固体推进剂用粘合剂研究进展

介绍了固体推进剂用粘合剂的研究进展,着重介绍了丁羟类、叠氮类、HTPE、NEPE以及硝基和硝酸酯类粘合剂的合成、工艺以及性能研究情况,并对未来固体推进剂用粘合剂的发展进行了展望。     

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.     

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.     

Curing of Glycidyl Azide Polymer (GAP) Diol Using Isocyanate,Isocyanate‐Free,Synchronous Dual,and Sequential Dual Curing Systems

Glycidyl azide polymer (GAP) is an important energetic binder candidate for new minimum signature solid composite rocket propellants, but the mechanical properties of such GAP propellants are often limited. The mechanical characteristics of composite rocket propellants are mainly determined by the nature of the binder system and the binder‐filler interactions. In this work, we report a detailed investigation into curing systems for GAP diol with the objective of attaining the best possible mechanical characteristics as evaluated by uniaxial tensile testing of non‐plasticized polymer specimens. We started out by investigating isocyanate and isocyanate‐free curing systems, the latter by using the crystalline and easily soluble alkyne curing agent bispropargylhydroquinone (BPHQ). In the course of the presented study, we then assessed the feasibility of dual curing systems, either by using BPHQ and isophorone diisocyanate (IPDI) simultaneously (synchronous dual curing), or by applying propargyl alcohol and IPDI consecutively (sequential dual curing). The latter method, which employs propargyl alcohol as a readily available and adjustable hydroxyl‐telechelic branching agent for GAP through thermal triazole formation, gave rise to polymer specimens with mechanical characteristics that compared favorably with the best polymer specimens obtained from GAP diol and mixed isocyanate curatives. The glass transition temperature (T_g) of non‐plasticized samples was heightened when triazole‐based curing agents were included, but when plasticized with nitratoethylnitramine (NENA) plasticizer, T_g values were very similar, irrespective of the curing method.     

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.     

Rheological studies on energetic thermoplastic elastomers

Energetic thermoplastic elastomers containing energetic groups, such as azido, nitrato, nitro, and so forth, are emerging as attractive binder systems for advanced solid rocket propellants. Poly[3,3‐bis(Azidomethyl) oxetane (BAMO)‐co‐3‐azidomethyl‐3‐methyl oxetane (AMMO)] comprising hard crystalline BAMO segment and the soft/amorphous AMMO segment in various molar ratios (80 : 20, 50 : 50 and 20 : 80) were synthesized during the present work. The homo polymers namely Poly‐BAMO and Poly‐AMMO were also synthesized. All the polymers and copolymers were characterized by spectral and thermal methods. They were found to be thermally stable. The most promising 80 : 20 copolymer softened at 56°C with T_g of −36°C. Rheological studies were also carried out to determine their suitability as a binder in explosive and propellant formulations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization of Aging Behavior of Butacene® Based Composite Propellants by Loss Factor Curves

Butacene® is a polymeric binder with ferrocenyl groups chemically bonded to HTPB backbone. Through incorporation in the AP−Al composite propellant formulation, it leads to high burning rates (BR) >20 mm/s at 7 MPa, and low pressure exponents n<0.5, allowing more flexibility to the rocket design, keeping the characteristics (process, mechanical properties, pot‐life) of HTPB binder formulations together with a lower vulnerability (IM) contribution by Butacene®. The key molecular level characteristic of such HTPB based elastomeric binder systems of solid composite rocket propellants (SCRP) is the glass‐rubber transition region, which is mainly defined by the molecular mobility of the components in the polymeric network during the transition from energy to entropy elasticity with respect to temperature. The molecular rearrangement regions or binder mobility fractions related to the glass‐rubber transition of such composite propellants during storage are important in terms of in‐service time estimations. They are detectable by dynamic mechanical analysis (DMA). Formulations with and without Butacene® were prepared and analyzed using the loss factor curves obtained by torsion DMA. A special modelling with so named Exponentially Modified Gaussian (EMG) distribution was used to define and quantify sub‐transition regions in the loss factor curve. SEM images revealed the network formation connected with AP bonding, which correlate to the tensile results. DMA loss factors revealed a strong oxidation with Butacene® containing formulations during aging. Burning rates of the formulations show slight increases with aging.     

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.     

