Living carbocationic polymerization

Summary The living synthesis of ,-di-tert.-chloropolyisobutylene ( ^t -Cl-telechelic PIB) has been accomplished by the use of the sterically hindered bifunctional initiator 1,3-di-(2-methoxy-2-propyl)-5-tert.-butylbenzene (tBu-m-DiCuOMe) in conjunction with BC1₃ coinitiator in CH₃Cl or CH₂Cl₂ diluents at –30°C and –10°C. The living nature of the polymerizations was demonstrated by linear ¯M_n versus W_PIB (g of PIB formed) plots starting at the origin and horizontal N (number of PIB moles) versus W_PIB plots. The molecular weight distributions are narrow (¯M_W/¯M_n < 2.0) and tend to decrease with increasing molecular weights. Number average end functionalities have been quantitated and found to be ¯F_n = 2.0±0.1.     

Polymers from renewable resources. VIII. Thermal properties of the interpenetrating polymer networks derived from castor oil–isophorone diisocyanate–polyacrylamides

Castor oil was reacted with isophorone diisocyanate varying the isocyanate/hydroxyl ratio to produce a number of polyurethanes (PUs). All the PUs were reacted with acrylamide and methacrylamide using ethylene glycol dimethacrylate as the crosslinker and benzoyl peroxide as the initiator. Thermogravimetric analysis of the polymers was conducted using a computer analysis method for assigning the kinetic mechanism. The degradation steps have been discussed in the light of the kinetic parameters. © 1995 John Wiley & Sons, Inc.     

Grafting vinyl monomers into nylon-6. II. Graft copolymerization of methyl methacrylate onto nylon-6 by hexavalent chromium ion

The feasibility of chromium(VI) to induce graft copolymerization of methyl methacrylate onto nylon-6 was investigated in the presence of nitrogen. The rate of grafting was determined by varying monomer concentration, chromium(VI) concentration, temperature, acidity of the medium, solvents, inorganic salts, and redox system. The graft yield increases significantly by increasing the monomer concentration. The graft yield increases with increase of [Cr(VI)] up to 0.025 mole/liter. With further increase of [Cr(VI)], the graft yield decreases. The increase of acid concentration up to 0.395 mole/liter results the increase in graft yield. Beyond this concentration the graft yield decreases. The graft yield increases with increase in temperature up to 55°C and thereafter it decreases. The graft yield is medium dependent. The graft yield increases with increasing thiourea concentration upto 0.0025 mole/liter but beyond this concentration, the percentage graft yield decreases. A suitable kinetic scheme has been proposed and the rate equation has been evaluated.     

Effect of flow rate and temperature on crystallization kinetics,crystallinity index,and elastic modulus of PEEK

Dynamic, in situ wide angle X-ray scattering (WAXS) studies of the melt crystallization of injection-molded poly(ether ether ketone) (PEEK) have been carried out using an X-ray diffractometer and a position-sensitive detector. A test cell has been fabricated to fit inside the diffractometer and yet work as a complete injection molding apparatus. The rate of crystallization has been shown to increase with decreasing crystallization temperature and/or increasing flow rate in the mold. The crystallization rate decreases dramatically with increase in melt soak time at 400°C. The crystallinity index, which affects the stiffness, toughness, and fracture behavior of PEEK, has been measured under various processing conditions, by wide angle X-ray scattering, so as to optimize the process parameters: molding time, mold temperature, melt temperature, soak time at melt temperature, and flow rate. It has been shown that the crystallinity and hence the elastic modulus increase with increase in crystallization temperature and/or flow rate. Chain orientation has been shown to be absent in the bulk of the injection-molded specimens under normal molding conditions.     

Production of agrochemical from waste polyesters

In this study, agrochemical was produced from waste polyesters. Reactions of waste polyesters [poly (ethylene terephthalate) (PET) and poly (butylene terephthalate) (PBT)] powder with ethylene glycol (EG) in the presence of tetrahydrofurane (THF) using 0.003 mol lead acetate as a catalyst were carried out in a batch reactor at 470 K and at atmospheric pressure conditions. Reactions were undertaken with various particle size ranges from 50 to 512.5 μm, and reaction time from 30 to 70 min for reactions of polyesters. Low molecular weight product of polyester was obtained during this process. In the next stage, hydroxylamine hydrochloride (HAHC), cyclohexylamine (CHA), and potasium hydroxide (KOH) solution were introduced to convert low molecular weight product of polyester into terephthalohydroxamic acid (TPHA) by introduction of HCl (Hydrochloric Acid) as per stoichiometric requirement. TPHA can be used as an agrochemical (insecticide) with appreciable efficiency. To increase the polyester conversion rate, external catalyst (0.003 mol lead acetate) was introduced during the reaction. The product was deposited on the surface of unreacted polyester, which was removed from the surface by introducing dimethyl sulfoxide (DMSO). To accelerate the reaction rate, DMSO, CHA, and THF were introduced during the reaction, which has an industrial significance. Depolymerization of polyester was proportional to the reaction time. Depolymerization of polyester was inversely proportional to the particle size of polyester. Analyses of value‐added product (TPHA) and byproducts [EG and BD (1,4‐butanediol)] as well as polyesters were undertaken. A kinetic model is developed, and experimental data simulated with it, which was consistent with the model. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2504–2510, 2006     

