• Korean Chemical Engineering Research
• /
• v.44 no.4
• /
• pp.417-423
• /
• 2006

A series of amine functionalized MCM-41 catalysts were prepared by aminopropyltrimethoxysilane grafting and their catalytic performance in Knoevenagel reaction of selected substrates was investigated. Water resistant and catalytically active amine grafted MCM-41 was prepared by post-synthetic silylation using methyltrimethoxysilane ; hydrogen bonding of the water molecules formed during the condensation reaction to the active N group was suppressed, which led to high TON of the reaction. Amine functionalized MCM-41 prepared by coating method produced high conversion, but the TON of the catalyst was much lower than that of the amine grafted MCM-41; pore volume of the functionalized MCM-41 decreased substantially and large portion of the immobilized amine is believed to be hydrogen bonded to each other, which can result in decrease in the basicity of the N group. A secondary amine group was prepared by room temperature condensation between aminopropylsilane and chloropropylsilane, and the MCM-41 grafted with the secondary amine group demonstrated the highest catalytic activity among the catalysts prepared.

• Applied Chemistry for Engineering
• /
• v.5 no.3
• /
• pp.517-523
• /
• 1994

The effects of cure kinetics and mechanism of DGEBA(diglycidyl ether of bisphenol A)/MDA(4,4'-methylene dianiline) with SN(succinonitrile) and HQ(hydroquinone) as an additive and accelerator were investigated. Cure kinetics was evaluated by Kissinger equation and fractional-life method through DSC analysis. The activation energy has hydroxyl group as an accelerator, the activation energy and the starting cure-temperature were lower than those of DGEBA/MDA/SN system. Cure mechanism of those systems was investigated through FT-IR according to the various SN contents. The ratio was SN : HQ = 4 : 1. It has been known that the cure reactions of an epoxy-diamine system are composed of primary amine-epoxy reaction, secondary amino-epoxy reaction and epoxy-hydroxyl group reaction. But in DGEBA/MDA/SN system, primary amino-CN group reaction and CN group-hydroxyl group reaction were added to the above mentioned reactions. These reactions attributed to the long main chain and the low crossliking density. And in DGEBA/MDA/SN/HQ system, hydroxyl group of HQ formed a transition state with epoxide group and amime group and also opened the ring of the epoxide group rapidly, then amino-epoxy reaction took place easily.

• Korean Journal of Materials Research
• /
• v.3 no.3
• /
• pp.272-275
• /
• 1993

To modify the toughness of epoxy for matrix, succinonitrile(SN) was introduced to diglycidy1 ether of bisphenol-A (DGEBA)/methylene dianiline(MDA)system. Cure reaction mdchanism of the DGEBA/MDA/SN system was strdied through Fourier transform infrared(FT-IR) spectrometry. As a result, the reaction of nitrile group of SN with secondary amine and with hydroxy1 group prevented the reaction of hydroxy1 group with epoxide group from crossoinding. Nitrile groups produced amide group by reacting with hydroxy1 groups and made a lowered crosslind density in chain networks.

• Korean Journal of Materials Research
• /
• v.3 no.1
• /
• pp.95-100
• /
• 1993

Abstract Fourier transform infrared (FT -IR) instrument was used to st.udy the thermoset behavior of DGEBA/MDA system with succinonit.rile. That was experimented with the samples which were cured from 8$0^{\circ}C$ to 17$0^{\circ}C$ every 3$0^{\circ}C$ for 1 hour and uncured with different SN content. respect.ively. It was known that prImary amine hydrogen reacted wit.h epoxide group, secondary amine hydrogen with epoxide group and hydroxyl with epoxide group. In addition. the reaction of primary amine hydrogen with nitrile gorup of SN and of hydroxyl group with nitrile group of SN came about. These t.wo reactions made chain bond length longer between main chains.

• Archives of Pharmacal Research
• /
• v.12 no.4
• /
• pp.239-242
• /
• 1989

Several physiological components containing a secondary amino group were capable of reacting sodium nitroprusside to form potentially carcinogenic nitrosamines under physiological conditions (pH 7.3, 37). In each case the products were identical to those produced upon reaction with nitrous acid at much lower pH values. Reaction rates measured with proline were shown to reflect a first order dependence on both amine and nitroprusside concentrations. The strong influences of pH on the reactions of sodium nitro prusside with amines were also observed. These results show sodium nitroprusside could be a very potent nitrosation agent under physiological conditions.