Low Risk Synthesis of Energetic Poly(3‐Azidomethyl‐3‐Methyl Oxetane) from Tosylated Precursors

Azidated oxetanic polymers such as poly(3‐azidomethyl‐3‐methyl oxetane), are under investigation as “energetic” binder to be used as an alternative to polybutadiene in solid rocket propellants. The classic synthetic route for the production of the polymer is through an azidated monomer where the N₃⁻ functionality has been previously introduced by nucleophilic displacement of a suitable, usually a halogen, leaving group. However, this could involve critical steps with manipulation of a highly unstable liquid monomer. Here it is shown that the azidation can be performed as the final step of the preparation by substitution of the tosyl group in a preformed polymer. The procedure assures good yield and purity of the product and satisfactory rate of reaction, being the energetic functionality always kept in a safe form, which shows low shock and friction sensitivity. Poly(3‐azidomethyl‐3‐methyl oxetane) was prepared by azidation of poly(3‐tosyloxymethyl‐3‐methyl oxetane) in dimethylsulfoxide, testing several operating conditions. Moreover, hypothesizing a second order kinetics, the rate constant and the activation energy for the azidation step have been estimated.     

3,3‐Bis(azidomethyl)oxetane (BAMO) Synthesis via Pentaerythritol Tosyl Derivates

3,3‐Bis(azidomethyl)oxetane (BAMO) is the most widely known azido oxetane in terms of the number of its polymers and copolymers applied as energetic binders e.g. in rocket propellants and plastic formulations of explosive materials. However, this compound continues to be a rather expensive monomer today. The aim of this study was to find a suitable synthetic route to produce this monomer in a large scale and to optimize it. The chosen route of synthesis was based on the application of tosyl pentaerythritol derivatives as the starting material. The BAMO synthesis by this method involves three stages, namely: pentaerythritol tosylation, tritosylpentaerythritol cyclization to 3,3‐bis(tosylmethyl)oxetane (BTMO), and substitution of the BTMO tosyl groups with azido groups. In this work all the stages of the synthesis were optimized. BAMO was obtained in an overall yield of 61 %. The structure of the obtained compounds was verified by two techniques, namely: ¹HNMR and FT‐IR.     

Investigation of epoxy‐resin‐modified asphalt binder

Epoxy asphalt (EA) binder has been used extensively for paving long‐span bridges in many countries because it shows excellent heat resistance, is free from bleeding, has a low‐temperature cracking resistance, and has aggregate scattering resistance. EA binders were prepared by the mixture of asphalt, epoxy resin, and a new curing agent (CR) with functional groups. The properties of the EA binder were characterized by their viscosity, tensile strength, elongation at break, compatibility, morphology, glass transition temperature (T_g), contact angle, and surface free energy. The curing process was analyzed. The results indicate that the curing temperature and asphalt content had significant effects on the properties of the EA binder. We observed that most of the strength was generated after the first 3 h at 165 °C; this provided good workability for EA pavement construction. The CR with various functional groups improved the compatibility and morphology of the EA binder. The test results show that T_g of the EA binder decreased and the contact angles increased with increasing asphalt content. It is worth noting the contact angles between water and the EA binder were always greater than 90°; this implied that the EA binder was hydrophobic and, hence, water repellent. The surface free energy and dispersion force increases with decreasing asphalt content. However, the polarity forces decreased with decreasing asphalt content. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43401.     

Preliminary Characterization of Propellants Based on p(GA/BAMO) and pAMMO Binders

In previous papers, the synthesis and characterization of OH‐terminated glycidyl azide‐r‐(3,3‐bis(azidomethyl)oxetane) copolymers (GA/BAMO) and poly‐3‐azidomethyl‐3‐methyl oxetane (pAMMO) by azidation of their respective polymeric substrates were described. The main objective was the preparation of amorphous azido‐polymers, as substitutes of hydroxy‐terminated polybutadiene (HTPB) in new formulations of energetic propellants. Here, the subsequent characterization of both the binders is presented. First of all, several isocyanates were checked in order to optimize the curing reaction, and then two small‐scale formulations of a propellant, based on aluminium and ammonium perchlorate, were prepared and characterized. Finally, the mechanical properties and burning rate were compared to those of a similar propellant based on HTPB as binder.     

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.     