Design of a password-based authenticated key exchange protocol for SIP

The Session Initiation Protocol (SIP) is a signaling communications protocol, which has been chosen for controlling multimedia communication in 3G mobile networks. In recent years, password-based authenticated key exchange protocols are designed to provide strong authentication for SIP. In this paper, we address this problem in two-party setting where the user and server try to authenticate each other, and establish a session key using a shared password. We aim to propose a secure and anonymous authenticated key exchange protocol, which can achieve security and privacy goal without increasing computation and communication overhead. Through the analysis, we show that the proposed protocol is secure, and has computational and computational overheads comparable to related authentication protocols for SIP using elliptic curve cryptography. The proposed protocol is also provably secure in the random oracle model.     

Design and performance of a punch mechanism based pellet injector for alternative injection in the large helical device

A low speed single barrel pellet injector, using a mechanical punch device has been developed for alternative injection in the large helical device. A pellet is injected by the combined operation of a mechanical punch and a pneumatic propellant system. The pellet shape is cylindrical, 3 mm in diameter and 3 mm in length. Using this technique the speed of the pellet can be controlled flexibly in the range of 100-450 m/s, and a higher speed can be feasible for a higher gas pressure. The injector is equipped with a guide tube selector to direct the pellet to different injection locations. Pellets are exposed to several curved parts with the curvature radii R(c) = 0.8 and 0.3 m when they are transferred in guided tubes to the respective injection locations. Pellet speed variation with pressure at different pellet formation temperatures has been observed. Pellet intactness tests through these guide tubes show a variation in the intact speed limit over a range of pellet formation temperatures from 6.5 to 9.8 K. Pellet speed reduction of less than 6% has been observed after the pellet moves through the curved guide tubes.     

Bipartite coherent-state quantum key distribution with strong reference pulse

We propose an optical scheme for quantum key distribution in which bits are encoded in relative phases of four bipartite weak coherent states ${|\alpha, \alpha\rangle, |-\alpha, -\alpha\rangle, |-\alpha, \alpha\rangle}$ and ${|\alpha, -\alpha \rangle}$ , with respect to a strong reference pulse. We discuss security of the scheme against eavesdropping strategies like, photon number splitting, photon beam splitting and intercept-resend attacks. It is found that present scheme is more sensitive against these eavesdropping strategies than the two-dimensional non-orthogonal state based protocol and BB84 protocol. Our scheme is very simple, requires only passive optical elements like beam splitters, phase shifters and photon detectors, hence is at the reach of presently available technology.     

The role of anergy in peripheral T cell unresponsiveness

When a T cell's encounter with specific antigen results in good signaling through the T cell antigen receptor yet does not lead to a proliferative response, the T cell enters a state of nonresponsiveness, or anergy. Anergy induction can result from a number of different situations, including antigen presentation by costimulation-deficient or "non-professional" antigen presenting cells, pharmacological blocking of T cell proliferation, or chronic stimulation of the T cell receptor by antigen. Anergy is a long-lived but temporary state characterized by a profound inability of the T cell to produce IL-2. Other effector functions may be affected to variable degrees. Anergy has been characterized most carefully under in vitro conditions, but several experimental models have demonstrated that T cells can also become anergic in vivo. This mechanism for tolerance induction may help to ensure that any mature autoreactive T cells which escape thymic deletion are unable to respond to host tissues. Furthermore, an understanding of the mechanism of anergy induction will most certainly lead to beneficial clinical applications, including improving graft acceptance and avoiding such deleterious immune responses as autoimmunity and allergy.     

Interaction of transport resistances with biochemical reaction in packed-bed solid-state fermentors: effect of temperature gradients

Subdermal superficial liposuction, first presented by the authors at the ISAPS Congress at Zurich in 1989, is performed with thin three-hole Mercedes cannulas (diameter ranges from 1.8 to 2 mm) to treat small and secondary adiposities and to allow better skin retraction. Suction of the subdermal layer of fat reduces the thickness and consistency of the superficial fat and enhances the possibility of skin retraction. In cases where there is a large adiposity of the abdomen, arms, or inner thighs, there is a conspicuous volume of fat whose weight tends to overstretch and to carry the overlying skin downward. In these cases we need to reduce the large fat volume to permit effective skin retraction. Therefore, we apply the principles of traditional liposuction with those of subdermal superficial liposuction to aspirate large amounts of fat from all the adipose layers. We call this technique Massive All Layer Liposuction (MALL). The amount of skin shrinkage after this "defatting" procedure is remarkable and the clinical results are very good. The MALL technique can be applied to other areas as well. In our experience this new liposuction technique has dramatically reduced the indications of abdominoplasties and dermolipectomies of inner thighs and arms.