• Applied Chemistry for Engineering
• /
• v.27 no.5
• /
• pp.551-554
• /
• 2016

Silver particles were synthesized by chemical reduction with ionic liquids. Structure of silver particles were significantly affected by the cation parts of the ionic liquids. With increasing the length of the cation part, the smaller silver particles were formed regardless of the anion type. This is mainly attributed to the different stability of the ionic liquid structure formed by physical bond between cation parts. Among seven ionic liquids, [Omim][$PF_6$] was the most effective for synthesizing silver particles.

• Journal of the Korean Chemical Society
• /
• v.17 no.1
• /
• pp.1-9
• /
• 1973

The purpose of this paper is to investigate the mechanism of Diels-Alder reaction by assuming pseudo molecular complex (PMC) which has characters both of ionic and radical bonds. We treated this complex quantum-chemically as an intermediate between the configuration without charge transfer (radical bond character) and the configuration corresponding to the charge transfer from Diene (R) to Dienophile (S) (ionic bond character). The wave function for the complex could be expressed as: ${\psi}_{complex} = {\psi}(R,S) +{ \rho}{\psi}(R^+,S^-)$ where ${\rho}$ is the extent of charge transfer which is a constant to measure the ionic character of PMC. It has been noticed that${\rho}$is related to the difference between Fr + Fr' and Fs + Fs' in free valence (F) when R is united to S through atom r in R to atom s in S and atom r' in R to atom s' in S, That is, ${\rho}{\alpha}$ ${\Delta}F = (Fr + Fr') - (Fs + Fs')$. We have calculated ${\Delta}F$values for more than forty Diels-Alder reactions. The calculated values of ${\Delta}F$ is reversely proportional to the values of Brown's paralocalization energy (Lp) as well as Dewar's differences of delocalization energy$({\Delta}Edeloc.)$ with good linearity. This approach also presents a way of predicting the possibility and the easiness of diene synthesis between any two conjugate compounds. According to the considerations, it could be concluded that Diels-Alder reaction takes place through the united ionic-radical mechanism rather than the separated ionic or radical mechanism.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.11
• /
• pp.3274-3278
• /
• 2013

$CF_2Cl{\cdots}Cl$, an elusive photo-isomer of $CF_2Cl_2$, has been observed in matrix IR spectra from the precursors exposed to radiation from laser ablation of transition-metals. Other plausible products, $CFCl_2{\cdots}F$ and $FClC{\cdots}F-Cl$ are not detected due to their considerably higher energies. Parallel to its previously reported analogues, the C-X bonds are considerably stronger than those of the reactant, and particularly the Cl atom that is weakly bound to the residual Cl atom forms an unusually strong carbon-halogen bond. NBO analysis reveals that the C-Cl bond is a true double bond, and the weak $Cl{\cdots}Cl$ bond is largely ionic, $F_2C=Cl^{\delta+}{\cdots}Cl^{\delta-}$. IRC computation reproduces smooth inter-conversion between the reactant and product, and the transition state is energetically close to the product, consistent with its prompt disappearance in the early stage of photolysis.

• Journal of the Korean Chemical Society
• /
• v.68 no.2
• /
• pp.65-73
• /
• 2024

The halide-acetylene anions, X^--HCCH (X = F, Cl, and Br) have been studied by using several different ab initio and DFT methods to determine structures, hydrogen-bond energies, vibrational frequencies of the anion complexes. Although the halide-acetylene complexes all have linear equilibrium structures, it is found that the fluoride complex is characterized with distinctively different structure and interactions compared to those of the chloride and bromide complexes. The performance of various density functionals on describing ionic hydrogen-bonded complexes is assessed by examining statistical deviations with respect to high level ab initio CCSD(T) results as reference. The density functionals employed in the present work show considerably varying degrees of performance depending on the properties computed. The performances of each density functional on geometrical parameters related with the hydrogen bond, hydrogen-bond energies, and scaled harmonic frequencies of the anion complexes are examined and discussed based on the statistical deviations.

• Bulletin of the Korean Chemical Society
• /
• v.28 no.12
• /
• pp.2299-2302
• /
• 2007

A series of quaternary ammonium-based ionic liquids (ILs) containing an alkyl carbonate group on the cation was first prepared and their physical and electrochemical properties including density, viscosity, thermal stability, electrochemical stability, and ionic conductivity were reported. These ILs exhibited wide electrochemical windows of at least 5.0 V and relatively high conductivities. In contrast to dialkyl-substituted ionic liquids, the ILs with an alkyl carbonate group on the cation showed much smaller drop in conductivities when mixed with a lithium salt, due to the interaction of lithium ions with carbonate groups. Upon interaction with a Li salt, the carbonyl stretching frequency of the carbonate group shifted to a lower frequency whereas the peak associated with C-O single bond moved to a higher frequency.