Reactive Energetic Plasticizers for Energetic Polyurethane Binders Prepared via Simultaneous Huisgen Azide‐Alkyne Cycloaddition and Polyurethane Reaction

Reactive energetic plasticizers (REPs) for use in glycidyl azido polymer (GAP) based polyurethane (PU) energetic binders were investigated. These REPs consisted of an activated terminal alkyne group that was expected to give rise to Huisgen azide‐alkyne 1,3‐dipolar cycloaddition within the specific pot life for a PU formulation to prevent the migration of plasticizers, and with a gem‐dinitro group as an energy resource. A quantitative miscibility investigation between the plasticizers and uncured GAP showed that REPs exhibited better miscibility than conventional energetic plasticizers. The plasticization effect of the REPs on the GAP prepolymer with respect to the reduction of the viscosity illustrated REPs can effectively reduce the viscosity of the GAP prepolymer from 6,015 cP to 150–240 cP at the processing temperature when 50 wt‐% of REP was added. A comparison of the click reactivity and activation energies (E_a) of REPs and GAP prepolymer elucidated that the reactivity of azide‐alkyne cycloaddition depended on the dipolarophilicity of REPs which could be controlled by adjusting the length of methylene spacer between electron‐withdrawing groups (EWG) and neighboring alkynes in REPs. Thermogravimetric analysis manifested REP/GAP‐based PU binders maintained the thermal stability of the control GAP‐based PU binder. The mechanical properties and impact insensitivity of the GAP‐based PU binders were also improved by the incorporation of REPs.     

Aging of ADN Rocket Propellant Formulations with Desmophen®‐Based Elastomer Binder

Desmophen® binder‐based rocket propellant formulations containing ammonium dinitramide (ADN) and different fuel filler types (Al, HMX) were manufactured and investigated. Desmophen® D2220 is a polyesterpolyol. Polyesters are seen as a binder possibility, because of the relatively low temperature of the glass transition region compared to polyether‐based prepolymers such as GAP. The analogous formulations with AP instead of ADN were also included for comparison. The aging was followed by SEM, DSC, and DMA measurements. The accelerated aging program was developed on the principle of thermal equivalent load and the generalized van’t Hoff rule with a scaling factor equal to F=2.9. The aging was performed in air (RH<10 %) at temperature values between 65 and 85 °C and aging times adjusted to a thermal equivalent load of 15 years at 25 °C. DMA measurements of the aged ADN/Desmophen®‐based propellants identified changes in the loss factor curve. In contrast to HTPB‐Al‐AP rocket propellant formulations, the loss factor curve of the ADN formulations with Desmophen®‐based elastomer binder shows only one main apparent peak. The loss factor curves were modeled with exponentially modified Gaussian functions, which have revealed the presence of a second hidden peak. It was found that the aging could be characterized by the time‐temperature dependence of the areas of the hidden peak. The area increased with aging, which is explained by scissioning of the polymer in the shell around the ADN particles. By this process the strength is reduced, which was recognized by the decrease in storage shear modulus.     

Synthesis and Characterization of Novel Azido Polymers: Hyperbranched Poly‐3‐azidomethyl‐3‐hydroxymethyl Oxetane

In the past thirty years, azido polymers have attracted wide attention in the field of energetic materials. Currently, the synthesized azido polymers have linear structure. In the present research, hyperbranched poly‐3‐azidomethyl‐3‐ hydroxymethyl oxetane (HBPAMHMO) was synthesized using an AB₂ monomer, and its physical and chemical properties were studied. The results showed that the molecular weight of HBPAMHMO increased along with the increasing ratio of r ([monomer]₀/[initiator]₀), together with very narrow PDI (from 1.12 to 1.34), and moreover, the degree of branching increased along with the increase in polymerization temperature. As compared to linear azido polymer with similar structure, it has lower glass transition temperature, sensitivity, higher combustion heat and mechanical properties, suggesting a great prospect for numerous applications.     

