Nashrieh Shimi va Mohandesi Shimi Iran

Nashrieh Shimi va Mohandesi Shimi Iran

Synthesis, Optimization, and Investigation of the Characteristics of the Triblock Copolymer Polypropylene Glycol-Poly Glycidyl Azide-Polypropylene Glycol

Document Type : Research Article

Authors
Fhimeh Ghoroghchian
Yadollah Bayat
Fatemeh Abrishami
Faculty of Chemistry and Chemical Engineering, Malek‐Ashtar University of Technology, Tehran, I.R. IRAN
Abstract
Due to the important role of the binder of compound engines, many studies have been done to improve their mechanical and thermal characteristics. Glycidyl azide polymer is used as an energetic binder in compound engines. The aim of this research is to improve the thermal properties and glass transition temperature of this energetic binder by copolymerizing it. So, the energetic triblock the copolymer of polypropylene glycol- glycidyl azide polymer- polypropylene glycol (PPG-GAP-PPG) (Mn = 1800 g/mol) was synthesized. For this purpose glycidyl azide polymer (GAP) (Mn = 1006 g/mol) was synthesized by poly epichlorohydrin The GAP was used as the initiator. The GAP triblock copolymer was synthesized by ring-opening polymerization of polypropylene oxide in the presence of boron trifluoride etherate (BF3·OEt2) as the catalyst. The synthesized triblock copolymer was characterized by Fourier-transform infrared (FT-IR) and nuclear magnetic resonance spectroscopy. The glass transition temperature (Tg) of the triblock copolymer was characterized by differential scanning calorimetry (DSC). The DSC result showed that the glass transition temperature (Tg) of the triblock copolymer (Tg = −63 °C) is lower than the neat low molecular weight GAP (Tg = −53 °C). The thermal stability of GAP and PPG-GAP-PPG triblock copolymer was investigated using differential thermogravimetric analysis (DTG). The result indicated that the triblock copolymer is more stable than the GAP. To optimize the synthesis conditions of the triblock copolymer PPG-GAP-PPG synthesis condition, the effect of temperature and catalyst on molecular weight, and copolymerization efficiency were investigated. The best mood for the synthesis of the triblock copolymer was the yield (86%) at 10-15 ºC, and 1% by weight of the catalyst.The DSC result showed that the glass transition temperature of the copolymer (Tg = -63° C) was lower than that of low molecular weight glycidyl azide (Tg = -53 ° C). In order to optimize the synthesis conditions of PPG-GAP-PPG triblock copolymer, the influence of temperature and catalyst variables on molecular weight and copolymerization efficiency was investigated. The highest yield (86%) was obtained at 10-15 ° C and 1% of catalyst.
Keywords
Triblock copolymer
Binder
Glycidyl azide polymer
Polypropylene glycol

