Isocyanate‐Free and Dual Curing of Smokeless Composite Rocket Propellants

Traditional composite rocket propellants are cured by treatment of hydroxyl‐terminated prepolymers with polyfunctional aliphatic isocyanates. For development of smokeless composite propellants containing nitramines and/or ammonium dinitramide (ADN), energetic binder systems using glycidyl azide polymer (GAP) are of particular interest. Polyfunctional alkynes are potential isocyanate‐free curing agents for GAP through thermal azide‐alkyne cycloaddition and subsequent formation of triazole crosslinkages. Propargyl succinate or closely related aliphatic derivatives have previously been reported for such isocyanate‐free curing of GAP. Herein, we present the synthesis and use of a new aromatic alkyne curing agent, the crystalline solid bisphenol A bis(propargyl ether) (BABE), as isocyanate‐free curing agent in smokeless propellants based on GAP, using either octogen (HMX) and/or prilled ADN as energetic filler materials. Thermal and mechanical properties, impact and friction sensitivity and ballistic characteristics were evaluated for these alkyne cured propellants. Improved mechanical properties could be obtained by combining isocyanate and alkyne curing agents (dual curing), a combination that imparted better mechanical properties in the cured propellants than either curing system did individually. The addition of a neutral polymeric bonding agent (NPBA) for improvement of binder‐filler interactions was also investigated using tensile testing and dynamic mechanical analysis (DMA). It was verified that the presence of isocyanates is essential for the NPBA to improve the mechanical properties of the propellants, further strengthening the attractiveness of dual cure systems.     

Isocyanate‐Free Curing of Glycidyl Azide Polymer with Bis–propargylhydroquinone

Bis‐propargylhydroquinone (BPHQ) is an alkyne functionalized isocyanate‐free curing agent for hydroxyl terminated azido polymers. Conventionally, glycidyl azide polymer (GAP) is cured by isocyanate based curatives, which are toxic and hygroscopic in nature. The reaction between hydroxyl end group of GAP and isocyanate is highly sensitive to moisture causing voids in the propellant, leading to poor mechanical properties. Herein, an alternate approach was adapted to exploit 1,3‐dipolar cycloaddition reaction between azido group of GAP and the triple bond (–C≡CH) of BPHQ without catalyst at 50 °C forming triazole crosslinked polymer. The curing behavior of GAP‐BPHQ system was studied by rheological method and based on the results the gel time was determined. In addition, the reaction between GAP and BPHQ was carried out with various GAP/BPHQ ratios (0.9 to 2.5) and effects on mechanical properties of resulting triazole polymers were investigated. Post curing hardness of GAP‐BPHQ binder system was tested by surface Shore‐A hardness measurement. The compatibility of BPHQ with energetic oxidizers such as ammonium dinitramide (ADN) and hydrazinium nitroformate (HNF) were also studied by differential scanning calorimetery (DSC) technique and showed good compatibility. The activation energy (E _a) of cured GAP‐BPHQ binder was evaluated by DSC using Ozawa and Kissinger methods and are found to be 33.55 and 33.16 kcal mol^–1, respectively. The advantage of this curing system between GAP and BPHQ is unaffected by moisture as compared to isocyanate based urethane systems and also no need to control humidity during the processing of propellant. The experimental results reveal that triazole crosslinked polymer system could be a better choice to develop novel energetic binder systems for explosives as well as propellants composition with improved performance and eco‐friendly nature.     

A Study on the Triazole Crosslinked Polymeric Binder Based on Glycidyl Azide Polymer and Dipolarophile Curing Agents

