Review of novel energetic polymers and binders – high energy propellant ingredients for the new space race

Figures & data

Figure 1. HTPB.

Table 1. Mechanical properties of glycidyl azide polymer (GAP) – A comparison of mechanical properties between urethane and triazole cured GAP. For reference, HTPB-based APCP has a tensile strength of 0.7 N mm-2 and elongation maximum of around 60–80%.

Polymer Mixture Formulation by part:/Type of curing	Tensile Strength (N mm^−2)	Shore A Surface Hardness	Elongation Maximum (%)	Elongation at Break (%)	E Modulus (N mm^−2)	Glass Transition Temp (°C)	References
GAP-PB-GAP 1:1 TDI/TMP/Urethane	1.7	9	-	110	-	−59	[21]
GAP-PB-GAP 1:1 TDI/TMP/Urethane	0.4	26	-	120	-	−59	[21]
GAP-PB-GAP copolymer/Urethane	0.3	-	13	14	0.9	-	[22]
GAP 93:7 BPS./Triazole	0.1	34	82	82	0.2	−38	[23]
GAP 91.4: 8.6 BPS./Triazole	0.2	58	57	57	0.6	−34	[23]
GAP N100/Urethane*	0.3	14	16	21	5.4	−44	[24]
GAP BPS/Triazole*	0.3	66	13	15	3.0	−42	[24]
GAP 1:1 BPHQ/Triazole	0.1	-	65	73	0.2	−32	[25]
GAP 1.4:1 BPHQ/Triazole	0.2	-	26	27	0.7	-	[25]
GAP 2.5:1BPHQ./Triazole	1	-	28	28	4.2	-	[25]
GAP 13.2:1 BPS/Triazole	0.1	9	82	82	0.2	−37	[23]
GAP 10.5:1 BPS/Triazole	0.2	26	57	57	0.6	−34	[23]
GAP Triol 12:3 BPS/Triazole	0.2	22	57	57	0.4	−36	[23]
GAP 6.8:1 N100/Urethane*	0.3	-	10.5	19	4.7	−55	[26]
GAP 1.4:1 PTPB/Triazole	0.8	-	-	73	1.9	−82	[27]
GAP 16.3:1 DDPM/Triazole	0.2	-	-	50	~2	−44	[28]
GAP 5.5:1 DDPM/Triazole	4.5	-	-	80	~9	−34	[28]
GAP 3.3:1 DDPM/Triazole	13.2	-	-	30	174	−5	[28]

Dashed cells represent no data or not reported, *The following formulations contain other solid mixtures or plasticizers that may shift the properties of the resulting polymer.

Figure 2. Synthesis of GAP (top), Poly-BAMO (middle), and Poly-AMMO (bottom) as described above.

Figure 3. Synthesis of poly(allyl azide) PAA (top), PZ-23, and PZ-24 (bottom). Synthesis of poly(allyl azide) PAA (right), PZ-23 and PZ-24 (left).

Figure 4. Synthesis of azido-polybutadiene(Azido-PB) (top) and azido-HTPB (bottom).

Figure 5. Synthesis of poly-GLYN (top) and end-modified poly-GLYN (bottom).

Figure 6. one-pot synthesis of nitro-HTPB.

Figure 7. Synthesis of polyvinyl tetrazole.

Figure 8. Synthesis of glycidyl tetrazole polymer (GTP).

Figure 9. Synthesis of end modified HTPB.

Figure 10. Synthesis of PANT polymer.

Figure 11. Synthesis of poly-DAT.

Table 2. Mechanical properties of various energetic polymers. For reference, HTPB-based APCP has a tensile strength of around 0.7 N mm⁻² and elongation maximum of around 60–80%.

Polymer Mixture: Formulation by weight % or by OH:NCO ratio:	Tensile Strength (N mm^−2)	Shore A Surface Hardness	Elongation Maximum (%)	Elongation at Break (%)	E Modulus (N mm^−2)	Glass Transition Temp (°C)	References
Azido-PB 2:8 EVA	6.0	-	-	820	7	−34	[36]
Azido-PB 3:7 EVA	5.3	-	-	710	10.8	−38	[36]
Azido-PB	-	-	-	-	-	−59	[36]
HTPB 11% APCP*	0.7	-	74	-	3.0	−66	[39]
Nitro-HTPB 9.1%. APCP*	0.6	-	78	-	2.6	−58	[39]
Nitro-HTPB 12.2%. APCP*	6.7	-	71	-	2.9	−54	[39]
Nitro-HTPB 11%. APCP*	0.8	-	38	-	3.1	−48	[9]
Nitro-HTPB 9.0%. APCP*	0.7	-	45	-	2.8	−52	[9]
HTPB 11%, DOA, IPDI. APCP*	0.7	-	68	-	3.1	−67	[9]
Nitro-HTPB 0.9:1 TDI	0.8	9	-	397	0.2	-	[40]
Nitro-HTPB 1:1 TDI	1.1	19	-	292	0.4	-	[40]
Nitro-HTPB 1.1:1 TDI	1.4	24	-	185	0.7	-	[40]
(Solid H2O2) SPHP Polymer LZY	0.5	-	-	>100	-	-	[46]
HTPB-CBDT 1:1 IPDI	1.3	-	-	187	0.01	-	[53]
HTPB-CBDT 1:1 2,6-TDI	4.6	-	-	74	0.07	-	[53]
HTPB-DT 1:1 IPDI	2.0	-	-	145	0.02	-	[53]
HTPB-DT 1:1 2,6-TDI	6.4	-	-	93	0.07	-	[53]
650 gmol PTHF 64.1%, Glycerin, IPDI	6.9	-	784	-	-	-	[58]
1400 gmol PTHF 79.4%, Glycerin, IPDI	1.8	-	828	-	-	-	[58]
2900 gmol PTHF 88.9%, Glycerin, IPDI	0.9	-	866	-	-	-	[58]
650 gmol PTHF 31.6%, GPO, IPDI	34	-	60	-	-	-	[59]
650 gmol PTHF 44.4%, GPO, IPDI	17	-	420	-	-	-	[59]
650 gmol PTHF 51.3%, GPO, IPDI	5	-	490	-	-	-	[59]
650 gmol PTHF 65.6%, GPO, IPDI	4	-	940	-	-	-	[59]
1400 gmol PTHF 49.9%, GPO, IPDI	7	-	280	-	-	-	[59]
1400 gmol PTHF 73.0%, GPO, IPDI	2	-	600	-	-	-	[59]