• Macromolecular Research
• /
• v.9 no.6
• /
• pp.332-338
• /
• 2001

Waterborne polyurethane as a new polymer electrolyte was synthesized by using relatively hydrophilic polyols. The morphology of polyurethane was changed as it was dispersed in water. In contrast to polyurethane ionomer, waterborne polyurethane did not form an ionic cluster but produced a binary system composed of hydrophilic and hydrophobic groups. In the colloidal system, the former and the latter existed at outward and inward, respectively. Waterborne polyurethane was prepared from poly(ethylene glycol) (PEG) /poly(propylene glycol) (PPG) copolymer, 4,4'-diphenylmethane diisocyanate(MDI), ethylene diamine as a chain extender, and three ionization agents, 1,3-propane sultone, sodium hydride and lithium hydroxide. PEG/PPG copolymer was used for suppressing the crystallinity of PEG and N-H bond was ionized for increasing the electrochemical stability of polyurethane. Low molecular weight poly(ethylene glycol) and poly(ethylene glycol dimethyl ether) (PEGDME) were used as plasticizers. DSC, FT-IR and $^1$H-NMR of the waterborne polyurethane were measured. Also, the ionic conductivity of solid polymer electrolytes based on waterborne polyurethane and various concentrations of low molecular weight poly(ethylene glycol) or PEGDME were measured by AC impedance.

• Elastomers and Composites
• /
• v.45 no.3
• /
• pp.165-169
• /
• 2010

Recently supramolecular network thermo-reversible crosslinking elastomer having flexibility, various functionality, and advantages of thermoplastic elastomer (TPE) such as recycle and easy processbility is introduced. Although thermo-reversible bonds such as hydrogen bond and ionic cluster is recognized as a common technology since 1990, control technology of bonding and dissociation of crosslink in supramolecular network is a recent technology. In this review, characteristics of thermo-reversible crosslinking elastomer having rheological properties of TPE and reinforcing behaviors of thermoset elastomer are summarized.

• Bulletin of the Korean Chemical Society
• /
• v.17 no.2
• /
• pp.168-172
• /
• 1996

The variations of the structural detail of layered perovskite-type oxides, Na2Ln2Ti3O10 (Ln=La, Nd, Sm, Gd), have been refined by Rietveld analyses of their powder X-ray diffraction data. Although the c-axis strongly decreases from Ln=La to Nd, Sm, or Gd, the length of Na-O bond along the c-axis that is regarded as the sodium layer spacing is not dependent on the unit cell parameter. Such a behavior is explained by the fact that Na-O bond is in competition with Ti-O one of the perovskite slab. Increased covalency of this Ti-O bond by the lattice contraction leads to weakening of the attaching strength of Na ion. This picture is consistent with the experimental observation that Na ion conductivity of Na2Ln2Ti3O10 increases from Ln=La to Nd, Sm, or Gd despite strong contraction of the unit cell volume.

• Journal of Adhesion and Interface
• /
• v.9 no.2
• /
• pp.24-31
• /
• 2008

In this work, calcium hydroxide and magnesium carbonate as metal ionic crosslinking agents were used to introduce ionic crosslinking points to the ethylene vinylacetate (EVA) emulsions for the enhancement of water resistance and mechanical properties of emulsion films. The properties of EVA emulsion film were investigated in crosslinking density, thermal features, surface energy, and mechanical properties, such as tensile strength, elongation at break and tear strength. With the increasing content of metal ionic crosslinking agent, the crosslinking density of the EVA emulsion film increases, resulting into the improvement of water resistance. The surface energy and mechanical properties of the EVA emulsion film, however, showed somewhat different behaviors. The highest surface energy, tensile strength, and tear strength were observed when 0.4% for calcium hydroxide and 0.5% for magnesium carbonate was added respectively, because the EVA emulsion containing carboxylic acid forms strong carboxylate-metal bond of ionically-crosslinked system. Therefore, it can be concluded that metal ionic crosslinking agents, such as magnesium carbonate and calcium hydroxide are considered to improve water resistance and mechanical properties of the EVA emulsion.

• Journal of the Korea Academia-Industrial cooperation Society
• /
• v.11 no.11
• /
• pp.4468-4472
• /
• 2010

SiOC films made by the inductively coupled plasma chemical vapor deposition were researched the relationship between the dielectric constant and the chemical shift. SiOC film obtained by plasma method had the main Si-O-C bond with the molecule vibration mode in the range of $930{\sim}1230\;cm^{-1}$ which consists of C-O and Si-O bonds related to the cross link formation according to the dissociation and recombination. The C-O bond originated from the elongation effect by the neighboring highly electron negative oxygen atoms at terminal C-H bond in Si-$CH_3$ of $1270cm^{-1}$. However, the Si-O bond was formed from the second ionic sites recombined after the dissociation of Si-$CH_3$ of $1270cm^{-1}$. The increase of the Si-O bond induced the redshift as the shift of peak in FTIR spectra because of the increase of right shoulder in main bond. These results mean that SiOC films become more stable and stronger than SiOC film with dominant C-O bond. So it was researched that the roughness was also decreased due to the high degree of amorphous structure at SiOC film with the redshift after annealing.