Instead of using urethane curing systems, which have long been used as solid propellants, a triazole curing system has been introduced into a new binder recipe in which azide groups in the polymer react with triple bonds of a dipolarophile curing agent. Commercially available glycidyl azide polymers (GAP) were used and an aliphatic curing agent, bispropargyl succinate (BPS), as well as an aromatic curing agent, 1,4‐bis(1‐hydroxypropargyl)benzene (BHPB), were synthesized as dipolarophile curing agent. Together with networks prepared under the triazole curing system, the networks under dual curing systems, which consist of an isocyanate curing agent and a dipolarophile curing agent, were prepared. Through swelling experiments, solubility parameters and crosslinking densities of the triazole crosslinked networks were determined by using Gee’s theory and Flory–Rhener theory. The mechanical properties of the triazole crosslinked networks were also investigated with different contents of the dipolarophile curing agent, along with the type of dipolarophile curing agent. The networks prepared under the triazole curing system did not show good mechanical properties. However, GAP‐based networks prepared under a dual curing system showed excellent mechanical properties with only a small amount of dipolarophile curing agent used. The effects of BPS and BHPB on the mechanical properties of the networks were much more distinguishable in networks prepared under a dual curing system rather than a single curing system.     

Neutral Polymeric Bonding Agents (NPBA) and Their Use in Smokeless Composite Rocket Propellants Based on HMX‐GAP‐BuNENA

Very few efficient bonding agents for use in solid rocket propellants with nitramine filler materials and energetic binder systems are currently available. In this work, we report the synthesis, detailed characterization, and use of neutral polymeric bonding agents (NPBA) in isocyanate‐cured and smokeless composite rocket propellants based on the nitramine octogen (HMX), the energetic binder glycidyl azide polymer (GAP), and the energetic plasticizer N‐butyl‐2‐nitratoethylnitramine (BuNENA). These polymeric bonding agents clearly influenced the viscosity of the uncured propellant mixtures and provided significantly enhanced mechanical properties to the cured propellants, even at low NPBA concentrations (down to 0.001 wt‐% of propellant). A modified NPBA more or less free of hydroxyl functionalities for interactions with isocyanate curing agent provided the same level of mechanical improvement as regular NPBA containing a substantial number of reactive hydroxyl groups. However, some degree of reactivity towards isocyanate is essential for function.     

Glycidyl Azide Polymer Crosslinked Through Triazoles by Click Chemistry: Curing,Mechanical and Thermal Properties

Glycidyl azide polymer (GAP) was cured through “click chemistry” by reaction of the azide group with bispropargyl succinate (BPS) through a 1,3‐dipolar cycloaddition reaction to form 1,2,3‐triazole network. The properties of GAP‐based triazole networks are compared with the urethane cured GAP‐systems. The glass transition temperature (T_g), tensile strength, and modulus of the system increased with crosslink density, controlled by the azide to propargyl ratio. The triazole incorporation has a higher T_g in comparison to the GAP‐urethane system (T_g−20 °C) and the networks exhibit biphasic transitions at 61 and 88 °C. The triazole curing was studied using Differential Scanning Calorimetry (DSC) and the related kinetic parameters were helpful for predicting the cure profile at a given temperature. Density functional theory (DFT)‐based theoretical calculations implied marginal preference for 1,5‐addition over 1,4‐addition for the cycloaddition between azide and propargyl group. Thermogravimetic analysis (TG) showed better thermal stability for the GAP‐triazole and the mechanism of decomposition was elucidated using pyrolysis GC‐MS studies. The higher heat of exothermic decomposition of triazole adduct (418 kJ ⋅ mol⁻¹) against that of azide (317 kJ ⋅ mol⁻¹) and better mechanical properties of the GAP‐triazole renders it a better propellant binder than the GAP‐urethane system.     

Mechanical Properties of Smokeless Composite Rocket Propellants Based on Prilled Ammonium Dinitramide

Ammonium dinitramide (ADN) is a high performance solid oxidizer of interest for use in high impulse and smokeless composite rocket propellant formulations. While rocket propellants based on ADN may be both efficient, clean burning, and environmentally benign, ADN suffers from several notable disadvantages such as pronounced hygroscopicity, significant impact and friction sensitivity, moderate thermal instability, and numerous compatibility issues. Prilled ADN is now a commercially available and convenient product that addresses some of these disadvantages by lowering the specific surface area and thereby improving handling, processing, and stability. In this work, we report the preparation, friction and impact sensitivity and mechanical properties of several smokeless propellant formulations based on prilled ADN and isocyanate cured and plasticized glycidyl azide polymer (GAP) or polycaprolactone‐polyether. We found such propellants to have very poor mechanical properties in unmodified form and to display somewhat unreliable curing. However, by incorporation of octogen (HMX) and a neutral polymeric bonding agent (NPBA), the mechanical properties of such smokeless formulations were significantly improved. Impact and friction sensitivities of these propellants compare satisfactorily with conventional propellants based on ammonium perchlorate (AP) and inert binder systems.     

