Hyperdeproteinized natural rubber prepared with urea

Preparation of hyperdeproteinized natural rubber was made from fresh latex and preserved high‐ammonia latex by treatment with urea in the presence of sodium dodecyl sulfate. Concentration of urea, temperature, and time for the incubation were investigated to remove the proteins effectively. Under the best conditions, the total nitrogen content and amount of allergenic proteins for the deproteinized rubbers were 0.005 wt % and 1.0 μg/ml, respectively, which were less than those of natural rubber deproteinized with proteolytic enzyme. The hyper‐deproteinized natural rubber was proved through FT IR spectroscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 555–559, 2004     

On loci of acrylonitrile polymerization with bisulfite-persulfate initiators under the conditions of low water/monomer ratio

In the preparation of acrylonitrile–vinylacetate copolymer (93:7 in weight) by continuous polymerization in aqueous medium using the complete mixing type reactor, the author and co-workers studied the effects of the water/monomer ratio on polymer properties and polymerization. They reported that the structure of a polymer particle becomes more compact with decreasing water/monomer ratio. This was noted in studying the physical properties of the polymer and the formation of polymer particles in this system. ^1,2 Here the author has performed kinetic studies based on the results of polymerization to determine the loci of the polymerization in the range of water/monomer ratio roughly from 1.75 to 4.0. Most of the primary radicals from the initiators attack the monomers in the aqueous phase to form monomer radicals attached to initiator fragments, and most of the monomer radicals grow to form polymer radicals until termination occurs in the aqueous phase. Hence, the loci of polymerization in this system are not the surfaces and inner parts of the polymer particles, the diameters of which are roughly from 20 to 60 μm observed by a microscope, but the aqueous phase excluding these particles.     

Synthesis of continuous-time dynamic quantizers for LFT type quantized feedback systems

This paper focuses on analysis and synthesis methods of continuous-time dynamic quantizers for LFT type quantized control systems. Our aim is to propose a numerical optimization design method of multiple (decentralized) quantizers such that a given linear system is optimally approximated by the given linear system with the multiple quantizers. Our method is based on the invariant set analysis and the LMI technique. In addition, we clarify that our proposed method naturally extends to multiobjective control problems similar to linear control. For implementation, this paper presents an analysis condition of the applicable interval of switching process of quantizer. Finally, it is pointed out that the proposed method is helpful through a numerical example.     

Detailed analyses of key phenomena in core disruptive accidents of sodium-cooled fast reactors by the COMPASS code

A five-year research project has been initiated in 2005 to develop a code based on the MPS (Moving Particle Semi-implicit) method for detailed analysis of key phenomena in core disruptive accidents (CDAs) of sodium-cooled fast reactors (SFRs). The code is named COMPASS (Computer Code with Moving Particle Semi-implicit for Reactor Safety Analysis). The key phenomena include (1) fuel pin failure and disruption, (2) molten pool boiling, (3) melt freezing and blockage formation, (4) duct wall failure, (5) low-energy disruptive core motion, (6) debris-bed coolability, and (7) metal–fuel pin failure. Validation study of COMPASS is progressing for these key phenomena. In this paper, recent COMPASS results of detailed analyses for the several key phenomena are summarized. Simulations of GEYSER and THEFIS experiments were performed for dispersion and freezing behaviors of molten materials in narrow flow channels. In particular, the latter experiment using melt–solid mixture is also related to fundamental behavior of low energy disruptive core. CABRI-TPA2 experiment was simulated for boiling behavior of molten core pool. Expected mechanism of heat transfer between molten fuel and steel mixture was reproduced by the simulation. Analyses of structural dynamics using elastoplastic mechanics and fracture criteria were performed for SCARABEE BE+3 and CABRI E7 experiments. These two analyses are especially focused on thermal and mechanical failure of steel duct wall and fuel pin, respectively. The present results demonstrate COMPASS will be useful to understand and clarify the key phenomena of CDAs in SFRs in details.     

Pressure Sensitive Adhesive Properties and Miscibility in Blends of Poly(vinyl ethylene-co-1,4-butadiene) with Hydrogenated Terpene Resin

The pressure sensitive adhesive (PSA) properties of two samples of poly(vinyl ethylene-co-1,4-butadiene) (V-BR) (vinyl content: 47.4 and 60 wt%) blended with hydrogenated terpene resin (CLEARON P125) were measured on blend compositions having CLEARON P125 contents (by weight) of 10%, 30% and 50%. The maximum values of 180° peel adhesion, rolling ball tack and probe tack were observed with a V-BR/CLEARON P125 70/30 blend, whereas the maximum values of holding power were obtained with a 50/50 V-BR/CLEARON P125 blend. In these blends, the miscibility between V-BR and CLEARON P125 was confirmed by means of SEM, DSC and light scattering. The influences of surface tension and dynamic mechanical properties on PSA properties were investigated. The surface tension values were essentially the same in all the V-BR/CLEARON P125 blends. Minimum values of storage modulus G′ and loss modulus G″ at room temperature in V-BR/CLEARON P125 blends were obtained with a 70/30 blend. Thus, it is believed that in V-BR/CLEARON P125 blends, 180° peel adhesion and tack are related to the dynamic mechanical properties.     