Subjects

[1] Mahkam M., Nabati M., Latifpour A., Aboudi J., Synthesis and Characterization of New Nitrogen-Rich Polymers as Candidates for Energetic Applications, Des Monomers Polym., 17(5): 453-457 (2014).
[2] Agrawal J.P., Hodgson R., “Organic Chemistry of Explosives”, John Wiley & Sons Inc., (2007).
[3] Menke K., Eisele S., Rocket Propellants with Reduced Smoke and High Burning Rates, Propellants, Explosives, Pyrotechnics., 22(3): 112-119 (1997).
[4] Mohan Y.M., Mani Y., Raju K.M., Synthesis of Azido Polymers as Potential Energetic Propellant Binders, J. Des Monomers Polym., 9(3): 201–236 (2006).
[5] Betzler F.M., Hartdegen V.A., Klapötke T.M., Sproll S.M., A New Energetic Binder: Glycidyl Nitramine Polymer, Cent. Eur. J. Energ. Mater., 13(2): 289-300 (2016).
[6] Iwama A., Hasue K., Takahashi T., Matsui K., Ishiura K., Hydrogenated Hydroxy‐Terminated Polyisoprene as a Fuel Binder for Composite Solid Propellants, Propellants, Explosives, Pyrotechnics., 21(1): 43-50 (1996 )
[7] Provatas A., Energetic Plasticizer Migration Studies, J. Energ. Mater., 21(4): 237-245 (2003).
[8] Ang H.G., Pisharath S., “Energetic Polymers, Binders and Plasticizers for Enhancing Performance”, Wiley –VCH Verlag GmbH & Co. KGaA, Weinheim., 109-111 (2012).
[9] Provatas A., “Energetic Polymers and Plasticisers for Explosive Formulations-A Review of Recent Advances”, Defence Science and Technology Organisation Melbourne (Australia) (2000).
[10] Badgujar D., Talawar M., Asthana S., Mahulikar P., Advances in Science and Technology of Modern Energetic Materials: An overview. J. Hazard. Mater., 151(2-3): 289-305 (2008).
[11] Macri B.J., Boron-Fuel-Rich Propellant Compositions, US3986909A, USA,  (1976).
[12] Sharmin E., Zafar F., “Polyurethane: An Introduction”, In Polyurethane, InTech ( 2012).
[13] Yang Y., Jiao D., Qiang H., Wang G., Molecular Simulation of Solubility Parameter for HTPB Solid Propellants, Chin. J. Energ. Mater., 2: (2008).
[14] Cheng T., Review of Novel Energetic Polymers and Binders – High Energy Propellant Ingredients for the New Space Race,  Des Monomers Polym., 22(1): 54–65 (2019).
[15] Pisharath S., Ang H.G., Thermal Decomposition Kinetics of a Mixture of Energetic Polymer and Nitramine Oxidizer, Thermochimica Acta., 459(1-2): 26-33 (2007).
[16] Abusaidi H., Ghaieni H.R., Ghorbani M., Influences of NCO/OH and Triol/Diol Ratios on the Mechanical Properties of Nitro-HTPB Based Polyurethane Elastomers, Iran. J. Chem. Chem. Eng. (IJCCE), 36(5): 55-63(2017)
[17] Manu S., Varghese T., Mathew S., Ninan K., Studies on Structure-Property Correlation of Cross‐Linked Glycidyl Azide Polymer, J. Appl. Polym. Sci., 114(6): 3360-3368 (2009).
[18] Manu S., Sekkar V., Scariah K., Varghese T., Mathew S., Kinetics of Glycidyl Azide Polymer‐based Urethane Network Formation, J. Appl. Polym. Sci., 110(2): 908-914 (2008).
[19] Selim K., Özkar S., Yilmaz L., Thermal Characterization of Glycidyl Azide Polymer (GAP) and GAP‐Based Binders for Composite Propellants; J. Appl. Polym. Sci.,77(3): 538-546 (2000).
[20] Gomez O., Ramon J., Arenas S., “Processes for Obtaining Hydroxy Finished Glycidyl Azide Polymer”, US5319037A, USA, (1993).
[21] Yang Z., Xin‐Ping L., Qing‐Xuan Z., Simulation Study of the Morphologies of Energetic Block Copolymers based on Glycidyl Azide Polymer, J. Appl. Polym. Sci., 129(1): 480-486 (2013).
[22] Frankel M., Grant L., Flanagan J., Historical Development of Glycidyl Azide Polymer, Journal of Propulsion and Power., 8(3): 560-563 (1992).
[23] Nazare A., Asthana S., Singh H., Glycidyl Azide Polymer (GAP)-An Energetic Component of Advanced Solid Rocket Propellants-A Review, Journal of Energetic Materials.,10(1): 43-63 (1992).
[24] Hori K., “Application of Glycidyl Azide Polymer to Hybrid Rocket Motor”, 45th AIAA/ASME/SAE/ASEE Joint Propulsion Conference & Exhibit, Denver, Colorado, USA, 2-5 August (2009).
[25] Wang X., Shu Y., Lu X., Mo H., Xu M., Synthesis and Characterization of PolyNIMMO-HTPB-PolyNIMMO Triblock Copolymer as A Potential Energetic Binder, Cent. Eur. J. Energ. Mater., 15(3): 456-467 (2018).
[26] Abrishami F., Zohari N., Zeynali V., Synthesis and Characterization of Poly (Glycidyl Nitrate‐Block‐Caprolactone‐Block‐Glycidyl Nitrate) (PGN‐PCL‐PGN) Triblock Copolymer as a Novel Energetic Binder, J. Propellants. Explos. Pyrotech., 42(9): 1032-1036 (2017).
[27] Bayat Y., Chizari M., Synthesis, Characterization and Stability of Triblock Copolymer based on Tetrahydrofuran and Glycidylazide as Binder, Polym. Sci. Ser. B., 60(5): 621-628 (2018).
[28] Chizari M., Bayat Y., Synthesis and Kinetic Study of a PCL-GAP-PCL Tri-Block Copolymer, Cent. Eur. J. Energ. Mater., 15(2): 243-257 (2018).
[29] Min S.B., Characterization of the Plasticized GAP/PEG and GAP/PCL Block Copolyurethane Binder Matrices and its Propellants, Propellants Explos Pyrotech., 33(2): 131-138 (2008).
[30] Eroglu M.S., Hazer B., Güven O., Synthesis and Characterization of Hydroxyl Terminated Poly ( Butadiene) – g – Poly ( Glycidyl Azide ) Copolymer as A New Energetic Propellant Binder, Polymer Bulletin., 36(6): 695 – 701 (1996).
[31] Chizari M., Bayat Y., Designing a Highly Energetic PCL-GAP-PCL-based PU Elastomer; Investigation of the Effect of Plasticizers on Its Properties, Cent. Eur. J. Energ. Mater., 16(1): 33-48 (2019).
 [32] Piao L., Dai Zh., Deng M., Chen X., Jing X., Synthesis and Characterization of PCL/PEG/PCL Triblock Copolymers by using Calcium Catalyst. Polymer., 44(7): 2025-2031 (2003).
[33] Abrishami F., Zohari  N., Zeynali V., Synthesis and Kinetic Study on the Thermal Degradation of Triblock Copolymer of Polycaprolactone‐Poly (Glycidyl Nitrate)‐Polycaprolactone (PCL‐PGN‐PCL) as an Energetic Binder, Polym. Adv. Technol., 30(3): 640-647 (2019).
[34] Song L.X., Guo X.Q., Du Y.F., Bai L., Thermal Degradation Comparison of Polypropylene Glycol and its Complex with Β-Cyclodextrin, Polym. Degrad. Stab., 95(4): 508-515 (2010).
[35] Ertem S., Emel Y., Cagla K., Garth L., Wilkes M., Iskender Y., Effect of Soft Segment Molecular Weight on Tensile Properties of Poly (Propylene Oxide) based Polyurethaneureas, Polymer, 21(53): 4614-4622 (2012).
[36] Min B.S., Synthesis of Azide-Terminated Glycidyl Azide Polymer with Low Molecular Weight, J. Korea Inst. Mil. Sci. Technol., 8(1): 69-80 (2005).
[37] Shanley  E.S., Melhem G.A., The Oxygen Balance Criterion for Thermal Hazards Assessment, Process Safety Progress., 14(1): 29-31 (1995).