Characterization of the Plasticized GAP/PEG and GAP/PCL Block Copolyurethane Binder Matrices and its Propellants

Though glycidyl azide polymer (GAP) is a well‐known and promising energetic polymer, propellants based on it suffer from poor mechanical and low‐temperature properties. To overcome these problems, plasticized GAP‐based copolymeric binders were prepared and investigated through the incorporation of flexible‐structural polyethylene glycol (PEG) and polycaprolactone (PCL) into a binder recipe under a Desmodur N‐100 polyisocyanate (N‐100)/isophorone diisocyanate (IPDI) (2 : 1, wt. ratio) mixed curative system. The nitrate esters (NEs) or GAP oligomer were used as energetic plasticizers at various ratios to the polymers. The GAP/PCL binders held the plasticizers much more than the GAP/PEG binders did. The glass transition temperatures (T_g) of segmented copolymeric binders were more dependent on the plasticizer level than the PEG or PCL content. The increase in the plasticizer content decreased the mechanical strength and modulus of binders, while the change of strain was modest. Finally, the NE plasticized GAP‐based solid propellants showed enhanced mechanical and thermal properties by the incorporation of PEG or PCL. The properties of GAP/PCL propellants were superior to those of GAP/PEG propellants.     

Smokeless GAP‐RDX Composite Rocket Propellants Containing Diaminodinitroethylene (FOX‐7)

Composite rocket propellants prepared from nitramine fillers (RDX or HMX), glycidyl azide polymer (GAP) binder and energetic plasticizers are potential substitutes for smokeless double‐base propellants in some rocket motors. In this work, we report GAP‐RDX propellants, wherein the nitramine filler has been partly or wholly replaced by 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7). These smokeless propellants, containing 60% energetic solids and 15% N‐butyl‐2‐nitratoethylnitramine (BuNENA) energetic plasticizer, exhibited markedly reduced shock sensitivity with increasing content of FOX‐7. Conversely, addition of FOX‐7 reduced the thermochemical performance of the propellants, and samples without nitramine underwent unsteady combustion at lower pressures (no burn rate catalyst was added). The mechanical characteristics were quite modest for all propellant samples, and binder‐filler interactions improved slightly with increasing content of FOX‐7. Overall, FOX‐7 remains an attractive, but less than ideal, substitute for nitramines in smokeless GAP propellants.     

Structure and mechanical properties of novel composites based on glycidyl azide polymer and propargyl‐terminated polybutadiene as potential binder of solid propellant

Instead of the traditional isocyanate curing system as the binder of solid propellant, a triazole curing system has been developed by the reaction of azide group and alkynyl group due to a predominant advantage of avoiding to the interference of humidity. In this work, the propargyl‐terminated polybutadiene (PTPB) was blended with glycidyl azide polymers (GAPs) to produce new composites under the catalysis of cuprous chloride at ambient temperature. The triazole‐crosslinked network structure was regulated by changing the molar ratio of azide group in GAP versus alkynyl group in PTPB, and hence various crosslinked densities together with the composition changes of GAP versus PTPB cooperatively determined the mechanical properties of the resultant composites. Furthermore, the formed triazole‐crosslinked network derived from the azide group in GAP and alkynyl group in PTPB resulted in the slight increase of glass transition temperatures and a‐transition temperatures, and improved the miscibility between GAP and PTPB. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40007.     