• Polymer(Korea)
• /
• v.26 no.5
• /
• pp.599-606
• /
• 2002

In this study, 4,4'-tetraglycidyl diaminodiphenyl methane (TGDDM)/polyamideimide (PAI) blends were cured using diaminodiphenyl sulfone (DDS). And the effect of addition of different PAI contents to neat TGDDM was investigated in the thermal, mechanical, and morphological properties of the blends. The cure behavior and thermal stability of the cured specimens were monitored by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), respectively. Also, the critical stress intensity factor (K$\_$IC/) was measured in UTM, and the phase separation behavior and final morphology of TGDDM/PAI blends were examined in scanning electron microscopy(SEM). As a result, the cure temperature and cure activation energy (E$\_$a/) were decreased with increasing the PAI content. The decreasing of cure temperature and cure activation energy were probably due to the presence of secondary amine group of PAI backbone used as co-initiator. But, the decomposition activation energy (E$\_$t/) and K$\_$IC/ value were increased up to 5. 10 phr of PAI content, respectively and they were decreased above the PAI contents. These results were explained on the basis of chain scission reaction by etherification. And morphology of blends observed from SEM was confirmed in co-continuous structures.

• Bulletin of the Korean Chemical Society
• /
• v.34 no.10
• /
• pp.2983-2988
• /
• 2013

Second-order rate constants ($k_N$) have been measured spectrophotometrically for the reactions of 4-chloro-2-nitrophenyl X-substituted-benzoates (1a-1h) with a series of cyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Hammett plot for the reactions of 1a-1h with piperidine consists of two intersecting straight lines, while the Yukawa-Tsuno plot exhibits an excellent linear correlation with ${\rho}_X $ = 1.25 and r = 0.58, indicating that the nonlinear Hammett plot is not due to a change in the rate-determining step (RDS) but is caused by ground-state stabilization through resonance interactions for substrates possessing an electron-withdrawing group in the benzoyl moiety. The Br${\o}$nsted-type plot for the reactions of 4-chloro-2-nitrophenyl benzoate (1d) with a series of cyclic secondary amines curves downward with ${\beta}_2$ = 0.85, ${\beta}_1$ = 0.24, and $pK_a{^o}$ = 10.5, implying that a change in RDS occurs from the $k_2$ step to the $k_1$ process as the $pK_a$ of the conjugate acid of the amine exceeds 10.5. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio associated with the reaction of 1d reveals that $k_2$ is dependent on the amine basicity, which is contrary to generally held views.

• Bulletin of the Korean Chemical Society
• /
• v.29 no.4
• /
• pp.767-771
• /
• 2008

Second-order rate constants have been measured spectrophotometrically for the Michael-type reaction of 1-(Xsubstituted phenyl)-2-propyn-1-ones (2a-f) with amines in $H_2O$ at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. A linear Brønsted-type plot is obtained with ${\beta}_{nuc}$ = 0.25 ${\pm}$ 0.02, a typical $\beta_{nuc}$ value for reactions which proceed through a stepwise mechanism with attack of amine on the electrophilic center being the rate-determining step. Secondary alicyclic amines are found to be more reactive than isobasic primary amines. The Hammett plot for the reactions of 2a-f with morpholine is not linear, i.e., the substrate with a strong electron-donating group (e.g., 4-MeO) exhibits a negative deviation from the Hammett plot. However, the Yukawa-Tsuno plot for the same reactions exhibits an excellent linear correlation with ρ = 0.62 and r = 0.82. Thus, it has been proposed that the nonlinear Hammett plot is not due to a change in the ra te-determining step but due to ground-state stabilization through resonance interactions.

• Journal of the Korean Chemical Society
• /
• v.43 no.3
• /
• pp.294-301
• /
• 1999

Geminal bisphosphonates have been well known to be effective inhibitors of various calciumrelated disorders such as Paget's disease, hypercalcemia of malignancy, and osteoporosis. To synthesize bisphosphonates, we have used the pentacovalent oxaphospholene prepared from methyl vinyl ketone and triethyl-phosphite. Υ-Ketobisphosphonates are obtained by bromination, applied Westheimer reaction, and hydrolysis of synthesized oxaphospholene. This compound was converted to the N-alkylated Υ-aminobisphosphonates by the reductive amination. Conversion of the resulting secondary amine to the tertiary one, followed by introduction of the second alkyl group on the nitrogen, was led to the synthesis of new N,N'-dialkylated Υ-aminobisphosphonates.

• Polymer(Korea)
• /
• v.36 no.6
• /
• pp.822-830
• /
• 2012

We used dipodal type bis[3-(trimethoxysilyl)propyl]amine (BTMA) silane coupling agent to modify silica nanoparticles to introduce secondary amino groups on the silica surface. These N-H groups were reacted with three different molecular weights (M.W. = 258, 575, and 700) of poly(ethylene glycol) diacrylates to introduce different attached layer thicknesses on the silica surface by Michael addition reaction. After Michael addition reaction, we used several analytical techniques such as fourier transform infrared spectroscopy (FTIR), elemental analysis (EA) and solid state $^{13}C$ cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance spectroscopy to characterize introduced structures. We found almost complete Michael addition reaction of both two acrylate groups of PDGDA with N-H groups of BTMA modified silica to form ${\beta}$-amino acid esters. Between equimolar ratio of pure BTMA and pure PEGDA reaction, only one acrylate group of two acrylate groups of PEGDA reacted with N-H groups of pure BTMA to form ${\beta}$-amino acid ester and the other remaining acrylate group can be used to form a polymer later.