electronically excited states are considered. Dyson orbitals are necessary for calculating electronic factors of angular distributions of photoelectrons, Compton profiles, electron momentum spectra, etc, and can be interpreted as states of the leaving electron. Formally, Dyson orbitals represent the overlap between an initial N-electron wave function and the N-1 electron wave function of the corresponding ionized system. For the ground state ionization, Dyson orbitals are often similar to the corresponding Hartree-Fock molecular orbitals (MOs); however, for ionization from electronically excited states Dyson orbitals include contributions from several MOs and their shapes are more complex. The theory is applied to calculating the Dyson orbitals for ionization of formaldehyde from the ground and electronically excited states. Partial-wave analysis is employed to compute the probabilities to find the ejected electron in different angular momentum states using the freestanding and Coulomb wave representations of the ionized electron. Rydberg states are shown to yield higher angular momentum electrons, as compared to valence states of the same symmetry. Likewise, faster photoelectrons are most likely to have higher angular momentum.     

Copolyethers with controlled structure: Mechanism of formation and microstructure

Cationic copolymerization of 3-membered cyclic ethers (oxiranes) with 5-membered cyclic ether (tetrahydrofuran) leads to linear copolyethers containing significant amount of cyclic fraction. When the copolymerization is conducted in the presence of diols, telechelic copolymers are formed by the process in which oxirane is incorporated into copolymer irreversibly by Activated Monomer mechanism, while tetrahydrofuran is incorporated reversibly by Active Chain End mechanism. Thus both kinetic and thermodynamic factors can be used to control the rate of the incorporation of comonomers. Studies of the kinetics of the competing reactions leading to formation of copolymer, studies of copolymer microstructure by ¹³C-NMR and analysis of the composition of the cyclic fraction, led to the correlation between the copolymer microstructure and the amount of cyclic fraction formed. The dependence of the cyclic fraction content on the reaction conditions was therefore explained.     

Branched polyether with multiple primary hydroxyl groups: polymerization of 3-ethyl-3-hydroxymethyloxetane

Cationic polymerization of 3-ethyl-3-hydroxymethyloxetane gives branched, soluble macromolecules with multiple glycolic end groups. There are approximately 3–4 “normal” units per one branched unit.