Thermomechanical and Morphological Characteristics of Cross‐Linked GAP and GAP–HTPB Networks with Different Diisocyanates

This paper describes the mechanical and thermal characterisation of cross‐linked glycidyl azide polymer (GAP) and GAP–hydroxyl terminated polybutadiene (HTPB) networks. Cross‐linked GAP and GAP–HTPB networks were prepared by reacting GAP diol and GAP–HTPB diol mixture with different diisocyanates. The physical and mechanical characteristics were found to be influenced by the type of isocyanate curing agents, [NCO]/[OH] equivalent ratios and concentration of GAP. For all the three types of curing agents, GAP–HTPB blends of 50 : 50 to 30 : 70 ratios show higher mechanical strength over the virgin networks of GAP or HTPB. Thermal decomposition of cross‐linked GAP–HTPB networks was evaluated by thermogravimetric analysis (TGA). The kinetic parameters for the decomposition of GAP–HTPB blends were found to be dependant on the concentration of GAP and HTPB in the blend. The cross‐linked GAP–HTPB blends were subjected to dynamic mechanical analysis (DMA). The glass transition characteristics of the blends were evaluated by DMA and it was found that blends prepared with GAP content up to 30% showed single transition in the loss tangent trace indicating no phase separation in the cured network.     

GAP推进剂粘合剂固化体系力学性能的研究

在保证推进剂加工工艺性能和能量性能的前提下,通过化学共聚的方法,选用主链柔顺性较好、且在推进剂中可单独用作含能粘合剂的3,3-双(叠氮甲基)氧丁环/四氢呋喃的共聚物(BAMO/THF)来改善聚叠氮缩水甘油醚(GAP)交联网络结构,在此基础上再加入合适的扩链剂和交联剂,所得弹性体的力学性能有大幅度的提高。当固化参数R=1.3,m(GAP)∶m(BAMO/THF)=75∶25,以1,4-丁二醇(BDO)为扩链剂,异佛尔酮二异氰酸酯(IPDI)/多异氰酸酯(N100)为固化剂,胶片的拉伸强度可达到1.03MPa,断裂伸长率达到505.3%。     

Kinetics of glycidyl azide polymer‐based urethane network formation

Reactions between hydroxyl‐terminated glycidyl azide polymer (GAP) and different isocyanate curatives such as toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), and methylene diicyclohexyl isocyanate (MDCI) at various temperatures viz. 30, 40, 50, and 60°C were followed by Fourier transform infra red spectroscopy. The reactions were found to follow second‐order kinetics. With TDI and IPDI at 30°C, a two‐stage reaction was observed. For GAP‐TDI system, the second stage was slower than the first while for GAP‐IPDI system, the second stage was faster than the first indicating dominance of autocatalytic effect. The stage separation occurred due to the difference in reactivity of the isocyanate groups and was found to narrow down with increase in temperature. The viscosity build up due to the curing reaction was followed for GAP‐TDI system for comparison. The stage separation was evident in the viscosity build up also. Rheokinetic analysis done based on data generated showed a linear correlation between viscosity build up and fractional conversion. The kinetic and activation parameters evaluated from the data showed the relative difference in reactivity of the three diisocyanates with GAP. Both the approaches suggested that the reactivity of the isocyanates employed for the present study could be arranged as TDI > IPDI ? MDCI. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fine‐tuning the mechanical properties of hydroxyl‐terminated polybutadiene/ammonium perchlorate‐based composite solid propellants by varying the NCO/OH and triol/diol ratios

Changes in the mechanical properties of hydroxyl‐terminated polybutadiene/ammonium perchlorate‐based composite solid propellants were studied during the curing period with respect to variations in the crosslink density, which was predominantly determined by the equivalent ratio of diisocyanate to total hydroxyl (NCO/OH ratio) and the equivalent ratio of triol to diol (triol/diol ratio). For this purpose, 16 propellants were prepared in different compositions through changes in the NCO/OH ratios (0.81, 0.82, 0.83, and 0.85) for each triol/diol ratio (0.07, 0.09, 0.11, and 0.13) and were tested for their mechanical properties immediately after curing. The propellants with an NCO/OH ratio of 0.82 had minimum stress, modulus, and hardness with maximum strain capability, whereas the propellants with an NCO/OH ratio of 0.85 showed just the opposite behavior. Variations in the isocyanate level seemed to have more effect on the mechanical properties at higher triol/diol ratios. It was also concluded that the propellants with triol/diol–NCO/OH combinations of 0.11–0.83, 0.11–0.85, 0.13–0.81, 0.13–0.83, and 0.13–0.85 were not acceptable for upper stage case‐bonded rocket applications because of either high tensile strength or high modulus. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2072–2079, 2002; DOI 10.1002/app.10605     

