On modifying properties of polymeric melts by nanoscopic particles

We study geometric and energetic factors that partake in modifying properties of polymeric melts via inserting well‐dispersed nanoscopic particles (NP). Model systems are cis‐1,4‐polybutadiene melts including a single atomic clusters of size varied in the range 10–150 atoms (3–7 Å in radius; 0.1–1.5% v/v). We modify the interactions between the chains and the particle by tuning attractive van der Waals interactions. Using molecular dynamics, we study equilibrium fluctuations and dynamical properties at the interface. The NPs move in the polymer matrix in two different regimes corresponding to trapped and free diffusion, depending on the NP size. Furthermore, degree of crowding around the NP by the polymer chains is quantified. Effect of NP size and interaction strength both on volume and volumetric fluctuations is manifested in mechanical properties, quantified here by bulk modulus, K. Tuning NP size and nonbonded interactions results in ～15% enhancement in K by addition of a maximum of 1.5% v/v NP. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Chain transfer agents in cationic photopolymerization of a bis‐cycloaliphatic epoxide monomer: Kinetic and physical property effects

The effects of chain transfer agents (CTA) on cationic ring‐opening polymerization of 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (EEC) were explored. EEC was polymerized in the presence of various CTAs, and epoxide conversions monitored via Raman spectroscopy. Polymer films were prepared and analyzed by dynamic mechanical analysis. Many of the organic alcohols studied greatly enhanced epoxide polymerization rates and conversion levels. The gel fraction of polymer specimens decreased rapidly with increasing amounts of octanol (gel fraction >90% up to 0.3 equiv OH) but remained high with increasing amounts of 1,2‐propanediol (gel fraction >90% up to 0.6 equiv OH). Increasing the size of primary alcohols had little effect on the polymerization rates and conversions. The polymerization rate decreased with increasing alcohol substitution (1°>2°>3°). Acidic alcohols had very low impact on conversion and polymerization rates relative to the neat epoxy resin. The glass transition temperature was inversely related to the size and amount of CTA. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Effect of the structure of titanium–magnesium catalysts on the morphology of polyethylene produced

The structure and formation of polyethylene (PE) particles on supported titanium–magnesium catalysts having different structural characteristics (sizes of microcrystallites, mesopores, and subparticles) were studied for the first time. Scanning electron microscopy was used to identify structural elements of the polymer particles formed over such catalysts and to reveal morphological changes in the growing polymer particles when the yield was increased from approximately 0.2 g PE/g catalyst to approximately 13 kg PE/g catalyst. A relationship was found between structural characteristics of the porous catalyst particles, morphology of the nascent polymer particles, and bulk density of the polymer powder. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2298–2308     

A new nonlinear optical silicate carbonate K2Ca[Si2O5](CO3) with a hybrid structure of kalsilite and soda-like layered fragments

Single crystals of a new silicate carbonate, K₂Ca[Si₂O₅](CO₃), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6₃22) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P6₃/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO₄) and the other of the high-temperature soda-like α-Na₂CO₃, Ca substituting for Na. The electro-neutral layer K₂[Si₂O₅] (denoted K) as well as the layer Ca(CO₃) (denoted S) may separately correspond to individual structures. In K₂Ca[Si₂O₅](CO₃) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability.     

复杂系统的逻辑结构判据问题

系统阐述了LAPP方法以及2004年以来的主要发展,并指出一些新的针对复杂系统的逻辑结构判据算法及相关问题的研究方向.     

Synthesis of Novel Semiconducting Aromatic Polyesteramids Containing Pyridine: Characterization of Nanometer-Sized Rod-Like Analogues and their Copper (II) Complexes

In this paper, new thermally stable isomeric unsubstituted polyesteramides have been successfully prepared by condensation of aromatic acids chlorides namely; isophthaloyl, pyridine-3,5-dicarbonyl and pyridine-2,6-pyridine-dicarbonyl dichlorides with the aminophenol isomers in NMP. Conducting the reaction in NMP/H₂O (90/10 v/v) followed by centrifugal separation furnished the desired polymers as rod-like nanoparticles. The morphology of obtained nanoparticles were studied by SEM. Mixing NMP with H₂O was essential for controlling the particles morphology and as a reaction accelerator.

Pyridine-containing polymers exhibit semi-conducting nature as their conductivities increase with increasing temperature, while no variation of the conductivity with the temperature was observed for their corresponding phenylene analogues. Introduction of the nitro group into the polymer backbone led to a red shift in the absorption and the obtained polymers have a bright yellow color, which is unusual with this polymer group. Copper (II) ions were complexed the polyesteramides-containing nitro group in a (1:1) ratio. Complexes of pyridine-containing polymers exhibit semiconducting nature changed to metallic characters on heating and their conductivities increased tens of magnitudes than their corresponding ligands. These new types of polymeric materials and their nano-sized rods may have numerous applications in nanotechnology and their properties can be tuned for specific applications such as conducting adhesives and coating materials.     

Heat-resistant pyridine-based poly(ether-ester)s: Synthesis, characterization and properties

A pyridine-based diacid was synthesized via nucleophilic substitution reaction of 4-hydroxy benzoic acid with 2,6-dichloropyridine in the presence of potassium carbonate. The diacid was characterized using FT-IR and 1H-NMR spectroscopic methods and also with elemental analysis. Polycondensation reaction of the diacid with different diols including 1,4-dihydroxy benzene, 1,5-dihydroxy naphthalene, bis-phenol A and bis-phenol-P resulted in preparation of pyridine-based poly(ether-ester)s. The polymers were characterized and their physical and thermal properties including inherent viscosity, molecular weight, solubility, thermal stability, thermal behavior and crystallinity were studied. They revealed high heat-resistance and improved solubility in polar solvents. Structure-property relations for the prepared polyester were also studied.     

Gap formulas for closed linear relations

A classical formula for the gap between two densely defined closed operators in a Hilbert space is extended to the case of linear relations. Copyright © 2014 John Wiley & Sons, Ltd.