Construction of excellent thermal latent system for the synthesis of networked epoxide polymers by sulfonium salts

An efficient thermally latent initiation system using dual sulfonium salts, consisting S‐benzylsulfonium salt 1 bearing counter anion and S,S‐dimethylsulfonium salt 2 bearing CH₃ counter anion, has been developed for the cationic polymerization of epoxides. Compared to the conventional system using 1 as a thermally latent initiator, the newly developed system allowed significant improvement of stability of epoxy formulations during storage at ambient temperature without sacrificing their curability at elevated temperatures. Such a remarkable performance is attributable to the nucleophilic attack of CH₃ to cationic species formed unavoidably by the reaction of 1 with epoxide. Such entrapment of cationic species into the corresponding dormant led to the inhibition of undesirable chain growth of polymers during storage of epoxy formulations. In addition, the dormant can undergo dissociation at elevated temperature to give cationic species, which can readily initiate the polymerization of epoxide. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2096–2102     

Cationic polymerization with p-substituted benzyl p-hydroxyphenyl methyl sulfonium salts: Effect of substituents and mechanistic aspects of initiation reaction

Various p-substituted benzyl p-hydroxyphenyl methyl sulfonium salts ( 2 ) were synthesized and their initiator activities were evaluated in bulk polymerization of glycidyl phenyl ether (PGE). The order of the activity was found to be 2b (X = CH₃) > 2a (X = H) ≈ 2c (X = Cl) > 2d (X = NO₂), indicating that the introduction of an electron-donating group enhanced the activity. In Hammett's plots, the logarithm of the ratio of the polymerization rates (log k_x/k_H) was correlated with σ⁺_ρ better than with σ_p and a negative ρ⁺ value (-1.18) was obtained. Reaction of 2a with benzyl mercaptan mainly gave dibenzyl sulfide and p-hydroxyphenyl methyl sulfide. The obtained results seemed to demonstrate that the OH group of the aryl group yielded no proton as initiator for the polymerization, whereas the benzyl group caused the polymerization, which was initiated by the corresponding benzyl cation formed by C? S bond cleavage. © 1993 John Wiley & Sons, Inc.     

Pyrazoles—A novel class of blocking agents for isocyanates

Pyrazoles were found as a novel class of blocking groups for isocyanates. Adhesive mixtures of pyrazole blocked isocyanates and amine terminated prepolymers like Jeffamines® (Texaco Chem. Co.) combine excellent reactivities (gelation times within minutes at 100–120°C), good latencies (more than 170 days at 40°C), and good adhesion properties on many substrates. The reactivity of pyrazole blocked isocyanates toward nucleophiles increases with the number of electron donor substituents on the pyrazole nucleus and, thus, can be fine tuned by the appropriate substitution pattern. This behavior contrasts sharply with that of phenolic blocked isocyanates, where reactivities with the same nucleophiles decrease with more and stronger electron donor substituents on the phenol nucleus. Therefore, different deblocking reaction mechanisms were proposed for pyrazole vs. phenol blocked isocyanates. The excellent latency of pyrazole blocked isocyanate/Jeffamine® mixtures is due to the insolubility of the two components at ambient temperature and the slow endothermic dissolution process at higher temperature. The good adhesion of formulations with pyrazole blocked isocyanates as reactive components on most plastic and metal substrates is ascribed to the primer action of the released blocking group. © 1994 John Wiley & Sons, Inc.     

Fast control latency uncertainty elimination for the BESIII ETOF upgrade

A new fanning topology is proposed to precisely fan out fast control signals in the Beijing Spectrometer(BESIII) end-cap time-of-flight(ETOF) electronics. However, uncertainty in transfer latency is introduced by the new fanning channel, which will degrade the precision of fast control. In this paper, latency uncertainty elimination for the BESIII ETOF upgrade is introduced. The latency uncertainty is determined by a Time-Digital-Converter(TDC) embedded in a Field-Programmable Gate Array(FPGA) and is eliminated by re-capturing at synchronous and determinate time. Compared with the existing method of Barrel-cap TOF(BTOF), it has advantages of flexible structure, easy calibration and good adaptability. Field tests on the BESIII ETOF system show that this method effectively eliminates transfer latency uncertainty.     

Global dynamics for an age-structured epidemic model with media impact and incomplete vaccination

Some studies show that the efficacy of vaccines may decline and the vaccine-induced immunity wanes with time elapsed since vaccination (e.g., BCG, HBV vaccines). Meanwhile, the use of media can effectively contain the emerging epidemics. In our work, an SVEIR epidemic model with media impact, age-dependent vaccination and latency is proposed, where the efficacy of vaccines depends on the time since vaccination. Uniform persistence and the sharp threshold dynamics are established, that is, the vaccination reproduction number completely determines the global dynamics of the model system. Our main results established can be extended to the SVEIR model with the general nonlinear infectious force function of monotonicity and concavity.     

Stability vs. optimality in selfish ring routing

We study asymmetric atomic selfish routing in ring networks, which has diverse practical applications in network design and analysis. We are concerned with minimizing the maximum latency of source-destination node-pairs over links with linear latencies. We show that there exists an optimal solution that is a 9-approximate Nash equilibrium, significantly improving the existing upper bound of 54 on the instability factor. We present fast implementation of the best response dynamics for computing a Nash equilibrium. Furthermore, we perform empirical study on the price of stability, narrowing the gap between the lower and upper bounds to 0.7436.     

Superluminal propagation and information transfer: A statistical approach in the microwave domain

Signal velocity is calculated in a medium with negative group delay (NGD). By accounting for the medium and the detector noise sources, the time varying probability of error at the detector [Pe(t)$\mathit{Pe}(t)$] is evaluated in the NGD channel and a normal dispersion channel. The scheme in which Pe(t)$\mathit{Pe}(t)$ falls below a threshold at earlier time, implies faster information transfer. It is found that the signal velocity depends on the detector type and the relative noise strength of the detector with respect to the channel. Finally, it is shown that NGD channels can be useful in applications that are limited by the detector noise.     

Approximation algorithm for minimizing total latency in machine scheduling with deliveries

We study the problem of minimizing total latency in machine scheduling with deliveries, which is defined as follows. There is a set of n jobs to be processed by a single machine at a plant, where job J_i is associated with its processing time and a customer i located at location i to which the job is to be delivered. In addition, there is a single uncapacitated delivery vehicle available. All jobs (vehicle) are available for processing (delivery) at time 0. Our aim is to determine the sequence in which the jobs should be processed in the plant, the departure times of the vehicle from the plant, and the routing of the vehicle, so as to minimize the total latency (job delivery time). We present a 6e16.309691-approximation algorithm for the problem.