GAP型交联改性双基推进剂黏合剂的力学性能

将GAP与异氰酸酯预聚后引入双基推进剂黏合剂中,研究了固化剂种类、R值、固化催化剂二月桂酸二丁基锡(T12)的含量和增塑比对黏合剂的交联网络结构参数RNB值和力学性能的影响。结果表明,随着R值以及(T12)含量的增大,黏合剂的RNB值增大。在与NC中活性-OH交联反应时,TDI的反应活性比IPDI的高。GAP-TDI/NC/NG胶片的最大抗拉强度和断裂延伸率分别可达1.09MPa和202.12%,Tg最低为-42.66℃。     

GAP型PU/PMMA聚合物互穿网络的力学性能研究

利用互穿聚合物网络技术 (IPN)对GAP粘合剂进行了力学性能改性 ,研究了组分比、引发剂用量、催化剂用量、固化参数、交联剂用量对以GAP为基体材料的PU/PMMA型IPN力学性能的影响 ;同时用动态力学谱 (DMA)分析了不同组分比下IPN的相容性     

Studies on structure property correlation of cross‐linked glycidyl azide polymer

Glycidyl azide polymer (GAP) has been evaluated for use as binder for solid propellants. The effects of various parameters like cross‐linking conditions, concentration of crosslinker, and the ratio of isocyanate to hydroxyl functional groups (NCO/OH ratio) on the mechanical properties were studied in detail. It was observed that the type of curing agent and the NCO/OH ratio have a strong influence on the gum‐stock properties. Similar impact was seen for cross‐linker concentration also. The swelling characteristics of the cross‐linked binder prepared with different NCO/OH ratios were evaluated with toluene and tetrahydrofuran (THF). The polarity and the solubility parameter of the solvents were found to influence the swelling of GAP. The NCO/OH ratio and cross‐linker concentration of the polymer were also found to affect the swelling characteristics. The sol fraction determined for the polymer was found to follow a similar pattern. The cross‐link density and average molecular weight between crosslinks (Mc) were determined from the swelling studies and also from the stress–strain relationship. The Mc values were found to be influenced by the NCO/OH ratio. Finally, the Mc values determined from the swelling data were correlated to the gum‐stock properties, and the model parameters were estimated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Curing characteristics of glycidyl azide polymer‐based binders

The curing of a glycidyl azide polymer (GAP) with a triisocyanate, Desmodur N‐100, was followed by measuring the hardness and viscosity. The thermal behavior of the cured samples were investigated by a differential scanning calorimeter (DSC) and thermal gravimetric analysis (TGA). Curing causes an increase in the glass transition temperature of GAP. The T_g of gumstocks also increases with an increasing NCO/OH ratio while the decomposition temperature remains practically unchanged. The ultimate hardness of the cured samples increases with an increasing NCO/OH ratio. The binder with a NCO/OH ratio of 0.8 was found to provide the most suitable thermal and physical characteristics for composite propellant applications. The increase in the glass transition temperature of gumstocks upon curing can be compensated by using a 1:1 mixture of bis‐2,2‐dinitropropyl acetal and formal as the plasticizer. The T_g value of gumstocks can be decreased to −46.7°C by adding 25% b.w. of a plasticizer which does not have any significant effect on the decomposition properties of the gumstocks. Furthermore, a remarkable decrease in the ultimate hardness of the gumstocks is achieved upon addition of a plasticizer, while the curing time remains almost unaffected. The addition of dibuthyltin dilaurate as a catalyst reduces the curing time of the gumstocks from 3 weeks to 5–6 days at 60°C. Use of the curing catalyst also results in the hardening of the gumstocks. The decomposition properties of the gumstocks remain practically unchanged while a noticeable increase is observed in the glass transition temperature with an increasing concentration of the catalyst. This can also be compensated by a reverse effect of the plasticizer. The gel time, an important parameter which determines the pot life of a propellant material, can be measured by monitoring the viscosity of the mixture, which shows a sharp increase when gelation starts. The addition of a curing catalyst shortens the gel time remarkably. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 65–70, 2001     

