• Proceedings of the Korean Society of Propulsion Engineers Conference
• /
• 2006.05a
• /
• pp.229-232
• /
• 2006

Two novel synthetic route proposed for Hydro-Terminated Poly(EO-ran-THF) and tri-block(PEC-PTHF-PEG) copolymer by cationic ring-opening polymerization of tetrahydrofuran(THF) and ethylene oxide(EO) and just by polymerization of EO on poly-THF, respectively. Polyurethane was synthesized from random and tri-block HTPE using N-100/IPDI mixture as curing agent, and TPB(Triphenylbismuth) as catalyst. The mechanical properties of resultant polyurethane after mixing with various ratio of isocyanate was also investigated. Finally, the post treatment process of HTPE based on amount of catalyst used in the synthesis was studied, to evaluate the optimum curing condition for the polyurethane propellant binder.

• Proceedings of the Korean Society of Propulsion Engineers Conference
• /
• 2008.05a
• /
• pp.221-226
• /
• 2008

Novel synthetic routes were proposed for hydroxy-terminated Poly(EO-co-THF) by Cationic ring-opening copolymerization of Tetrahydrofuran(THF) and Ethylene oxide(EO). It was carried out using Boron trfluoride tetrahydrofuranate($BF_3$ THF complex) as catalyst in the presence of 1,4-butandiol. The resultant products are well-defined linear polyetherpolyol. Polyurethane(TPU) were prepared using resultant polyetherpolyol with IPDI/N-100 as curing agent and TPB(Triphenylbismuth) /MA(Maleic anhydride) mixture as cure catalyst. Mechanical properties of TPU prepared from poly(EO-co-THF) polyol were investigated and compared with polyurethane using ATK HTPE.

• Proceedings of the Korean Society of Propulsion Engineers Conference
• /
• 2005.11a
• /
• pp.417-421
• /
• 2005

Novel two synthetic technics using cationic ring-opening copolymerization of tetrahydrofuran (THF) and ethylene oxide (EO), or just polymerized EO on Poly-THF, could lead to random hydroxyl-terminated poly(EO-ran-THF) or tri-block PEG-PTHF-PEC, respectively. These reactions were carried out using $BF_3O(C_2H_5)_2$ as catalyst, 1,4-butanediol or PTHF as diol initiator. Copolymer structures were controlled by monomer feed ratio, or initial PTHF and EO monomer added amount. The molecular weight of polymer was merely dependant on the ratio of [monomer]/[diol], but not on catalyst. Well-defined random and block hydroxyl-terminated copolyether was found to be as the prepolymer for the propellant binder from the experiment to polyurethane with them.

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

• Bulletin of the Korean Chemical Society
• /
• v.9 no.3
• /
• pp.176-179
• /
• 1988

3-Methoxy-4-cyano-2,9-dioxabicyclo[4.3.0]non-3-e ne (1) was prepared by (4 + 2) cycloaddition reaction of methyl ${\alpha}$-cyanoacrylate with 2,3-dihydrofuran. Compound 1 was ring-open polymerized by cationic catalyst such as boron trifluoride etherate to obtain alternating head-to-head (H-H) copolymer (2) of methyl $\alpha$ -cyanoacrylate and 2,3-dihydrofuran. For comparison, head-to-tail (H-T) copolymer (3) was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $^1H$-NMR and IR spectra, but in the $^{13}C$-NMR spectra significant differences were observed between the H-H and H-T copolymers. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.3 dl/g.

• Bulletin of the Korean Chemical Society
• /
• v.8 no.2
• /
• pp.96-101
• /
• 1987

2-Ethoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyran (1_a$), 2-n-butoxy-6-methoxy-5-cyano-3,4-dihydro-2H-pyr an (1b), 2-isobutoxy-6-methoxy-5-cyano-3,4-dihydro-2H-py ran ($1_c$), and 2-ethoxy-6-methoxy-3-methyl-5-cyano-3,4-dihydro -2H-pyran ($1_d$) were prepared by (4 + 2) cycloaddition reaction of methyl $\alpha$-cyanoacrylate with the corresponding alkyl vinyl ethers. Compounds $1_{a-d}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, head-to-tail (H-T) copolymer $3_a$ was also prepared by free radical copolymerization of the corresponding monomers. The H-H copolymer exhibited minor differences in its $1_H% NMR and IR spectra, but in the $^{13}C$ NMR spectra significant differences were observed between the H-H and H-T copolymers. Glass transition temperature ($T_g$) of H-H copolymer was higher than that of the H-T copolymer, but thermal decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. Compounds $1_a$, $a_b$, and $1_c$, copolymerized well with styrene by cationic catalyst, but compound 1d failed to copolymerize with styrene. All of the H-H and H-T copolymers were soluble in common solvents and the inherent viscosities were in the range 0.2-0.4 dl/g.

• Bulletin of the Korean Chemical Society
• /
• v.8 no.2
• /
• pp.102-105
• /
• 1987

2-Methoxy-6-methyl-3,4-dihydro-2H-pyran ($1_a$), 2-ethoxy-3,6-dimethyl-3,4-dihydro-2H-pyran ($1_b$), and 2-ethoxy-3-methyl-6-ethyl-3,4-dihydro-2H-pyran ($1_c$) were prepared by (4 + 2) cycloaddition reaction from the corresponding vinyl ketones and alkyl vinyl ethers. Compounds $1_{a-c}$ were ring-open polymerized by cationic catalyst to obtain alternating head-to-head (H-H) copolymers. For comparison, copolymer of head-to-tail (H-T) was also prepared by free radical copolymerization of the mixture of the corresponding monomers. The H-H copolymer exhibited some differences in its $^1H$ NMR and IR spectra. However, significant differences were showed between the H-H and H-T copolymers in the $^{13}C$ NMR spectra. Also noteworthy was that$T_g$ value of H-H copolymer was higher than that of the corresponding H-T structure. Decomposition temperature of the H-H copolymer was lower than that of the H-T copolymer. All the H-H and H-T copolymers were soluble in common solvents.