• Journal of the Korea Institute of Military Science and Technology
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• v.12 no.2
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• pp.228-235
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• 2009

We synthesized glycidyl azide monomer(GAM) as a monomer for polymerization of glycidy azide polymer(GAP) which is a promising energetic prepolymer for a plastic-bonded explosive. Using quantitative real-tim in-situ infrared(in-situ IR) spectroscopy, kinetic study on the cationic ring opening polymerization of GAM was carried out. The reaction rate was obtained from monitoring the change of ether C-O stretching band($1050cm^{-1}$) in series IR spectra. The reaction was in accordance with the first-order reaction law for each of reaction temperature at 100/1 mole ratio of [GAM]/[$BF_3*etherate$]. In the ring opening polymerization of GAM, with ratio of [GAM]/[$BF_3*etherate$] to equal 100/1 at various temperature, the activation parameters obtained from the evaluation of kinetic data were ${\Delta}H^*$=14.34kcal/mol, ${\Delta}S^*=-12.31cal/mol{\cdot}K$ and $E_a$=14.89kcal/mol.

• Journal of the Korea Institute of Military Science and Technology
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• v.8 no.1 s.20
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• pp.69-80
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• 2005

A synthesis of azide-terminated glycidyl azide polymer, GAP-A, was carried out by tosylation and azidation of polyepichlorohydrin(PECH) prepared by cationic ring-opening polymerization. Polyepichlorohydrin was prepared by cationic activated monomer polymerization using ethylene glycol and $BF_3{\cdot}OEt_2$ as an initiator and a catalyst at $\~10^{\circ}C$. Tosylation of polyepichlorohydrin was performed using traditional TsCl/pyridine method and was also carried out using TsCl/amine catalysts to reduce the reaction time significantly. Azidation of tosyl-terminated PECH(OTs-PECH) was performed using $NaN_3$ as an azidation reagent in DMF solvent at high temperature and was unexpectedly completed within 2 hours.

• Proceedings of the Korean Society of Propulsion Engineers Conference
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• 2008.11a
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• pp.231-236
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• 2008

The well-defined copolymers derived from Epichlorohydrin(ECH), Tetrahydrofuran(THF) were synthesized by Cationic ring-opening polymerization(CROP) with 1,4-Butandiol, a initiator, and $BF_3THF$ Complex, a catalyst via Activated monomer mechanism, which could lead to hydroxyl-terminated polyethers. The molecular weight of polymers were dependant on the ratio of [monomer]/[diol], Copolymer structures were controlled by monomers feed ratio, ECH and THF added. This polymers were functionalized from Chlorine group to Azide group using $S_N2$ reaction. Synthesized polymers were found to be as the prepolymer for polyurethane. Polyurethane was synthesized in the presence of N-100/IPDI mixture, a curing agent, and TPB(triphenyl bismuth)/MA(Maleic anhydride) mixture, a catalyst system. The curing behavior and mechanical properties of polyurethane after mixing with various prepolymer’s composition and the molecular weight were studied.

• Applied Chemistry for Engineering
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• v.31 no.3
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• pp.267-276
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• 2020

Poly(epichlorohydrin) copolyol series (PECH copolyols) were synthesized via cationic ring-opening copolymerization (ROCP) of oxirane-based monomers and effects of reaction temperature, solvent type, and initiator were studied. As a comonomer, two types of alkylene oxides were used, and polymerization conditions were conducted both with diethylene glycol (DEG) as an initiator in methylene chloride (MC) solvent and tripropylene glycol (TPG) in toluene solvent. In order to induce the active monomer (AM) mechanism in the ring-opening copolymerization reaction, the monomer was injected by an incremental monomer addition (IMA) method using a syringe pump, and the polymerization was performed at -5 ℃. PECH copolyol, a synthesized ephichorohydrin (ECH)-based copolyol, was converted to glycidyl azide-based energy-containing copolyol (GAP copolyol) by azadizing the ECH unit through a substitution reaction. It was confirmed that the synthesized azide copolyol had little effects on changes of the solvent and the initiator. Also, the molecular weight increased 500 after the azide reaction, thereby the GAP copolyol was polymerized as designed. As the content of the comonomer increased, both the T_g and viscosity tended to decrease due to the influence of the alkyl chain length. It is possible to fundamentally prevent CH₃N₃ amount produced in the azide reaction process, and it is expected that a large-scale process could be achievable.