• 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.

• Journal of the Korean Chemical Society
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• v.35 no.6
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• pp.765-767
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• 1991

• Journal of the Korean Chemical Society
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• v.30 no.6
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• pp.556-558
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• 1986

• Applied Chemistry for Engineering
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• v.32 no.2
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• pp.224-227
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• 2021

A rapid and selective copper-catalyzed amination of aryl halides with sodium azide was established by using 10 mol % of CuI, and 20 mol % of N,N'-dimethylethylenediamine in DMSO under microwave irradiation for 10 min. The catalytic system with 4-substituted aryl iodides was found to be the most effective leading to a nearly complete conversion.

• 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.

• Korean Chemical Engineering Research
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• v.53 no.3
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• pp.282-288
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• 2015

A new energetic thermoplastic elastomer based on the azidated polybutadiene(Az-PBD)/ethylene vinyl acetate copolymer (EVA) blends was prepared, and structure and properties of the blends were invetigated by SEM, DSC, DMA, tensile testing and combustion test. The Az-PBD was synthesized via a two-step process involving the addition reaction of commercially available 1,2-PBD with $Br_2$ and subsequent nucleophilic substitution reaction of the brominated PBD with $NaN_3$. EVA/Az-PBD with 90/10, 80/20, 70/30 (wt/wt) was prepared by a solution blending. SEM, DSC, and DMA results revealed that the blends are partially compatible and Az-PBD is dispersed in continuous EVA matrix. Tensile test showed that modulus and tension set increased while elongation-at-break of the blends decreased with increasing Az-PBD content in the blends, but all the blends showed a elongation at break as high as 700% and a tension set of less than 5%, indicating that the blends are typically elastomeric. Combustion test showed that, with increasing Az-PBD content in the blend, higher energy can be released.

• Polymer(Korea)
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• v.33 no.2
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• pp.158-163
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• 2009

In this study, we synthesized a series of dendritic polystyrene-b-linear poly (t-butyl acrylate) copolymers with well-defined molecular architectures. The hydroxyl group located at the focal point of the second generation dendron bearing polystyrene ($M_n$ = 1000 g/mol) peripheries was converted into amine group via the following stepwise reactions: 1) tosylatoin, 2) azidation, and 3) reduction. On the other hand, the linear poly (t-butyl acrylate)s were prepared by an atom transfer radical polymerization (ATRP) of t-butyl acrylate where benzyl 2-bromopropanoate and Cu(I)Br/PMDETA were used as initiator and catalyst, respectively. To convert the end group of prepared poly (t-butyl acrylate) s into carboxylic acid, a debenzylation was performed using Pd/C catalyst under $H_2$ atmosphere. In the final step, dendritic-linear block copolymers were obtained through a simple amide coupling reaction mediated by 4-(dimethylamino) pyridine(DMAP) and N,N'-diisopropylcarbodiimide(DIPC). The resulting diblock copolymers were shown to have well-defined molecular weights and narrow molecular weight distributions as supported by $^1H$-NMR spectroscopy and gel permeation chromatography(GPC).