Process Intensification of Living Cationic Polymerization of Isobutylene by a Flow Reaction System

Increasing the reaction temperature of the living cationic polymerization of isobutylene is crucial for industrial production due to the cost of refrigeration. The reaction temperature increase was achieved with an accelerated reaction rate using a flow reaction system. The polymerization conditions, including the flow reactor design, were based on the results of kinetic studies. Utilizing a milli‐scale flow reactor, polyisobutylene, which has a narrow molecular weight distribution, was obtained within a considerably short residence time at a high temperature. Furthermore, it was confirmed that the value of M_w/M_n correlates with the product of the Reynolds number and the angle of collision.     

Copolymerization of phenylacetylene with various acetylenes by W- and Mo-based catalysts

In the copolymerization of phenylacetylene with various acetylenes catalysed by WCl₆·Ph₄Sn, the relative reactivity of monomer decreased with increasing steric effect of monomer, e.g. HC  Cn-Bu, HC  Cn-Hex > HC  CPh, HC  Cs-Bu > HC  Ct-Bu, MeCCPh, CICCPh. While 1-chloro-2-phenylacetylene (a disubstituted acetylene) showed high reactivity in the homopolymerization by Mobased catalysts, the reactivity was remarkably depressed in the presence of phenylacetylene as comonomer. Based on these results, the relative reactivity of the acetylenic monomers in copolymerization was explained in terms of competitive coordination of monomers to the propagating end.     

Phosphonitrilic chloride: 37. Reaction of 1,1-diamino-3,3,5,5-tetrakis (2,2,2-trifluoroethoxy) cyclotriphosphazene with organosilanes

The Spiro compound N₃P₃(OCH₂CF₃)₄(NH)₂Si(CH₃)₂ formed by reaction of 1,1-diamino-3,3,5,5-tetrakis(2,2,2-trifluoroethoxy)cyclotriphosphazene N₃P₃(OCH₂CF₃)₄(NH₂)₂ and dimethyldichlorosilane Cl₂Si(CH₃)₂ is a yellow or orange coloured oil soluble in organic solvents, vapourized at 160°C without decomposition, and not hydrolysed appreciably in boiling water. Linear compounds are formed by reaction of N₃P₃(OCH₂CF₃)₄(NH₂)₂ with diphenyldichlorosilane or phenyltrichlorosilane owing to hindrance of the phenyl radical. These compounds are amorphous or tacky solids, soluble in organic solvents and stable to water.     

Synthesis and properties of poly (organophosphazenes) ionomers [NP(HNC6H5)2−(x+y)(HNC6H4SO3H) x (HNC6H4SO3Li) y ] n

Poly(anilino sulphamicphosphazenes) such as [NP(HNC₆H₅)_2–x (HNC₆H₄SO₃H) _x ] _n for polymer (I) x=0.3 and for polymer (II) x=0.8 were prepared by the reaction of poly(anilinophosphazene) [NP(HNC₆H₅)₂] _n and sulphonic chloride HSO₃Cl in tetrachloroethane solvent several timeS. Also, H protons in the polymer (I) and (II) were prepared from lithum hydroxide in aqueous solution. It was found, by chemical analysis, that the product prepared with (I) and (II) had compositions such as [NP(HNC₆H₅)_1.7 (HNC₆H₄SO₃H)_0.1(HNC₆H₄SO₃Li)_0.2] _n (III) and [NP(HNC₆H₅)_1.2(HN-C₆H₄SO₃Li)_0.8] _n (IV). Also, the resistivity of products (III) and (IV) were determined and found to be 3.3×10⁷ and 1.5×10⁷ cm^–1, respectively.     

Nanocrystallization of Pd74Si18Au8 metallic glass

The crystallization process of Pd₇₄Si₁₈Au₈ amorphous alloy has been investigated by transmission electron microscopy, small angle X-ray scattering and three-dimensional atom probe techniques. Although literature suggests that the alloy decomposes into two glassy phases prior to the crystallization, we found that the crystallization occurs directly from a single amorphous phase by the primary crystallization of fcc Pd–Au solid solution, followed by the polymorphous crystallization of the remaining amorphous phase to a Pd₃Si phase.     

Multicomponent diffusion in phase-separating polymer blends with different frictional interactions: a mean-friction model

We present a compact formula for describing the mean frictional forces acting on a molecule in multicomponent systems. The friction-based diffusion theory of Zielinski and Hanley was extended to newly include the friction-average molar velocity as a reference frame. The results showed that the previous diffusion theories are unified by the friction-average concept by properly choosing the average velocity. The present model based on the diffusivity-related molar average velocity provides better predictions for the diffusive flux in a ternary miscible liquid compared to the other existing theories. The application of the model in phase-separating ternary systems revealed that the introduction of a highly diffusive third component into demixing polymer blends promotes a particular enhancement of the spinodal decomposition due to the difference in the frictional interactions between polymers.     

Design and testing of ITER ECH & CD transmission line components

Initial testing on the Japan Atomic Energy Agency Gyrotron Test Stand of ITER-relevant TL components, has shown reasonable efficiencies, but identified that trapped modes between closely located miter bends, as well as mode conversion at miter bends can lead to excessive heating of the connecting waveguides. General Atomics has designed, built, and will test components to address this issue as well as ITER relevant components that have not been tested at the levels of 1 MW, 170 GHz, for extended pulse lengths. Some of the components that will be tested are ultra low loss miter bends, dc breaks, polarizers, power monitors, bellows, waveguide switches, waveguide cooling clamps, etc. Details of the components and test results will be presented.     

Effects of fatty acid and emulsifier on the complex formation and in vitro digestibility of gelatinized potato starch

The effects of fatty acid, monoacylglycerol, and polyglycerol fatty acid ester with varying chain length in their acyl chains on the extent of complex formation (complex index) and in vitro enzymatic digestibility of gelatinized potato starch were investigated. The complex index increased with increase in the concentration of the ligands (fatty acid, monoacylglycerol, and polyglycerol fatty acid ester), with the plateau in the complex index value depending on the type of ligands. In comparison of complex index among fatty acid-samples, the complex index maximum increased as the chain length increased up to octanoic acid and then decreased. In comparison of complex index among fatty acid-, monoacylglycerol-, and polyglycerol fatty acid ester-samples at each acyl chain, the complex index maximum followed the order polyglycerol fatty acid ester > monoacylglycerol > fatty acid. Fatty acid, monoacylglycerol, and polyglycerol fatty acid ester with long acyl chains greatly reduced the enzymatic hydrolysis of starch. Polyglycerol fatty acid ester with palmitic acid chains was the strongest inhibitor of starch hydrolysis, suggesting that further complex formation may occur during the hydrolysis of gelatinized starch (enzyme-annealing).