Purification of steryl esters from soybean oil deodorizer distillate

Soybean oil deodorizer distillate (SODD) contains steryl esters in addition to tocopherols and sterols. Tocopherols and sterols have been industrially purified from SODD but no purification process for steryl esters has been developed. SODD was efficiently separated to low b.p. substances (including tocopherols and sterols) and high b.p. substances (including 11.2 wt% DAG, 32.1 wt% TAG, and 45.4 wt% steryl esters) by molecular distillation. The high b.p. fraction is referred to as soybean oil deodorizer distillate steryl ester concentrate (SODDSEC). We attempted to purify steryl esters after a lipase-catalyzed hydrolysis of acylglycerols in SODDSEC. Screening of industrially available lipases indicated that Candida rugosa lipase was most effective. Based on the study of several factors affecting hydrolysis, the reaction conditions were determined as follows: ratio of SODDSEC/water, 1∶1 (w/w); lipase amount, 15 U/g reaction mixture; temperature, 30°C. When SODDSEC was agitated for 24 h under these conditions, acylglycerols were almost completely hydrolyzed and the content of steryl esters did not change. However, study with a mixture of steryl oleate/trilinolein (1∶1, w/w) indicated that about 20% of constituent FA in steryl esters were exchanged with constituent FA in acylglycerols. Steryl esters in the oil layer obtained by the SODDSEC treatment with lipase were successfully purified by molecular distillation (purity, 97.3%; recovery, 87.7%).     

Development of stealth nanoparticles coated with poly(2-methoxyethyl vinyl ether) as an alternative to poly(ethylene glycol)

Poly(ethylene glycol) (PEG) modification, also known as PEGylation, has been extensively used to improve the stability of nanoparticles for nanomedical applications. However, PEG exhibits antigenicity in some formulations, motivating researchers to explore alternative polymers. Herein, poly(vinyl ether) (PVE) derivatives are highlighted as promising alternatives to PEG because they form intermediate water molecules that suppress non-specific protein adsorption and platelet adhesion to the material surface. We prepared a water-soluble PVE derivative, poly(2-methoxyethyl vinyl ether) (PMOVE), and utilized it as a surface modifier for gold nanoparticles (AuNPs) as model nanoparticles. PMOVE with a thiol terminus was synthesized and confirmed to form an intermediate water molecule using differential scanning calorimetry. Similar to the synthesis of PEGylated AuNPs (PEG-AuNPs), PMOVE-modified AuNPs (PMOVE-AuNPs) were successfully fabricated with an appreciably high density of PMOVE palisades via a thiol-gold coordination reaction. Similar to PEG-AuNPs, PMOVE-AuNPs showed reduced serum protein adsorption and prolonged blood circulation. Additionally, no significant cytotoxicity was observed after incubation of a murine macrophage cell line, RAW264.7, with PMOVE-AuNPs. Our results indicate that the PMOVE modification increases the stealthiness of nanoparticles that is equivalent to that achieved by PEGylation.     

In situ FTIR study on reaction pathways in Ni(CO)4/CH3OK catalytic system for low-temperature methanol synthesis in a liquid medium

An in situ infrared spectroscopic study was conducted to elucidate the reaction pathways for low-temperature methanol synthesis in a catalytic system composed of Ni(CO)₄ and CH₃OK (denoted as Ni(CO)₄/CH₃OK). The reaction was conducted in a liquid medium at 313–333 K with an initial pressure of 3.0 MPa. When CH₃OK was added to Ni(CO)₄ solution at 293 K, different carbonylnickelates, [Ni₅(CO)₁₂]²⁻, [Ni₆(CO)₁₂]²⁻ and [Ni(CO)₃(COOCH₃)]⁻, were immediately formed from Ni(CO)₄. The species and the composition of the carbonylnickel complexes varied with temperature. The variations in concentrations of methanol (MeOH) and methyl formate (MF) during the run, which were determined from their IR absorptions, indicated a pattern characteristic of consecutive reactions with MF as an intermediate. Thus, it was shown that methanol was produced through the carbonylation of MeOH to MF and the subsequent hydrogenation of MF to MeOH. Stable hydridocarbonylnickel anions, [HNi(CO)₃]⁻ and/or [HNi₂(CO)₆]⁻, were observed together with a small amount of Ni(CO)₄ throughout the methanol synthesis. Since Ni(CO)₄ alone showed no activity for the hydrogenation of MF, the hydridocarbonylnickel anions generated in the presence of CH₃OK must be responsible for the reaction. The dual role of CH₃OK in the catalytic system was stated.     

Preparation and graft‐copolymerization of hydrogenated natural rubber in latex stage

Preparation and graft‐copolymerization of hydrogenated natural rubber are performed in latex stage after removal of proteins from the rubber with urea and surfactant. Hydrogenation of deproteinized natural rubber (DPNR) latex is carried out with palladium catalyst under hydrogen atmosphere. The hydrogenated DPNR (HDPNR) is crosslinked with a peroxide followed by graft‐copolymerization of styrene (Sty) and acrylonitrile (AN) in latex stage in order to prepare a graft‐copolymer of crosslinked HDPNR with poly(Sty‐co‐AN) (HDPNR‐graft‐PSAN). Characterization of the products is performed by nuclear magnetic resonance spectroscopy. The conversion of hydrogenation is investigated with respect to the catalyst feed, acidity (pH), and dry rubber content. In the resulting HDPNR‐graft‐PSAN, mole fraction of AN and Sty is 1.4 and 5.8 mol %, respectively. The graft‐copolymer is used to improve properties of PSAN as an impact modifier. The Charpy impact strength of crosslinked HDPNR‐graft‐PSAN/PSAN is about eight times as high as that of PSAN. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42435.