An Advanced GAP/AN/TAGN Propellant. Part I: Ballistic Properties

A solid rocket propellant based on glycidyl azide polymer (GAP) binder plasticized with nitrate esters and oxidized with a mixture of ammonium nitrate (AN) and triaminoguanidine nitrate (TAGN) was formulated and characterized. Non‐lead ballistic modifiers were also included in order to obtain a propellant with non‐acidic and non‐toxic exhaust. This propellant was found to exhibit a burning rate approximately twice that of standard GAP/AN propellants. The exponent of the propellant is high compared to commonly used composite propellants but is still in the useable range at pressures below 13.8 MPa. This propellant may present a good compromise for applications requiring intermediate burn rate and impulse combined with low‐smoke and non‐toxic exhaust.     

GAP黏合剂胶片力学性能的影响因素

应用静态拉伸、动态力学和核磁交联密度仪等方法研究了增塑剂正丁基硝氧乙基硝胺(BuNENA)、固化剂多异氰酸酯(N-100)和甲苯二异氰酸酯(TDI)、交联剂三羟甲基丙烷(TMP)、扩链剂1,4-丁二醇(BDO)对改性聚叠氮缩水甘油醚(GAP)黏合剂胶片力学性能的影响。结果表明,增塑比(Pl/Po)由0.6增至1.6,GAP黏合剂胶片的拉伸强度由0.22MPa降至0.06MPa,交联密度由6.7×10-5 mol/mL降至4.9×10-5 mol/mL,延伸率略有提升。调节N-100/TDI双固化体系,可提高GAP黏合剂胶片的强度和延伸率,当N-100和TDI的固化参数分别为0.36、1.44时,胶片强度和延伸率分别为0.24MPa和558.7%。加入质量分数0.5%的交联剂TMP可使GAP黏合剂胶片强度升至0.32MPa,延伸率降至278.5%。加入质量分数0.1%的扩链剂BDO,可使胶片强度和延伸率分别达到0.33MPa和323.1%。     

Synthesis of Carbon‐Rich Hybrid Foam from GAP‐Modified Polyurethane

4,4′‐Diisocyanato diphenylmethane (MDI)‐based polyurethanes melt and start to burn at 150–200 °C. Mainly H₂O, CO₂, CO, HCN, and N₂ are formed. The new modified polyurethane shows a different pyrolysis behavior. GAP‐diol (glycidyl azide polymer), which was used as a modifying agent, is a well‐known energetic binder with a high burning velocity and a very low adiabatic flame temperature. The modified polyurethane starts to burn at approximately 190 °C because of the emitted burnable gases, but it does not melt. The PU foam shrinks slightly and a black, solid, carbon‐rich hybrid foam remains. TGA and EGA‐FTIR revealed a three‐step decomposition mechanism of pure GAP‐diol, the isocyanate‐GAP‐diol, and PU‐GAP‐diol formulations. The first decomposition step is caused by an exothermic reaction of the azido group of the GAP‐diol. This decomposition reaction is independent of the oxygen content in the atmosphere. In the range of 190–240 °C the azido group spontaneously decomposes to nitrogen and ammonia. This decomposition is assumed to take place partly via the intermediate hydrogen azide that decomposes spontaneously to nitrogen and ammonia in the range of 190–240 °C. The second decomposition step was attributed to the depolymerization of the urethane and bisubstituted urea groups. The third decomposition step in the range of 500–750 °C was attributed to the carbonization process of the polymer backbone, which yielded solid, carbon‐rich hybrid foams at 900 °C. In air, the second and the third decomposition step shifted to lower temperatures while no solid carbon hybrid foam was left. Samples of PU‐GAP‐diol, which were not heated by a temperature program but ignited by a bunsen burner, formed a similar carbon‐rich hybrid foam. It was therefore concluded that the decomposition products of the hydrogen azide, ammonia and mainly nitrogen act as an inert atmosphere. FTIR, solid‐state ¹³C‐NMR, XRD, and heat conductivity measurements revealed a high content of sp²‐hybridized, aromatic structures in the hybrid foam. The carbon‐rich foam shows a considerable hardness coupled with high temperature resistance and large specific surface area of 2.1 m²⋅g⁻¹.