Thermal structural damage and thermal decomposition characterization of GAP propellants with nitrate ester plasticizers

GAP and nitrate ester compounds are introduced into the solid propellant formulation as energetic binders and energetic plasticizing agents, respectively, to further enhance the energy level of solid propellants. However, under abnormal thermal conditions, various components within GAP propellants, especially nitrate ester plasticizers, can collectively result in the generation of a large number of voids within the propellant due to factors such as thermal stress and slow component decomposition. This phenomenon can impact the safety of solid rocket engines, necessitating research into their thermal decomposition processes and thermal damage structures. In this study, the thermal decomposition characteristics and gas products of GAP propellants with different nitrate ester plasticizer formulations were investigated using DSC-TG and FT-IR. The damage structure of GAP propellants heated under unignited conditions was studied through Micro-CT, examining the influence of heating conditions and nitrate ester plasticizers on the thermal damage structure of GAP propellants. During heating, the thermal damage structure of GAP propellants was found to include voids generated within the GAP binder and cracks at the interface between the GAP binder and particles, with nitroglycerin as a plasticizer exacerbating the thermal damage of GAP propellants (about 2.2–2.9 times).     

Viscoelastic and thermal decomposition behaviors of polytetrahydrofuran binder prepared using glycerin as a crosslinking modifier

Polytetrahydrofuran (PTHF) is an effective binder ingredient used for improving the performance of propellants. PTHF becomes sufficiently rubbery for use as a binder with the addition of an adequate crosslinking modifier. This study investigated the viscoelastic and thermal decomposition behaviors of the PTHF binder prepared using glycerin as a crosslinking modifier, as well as the influence of the molecular weight of PTHF on the characteristics of the PTHF binder. The curing behavior of the PTHF binder was suitable for the manufacture of propellants, and the superior tensile properties of the PTHF binder made it suitable for use as a propellant binder. The degree of crosslinking of the samples decreased as the molecular weight of the PTHF increased. The PTHF binder has unique dynamic mechanical properties owing to its melting and chemical structure, and these properties were dependent on the molecular weight of PTHF. The glass transition temperature (T_g) and the loss tangent at T_g decreased as the molecular weight of the PTHF increased. The temperature and frequency dependence of the PTHF binder were influenced by the melting point of PTHF. The viscoelastic properties of the binder prepared using PTHF with a molecular weight of 650 followed the time–temperature superposition principle. The activation energy for the relaxation of this binder varied remarkably at the melting point of PTHF. The thermal decomposition behavior indicated that at low temperatures, the consumption rate of the binder with low‐molecular‐weight PTHF was slightly larger than that of the binder with high‐molecular‐weight PTHF. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Thermal Decomposition of RDX Composite Propellants

The thermal decomposition characteristics of RDX, binders, and RDX composite propellants were studied using thermal analytical techniques. Three kinds of binders were tested to elucidate the role of binder on the burning rate of the propellants. There were no apparent correlations between the thermal decomposition rates of binders and the burning rates of propellants, whereas there was a correlation between the decomposition temperature and the burning rate of the propellants. It is found that the major factor which controls the burning rate is the initial thermal-decomposition stage of the binders. Thus, the burning rate of nitramine composite propellants appeared to be largely dependent on the physical and chemical properties of binder.     

Thermal characterization of glycidyl azide polymer (GAP) and GAP‐based binders for composite propellants

Differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) were used to investigate the thermal behavior of glycidyl azide polymer (GAP) and GAP‐based binders, which are of potential interest for the development of high‐performance energetic propellants. The glass transition temperature (T_g) and decomposition temperature (T_d) of pure GAP were found to be −45 and 242°C, respectively. The energy released during decomposition (ΔH_d) was measured as 485 cal/g. The effect of the heating rate on these properties was also investigated. Then, to decrease its T_g, GAP was mixed with the plasticizers dioctiladipate (DOA) and bis‐2,2‐dinitropropyl acetal formal (BDNPA/F). The thermal characterization results showed that BDNPA/F is a suitable plasticiser for GAP‐based propellants. Later, GAP was crosslinked by using the curing agent triisocyanate N‐100 and a curing catalyst dibuthyltin dilaurate (DBTDL). The thermal characterization showed that crosslinking increases the T_g and decreases the T_d of GAP. The T_g of cured GAP was decreased to sufficiently low temperatures (−45°C) by using BDNPA/F. The decomposition reaction‐rate constants were calculated. It can be concluded that the binder developed by using GAP/N‐100/BDNPA/F/DBTDL may meet the requirements of the properties that makes it useful for future propellant formulations. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 538–546, 2000