Reversible addition-fragmentation chain transfer mediated radical polymerization of asymmetrical divinyl monomers targeting hyperbranched vinyl polymers

Reversible addition-fragmentation chain transfer (RAFT) mediated radical polymerizations of allyl methacrylate and undecenyl methacrylate, compounds containing two types of vinyl groups with different reactivities, were investigated to provide hyperbranched polymers. The RAFT agent benzyl dithiobenzoate was demonstrated to be an appropriate chain-transfer agent to inhibit crosslinking and obtain polymers with moderate-to-high conversions. The polymerization of allyl methacrylate led to a polymer without branches but with five- or six-membered rings. However, poly(undecenyl methacrylate) showed an indication of branching rather than intramolecular cycles. The hyperbranched structure of poly(undecenyl methacrylate) was confirmed by a combination of H-1, C-13, H-1-H-1 correlation spectroscopy, and distortionless enhancement by polarization transfer 135 NMR spectra. The branching topology of the polymers was controlled by the variation of the reaction temperature, chain-transfer-agent concentration, and monomer conversion. The significantly lower inherent viscosities of the resulting polymers, compared with those of linear analogues, demonstrated their compact structure,

2-cyanoprop-2-yl dithiobenzoate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2-cyanoprop-2-yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANS were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. H-1 NMR analysis confirmed the high chain-end functionality of the resultant polymers.

A novel route to polyethylene-polystyrene blends through the fragmentation of porous polystyrene beads supported metallocene in ethylene polymerization

Polyethylene-polystyrene blends were synthesized by in situ ethylene polymerization with polystyrene porous beads supported metallocene; the influence of fragmenting support beads on the morphology and the mechanical performance of the blends was investigated.

Dibenzyl trithiocarbonate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile

Reversible addition-fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain-transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain-transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain-transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 NMR analyses have confirmed the chain-end functionality of the resultant polymer.

Fragmentation reactions of adduct ions [M+CH3CO](+) of isomeric phenylenediamines

The dissociation routes of the adduct ions [M+CH3CO](+) formed by ion-molecule reaction of isomeric phenylenediamines with acetyl ion from acetone under chemical ionization condition were investigated by using collision-induced dissociation (CID) technique performed at ion kinetic energies of 40eV. The adduct ions are intermediate ion-neutral complexes.

Mass spectrometry study combined with theoretical calculation on the unimolecular fragmentation of tetrahydroimidazole-substituted methylene beta-diketones

Studies of low-energy collision-induced dissociation and isotopic labeling on ionized tetrahydroimidazole-substituted methylene P-diketones by tandem mass spectrometry showed that their unimolecular fragmentations may involve the reactions of intermediate ion/neutral complexes and multistep rearrangements. The corresponding mechanisms were proved by semiemipirical calculations of PM3 and AM1 methods.

Sites of protonation and unimolecular fragmentation of protonated N-hydroxyphthalimide in the gas phase

The low energy collision-induced dissociation, linked scan techniques and isotopic labeling experiment were used to investigate the unimolecular fragmentation of protonated N-hydroxyphthalimide under electron impact and chemical ionization conditions. It was found that this compound shows an unusual reactivity towards protonation. Two possible sites of protonation have been proposed to explain the corresponding fragmentation processes, one is that the protonation takes place on the oxygen atom of hydroxyl group, resulting in the loss of water and the other is the formation of an intermediary proton-bound complex in the fragmentation process, giving rise to the fragment ions of m/z 133 and m/z 135. The results show both cases are coexistence in the fragmentations of protonated N-hydroxyphthalimide, and the unimolecular fragmentation pathways are available.

Theoretical study on the unimolecular fragmentation of ionized tetrahydroimidazole-substituted methylene beta-diketones

Semiempirical molecular orbital calculations on the unimolecular mass spectrometric fragmentation of tetrahydroimidazole-substituted methylene beta-diketones are carried out by Austin Model 1 method, and the calculated results give a strong support to our experimental results reported previously. The optimum of the investigated molecular configuration indicates that the two hydrogen atoms attached to nitrogen atom have different activities due to their chemical environment; the relative energies of the ions in fragmentation pathway of ionized tetrahydroimidazole-substituted methylene beta-diketones provide indirectly an evidence for both the existence of ion/neutral complex and the stabilities of these ions.