Not reported, *The following formulations contain other solids or plasticizers that may shift the properties of the resulting polymer.

Figure 12. A comparison of performance when swapping out HTPB for energetic polymers in ammonium perchlorate based propellant formulation.

Vasudevan V, Sundararajan G. Synthesis of GAP-PB-GAP triblock copolymer and application as modifier in AP/HTPB composite propellant. Propellants Explos Pyrotech. 1999;24(5):295–300.

 Web of Science ®Google Scholar

Eroglu MS, Hazer B, Güven O. Synthesis and characterization of hydroxyl terminated poly (butadiene)-g-poly (glycidyl azide) copolymer as a new energetic propellant binder. Polym Bull. 1996;36(6):695–701.

 Web of Science ®Google Scholar

Keicher T, Kuglstatter W, Eisele S, et al. Isocyanate-free curing of glycidyl azide polymer (GAP) with Bis-Propargyl-Succinate (II). Propellants Explos Pyrotech. 2009;34(3):210–217.

 Web of Science ®Google Scholar

Menke K, Heintz T, Schweikert W, et al. Formulation and properties of ADN/GAP propellants. Propellants Explos Pyrotech. 2009;34(3):218–230.

 Web of Science ®Google Scholar

Sonawane S, Anniyappan M, Athar J, et al. Isocyanate-free curing of glycidyl azide polymer with Bis–propargylhydroquinone. Propellants Explos Pyrotech. 2017;42(4):386–393.

 Web of Science ®Google Scholar

Jensen TL, Unneberg E, Kristensen TE. Smokeless GAP-RDX composite rocket propellants containing diaminodinitroethylene (FOX-7). Propellants Explos Pyrotech. 2017;42(4):381–385.

 Web of Science ®Google Scholar

Ding Y, Hu C, Guo X, et al. Structure and mechanical properties of novel composites based on glycidyl azide polymer and propargyl‐terminated polybutadiene as potential binder of solid propellant. J Appl Polym Sci. 2014;131(7):Article ID 40007, 1–8.

 Web of Science ®Google Scholar

Hu C, Guo X, Jing Y, et al. Structure and mechanical properties of crosslinked glycidyl azide polymers via click chemistry as potential binder of solid propellant. J Appl Polym Sci. 2014;131(16):Article ID 40636, 1–7.

 Web of Science ®Google Scholar

Yoon SW, Choi MC, Chang YW, et al. Preparation of azidated polybutadiene (Az-PBD)/Ethylene-Vinyl acetate copolymer (EVA) blends for the application of energetic thermoplastic elastomer. Korean J Chem Eng. 2015;53(3):282–288.

 Google Scholar

Wang W, Han SM, Zhang DL, et al. Synthesis and curing of epoxy-teminated poly(glycidyl nitrate). Chin J Energy Mater. 2017;25(1):49–52.

 Google Scholar

Abusaidi H, Ghorbani M, Ghaieni HR. Development of composite solid propellant based on nitro functionalized hydroxyl-terminated polybutadiene. Propellants Explos Pyrotech. 2017;42(6):671–675.

 Web of Science ®Google Scholar

Paraskos AJ, Dewey MA, Edwards W, inventors; Alliant Techsystems Inc, assignee. One pot procedure for poly (glycidyl nitrate) end modification. United States patent US 7,714,078. 2010.

 Google Scholar

Zhang Y, Pang A, Xiao J, et al. A novel kind of green solid propellant containing H2O2 Cured at room temperature (SPHP). Propellants Explos Pyrotech. 2015;40(5):772–778.

 Web of Science ®Google Scholar

Rao BN, Yadav PJ, Malkappa K, et al. Triazine functionalized hydroxyl terminated polybutadiene polyurethane: influence of triazine structure. Polymer. 2015;77:323–333.

 Web of Science ®Google Scholar

Kohga M, Naya T, Shioya S. Viscoelastic and thermal decomposition behaviors of polytetrahydrofuran binder prepared using glycerin as a crosslinking modifier. J Appl Polym Sci. 2013;128(3):2089–2097.

 Web of Science ®Google Scholar

Kohga M. Mechanical characteristics and thermal decomposition behavior of polytetrahydrofuran binder using glycerol propoxylate (Mn= 260) as crosslinking agent. Propellants Explos Pyrotech. 2013;38(3):366–371.

 Web of Science ®Google Scholar