Effect of intramolecular reactions in multifunctional step growth polymerizations in cascades of continuous-flow,stirred-tank reactors

A simple kinetic model describing intramolecular reactions in multifunctional step growth polymerizations of RA_j monomers is presented. The model is far simpler than more detailed kinetic or Monte Carlo models which pose severe numerical difficulties close to gelation. The formulation presented is quite general, but it requires a relationship for the ensemble-cum-time average number of rings, r _n, per molecule having n RA_j units. A very simple yet intuitively correct equation has been chosen for r _n, which involves an empirical parameter ?? Results on cascades of homogeneous continuous-flow stirred-tank reactors (HCSTRs) show trends which are physically expected. The present formulation could possibly be used for scale-up of HCSTRs, with ?? obtained experimentally. It is hoped that future studies using rigorous models would lead to more fundamental and improved relationships for r _n.     

替换机械式开关的单IC基电子电路

简单廉价电路使用一个低成本按键开关就可以触发电源的开关.该电路可替换更高价格及外形较大的按键式机械开关.按键开关触发一个单稳电路.     

Colloid cyst xanthogranuloma of the third ventricle--a case report

Diagnosis and treatment of malignant pericardial effusion are difficult in clinical practice. This paper reports the feasibility and reliability of percutanous trans-catheter intervention for the diagnosis and treatment of malignant pericardial effusion. Under echocardiagraphic guidence, pericardial puncture was performed and a heamostasis sheath was placed in situ by Seldinger technique. Through the sheath multiple biopsies of the pericardium were taken for pathological examination. A pigtail catheter was inserted to drain off the effusion. According to pathological report suitable anti-cancer drugs were instilled into the pericardial cavity through indwelling catheter for 3-5 days. The catheter was withdrawn when fluid did not re-accumulate. Diagnosis was made in over 96.0% of the cases. Upon follow-up for 3-6 months, complete remission was seen in 96.0% of the treated patients. No significant complication was found in all patients. Percutaneous trans-catheter intervention is a useful approach for the diagnosis and treatment of malignant pericardial effusion.     

Optimum step length selection rule in modified HL–RF method for structural reliability

This paper presents the implementation concepts of a step length selection rule in a modified Hasofer-Lind and Rackwitz-Fiessler (HL–RF) method in order to improve its performance. Several step length selection rules in the context of structural reliability were studied and implemented in order to make the modified HL–RF method more robust and efficient. It has been demonstrated that a variant of Goldstein's rule, which is popularly known as the Armijo rule, is one of the most efficient step length selection rules. It is observed in this study that a proper step length selection rule will not only make the algorithm more robust but also improves the other parameters such as efficiency, capacity, etc. An iterative procedure, which enables systematic implementation into a computer program has been given. Several case studies have been taken from the literature to demonstrate and validate the proposed algorithm. A general-purpose software has been developed to solve a variety of structural reliability problems including those, which are complex and non-linear. In addition, non-normal distributions, such as lognormal, extreme value distributions, etc., are incorporated in this software.     

Simulation of nylon 6 polymerization in tubular reactors with recycle

In the hydrolytic polymerization of ?-caprolactam, the ring opening of the monomer is much slower than the polyaddition reaction. Hence, the mixing of aminocaproic acid to the feed results in a faster conversion of the monomer. Industrially, this fact is exploited by using a recycle stream. An isothermal plug flow reactor (PFR) with a recycle is simulated in this study, using two techniques: the method of successive substitutions and Wegstein's method. It is found that, under certain operating conditions, the use of a recycle stream gives higher monomer conversions and lower cyclic dimer concentrations than either a PFR or a homogeneous continuous-flow stirred-tank reactor (HCSTR), with the degree of polymerization almost the same as that obtained in an HCSTR, and thus offers a considerable advantage. However, when a recycle reactor is coupled with a subsequent flashing operation and a finishing reactor, these advantages are considerably reduced.     

Modelling of phenol—formaldehyde polymerization reaction

In the condensation polymerization of phenol and formaldehyde, the ortho and para positions exhibit different reactivities. In addition, along a polymer chain, internal reactive sites have lower reactivity, possibly due to shielding phenomena^1,2. A detailed kinetic model for novalac formation has been proposed accounting for all these factors. Five different kinds of reactive sites have been shown to exist on a polymer chain and the reactivity of a given reaction has been assumed to be governed completely by the reactive site involved in it. A mass balance has been written for each site and the equations have been solved numerically to examine the effect of different parameters on the course of the condensation polymerization. The model predicts polymer chains with small levels of branching, which is consistent with experimental observations.     

Multiobjective optimization of an industrial nylon‐6 semi batch reactor using the a‐jumping gene adaptations of genetic algorithm and simulated annealing

The elitist nondominated sorting genetic algorithm (NSGA‐II) and multiobjective simulated annealing (MOSA) with the robust fixed‐length jumping gene adaptation (aJG) are used to solve three computationally intensive multiobjective optimization problems for an industrial semi batch nylon‐6 reactor. In Problems 1 and 2, the batch time and the final concentration of the undesirable side‐product (cyclic dimer) are minimized while maintaining desired values of the degree of polymerization of the product and the monomer conversion (monomer conversion is maximized as a third objective in Problem 3). The histories of two decision variables, pressure [or vapor release rate] and jacket fluid temperature, are used to obtain the Pareto optimal fronts. The study predicts considerable improvement over earlier results when (i) a single‐stage steam jet ejector is used to create subatmospheric pressures in the reactor, (ii) when the jacket fluid temperature is taken as a function of time, and (iii) when some amino caproic acid (from the depolymerization of scrap nylon‐6) is added to the feed. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Conditions needed for satisfactory measurement of mass transfer coefficients,internal diffusivity and adsorption rate constants

Conditions are developed for the accurate measurement of mass transfer coefficients, internal diffusivity and adsorption rate constants using pulse gas chromatography within the limits of the approximation of the Kubin-Kucera model for adsorption in a packed bed. Physisorption rates are shown to be many orders of magnitude higher than those measurable. Thus, pulse chromatography cannot be used to determine physisorption rate constants. Mass transfer coefficients at low Reynolds Numbers are shown to be measurable under severely restricted conditions.     

Simulation of molecular weight distribution and cyclic oligomer formation in the polymerization of nylon 6

The reversible polymerization of nylon 6 including ring opening, polycondensation, polyaddition, and cyclization reactions as well as the reaction with monofunctional acids was simulated for an isothermal batch reactor at 235°C. The cyclic oligomer concentrations, the molecular weight distributions, and its moments have been computed using a chain length-dependent equilibrium constant for the cyclization reaction. Even though the cyclization step does not influence the monomer conversion considerably, it does effect the molecular weight distribution and its moments.