金属长杆撞击带薄盖板约束炸药的引爆现象研究

通过实验的方法研究了金属长杆撞击带薄盖板约束炸药的引爆现象。观察带有随机偏航角的金属长杆以不同速度撞击炸药的响应情况。找出了金属长杆在不同入射角度和炸药约束条件下，炸药的冲击爆轰阈值。讨论了判别未知炸药发生爆轰、延迟爆轰、非爆轰性爆炸、点火后淬熄和不反应的试验测量手段和方法。结果表明：冲击引爆阈值速度，对于不覆板的裸炸药，随入射角度（0、30、45）的增加而增加；随着覆板厚度的增加而增加。炸药的侧向约束情况对发生延迟爆轰有影响。射弹偏航也是影响炸药引爆的因素之一。Jacobs 判据是关于炸药冲击引爆阈值的经验判据，它可以适用于8701 炸药，文中给出了对平头钢弹、钢覆板情况下,用实验数据拟合的Jacobs公式。由于其它机理引发延迟爆轰（XDT）的现象是存在的，Jacobs 判据对这类现象不适用。

Evaluation of the Cumulative Formation of High-Speed Liquid Jets

This paper describes the generation of pulsed, high-speed liquid jets using the cumulation method. This work mainly includes (1) the design of the nozzle assembly, (2) the measurement of the jet velocity and (3) flow visualization of the injection sequences. The cumulation method can be briefly described as the liquid being accelerated first by the impact of a moving projectile and then further after it enters a converging section. The experimental results show that the cumulation method is useful in obtaining a liquid jet with high velocity. The flow visualization shows the roles of the Rayleigh-Taylor and Kelvin-Helmholtz instabilities in the breakup of the liquid depend on the jet diameter and the downstream distance. When the liquid jet front is far downstream from the nozzle exit, the jet is decelerated by air drag. Meanwhile, large coherent vortex structures are formed surrounding the jet. The liquid will break up totally by the action of these vortices. Experimental results showing the effect of the liquid volume on the jet velocity are also included in this paper. Finally, a method for measuring the jet velocity by cutting two carbon rods is examined.

The application of B-P constitutive equations in finite element analysis of high velocity impact

We present in this paper the application of B-P constitutive equations in finite element analysis of high velocity impact. The impact process carries out in so quick time that the heat-conducting can be neglected and meanwhile, the functions of temperature in equations need to be replaced by functions of plastic work. The material constants in the revised equations can be determined by comparison of the one-dimensional calculations with the experiments of Hopkinson bar. It can be seen from the comparison of the calculation with the experiment of a tungsten alloy projectile impacting a three-layer plate that the B-P constitutive equations in that the functions of temperature were replaced by the functions of plastic work can be used to analysis of high velocity impact.

Shocked Flows Induced by Supersonic Projectiles Moving in Tubes

A numerical study on shocked flows induced by a supersonic projectile moving in tubes is described in this paper. The dispersion-controlled scheme was adopted to solve the Euler equations implemented with moving boundary conditions. Four test cases were carried out in the present study: the first two cases are for validation of numerical algorithms and verification of moving boundary conditions, and the last two cases are for investigation into wave dynamic processes induced by the projectile moving at Mach numbers of M-p = 2.0 and 2.4, respectively, in a short time duration after the projectile was released from a shock tube into a big chamber. It was found that complex shock phenomena exist in the shocked flow, resulting from shock-wave/projectile interaction, shock-wave focusing, shock-wave reflection and shock-wave/contact-surface interactions, from which turbulence and vortices may be generated. This is a fundamental study on complex shock phenomena, and is also a useful investigation for understanding on shocked flows in the ram accelerator that may provide a highly efficient facility for launching hypersonic projectiles.