关于GAP的研究进展

综述了聚叠氮缩水甘油醚(GAP)增塑剂及GAP粘合剂的合成方法,将GAP基粘合剂分类为GAP基热固性含能粘合剂以及GAP基热塑性含能粘合剂,其中GAP基热固性含能粘合剂主要包括了GAP共混改性、支化GAP基热固性含能粘合剂,GAP基热塑性含能粘合剂主要包括了嵌段型GAP基、接枝型GAP基热塑性含能弹性体。对应用更为广泛的GAP基热塑性含能粘合剂的发展趋势和应用前景进行了展望。     

关于GAP的研究进展

综述了聚叠氮缩水甘油醚(GAP)增塑剂及GAP粘合剂的合成方法,将GAP基粘合剂分类为GAP基热固性含能粘合剂以及GAP基热塑性含能粘合剂,其中GAP基热固性含能粘合剂主要包括了GAP共混改性、支化GAP基热固性含能粘合剂,GAP基热塑性含能粘合剂主要包括了嵌段型GAP基、接枝型GAP基热塑性含能弹性体。对应用更为广泛的GAP基热塑性含能粘合剂的发展趋势和应用前景进行了展望。     

GAP增塑剂合成研究进展

概述聚叠氮缩水甘油醚(GAP)增塑剂的合成方法、合成路线及新进展,重点介绍了端羟基GAP、端叠氮基GAP、端酯基GAP和端酯基端叠氮基GAP增塑剂的合成。     

叠氮增塑剂研究进展

介绍了叠氮增塑剂的合成方法、应用性能及研究现状,重点介绍了GAP增塑剂的合成进展和应用前景,分析比较了硝基类、硝酸酯类、硝胺类等叠氮增塑剂的能量特性和热安定性。     

含能粘合剂合成研究新进展

评述了含能粘合剂即那些符合理想粘合剂分子结构,具有潜在应用价值的以环氧乙烷、环氧丁烷为母体的含能单体的均聚物和共聚物的合成进展,包括合能预聚物的合成,含能热塑性弹性体的合成,以及不同引发剂引发的阳离子开环聚合的反应机理。讨论了聚环氧氯丙烷的开环聚合研究进展,反应条件对叠氮化的影响,等规立构和手性GAP合成的尝试,以及聚缩水甘油醚硝酸酯的合成研究现状。详述了可控聚合反应条件的实现,介绍了叠氮、硝酸酯基、硝胺基、二氟氨基等取代的环氧丁烷单体及其聚合研究进展,包括3,3-不对称环氧丁烷和多官能度环氧丁烷及其聚合物的合成研究最新进展。还介绍了含能热塑性弹性体的性质及其单体选择原则,含能聚氨酯(PU)热塑性弹性体的合成,阳离子顺序聚合制备含能热塑性弹性体和活性阳离子开环聚合制备含能热塑性弹性体的方法。     

有机硅粘合剂在耐火云母带上的应用

概述了耐火云母带用粘合剂的性能要求、发展概况,介绍了有机硅粘合剂在耐火云母带上的应用情况,讨论了有机硅粘合剂的合成原理、合成方法。     

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。     

PD涂料染色粘合剂的研制

本文介绍了一种新型染色粘合剂——PD涂料染色粘合剂的研制情况,着重讨论了该粘合剂的成分选择、乳液系统的确定以及合成反应工艺。     

聚缩水甘油醚硝酸酯合成研究进展

聚缩水甘油醚硝酸酯是近期国外重点研究的高能固体推进剂含能粘合剂之一。介绍美国聚硫公司、英国防卫研究所和ICI炸药公司对其研究概况 ,重点介绍由缩水甘油醚硝酸酯经阳离子开环聚合合成聚缩水甘油醚硝酸酯研究进展     

新型软木粘合剂的合成

主要介绍软木粘合剂的合成原理以及影响粘合剂性能的有关因素，并对采用种子乳液聚合法合成软木粘合剂进行探讨。     

Compounding of Glycidyl Azide Polymer with Nitrocellulose and its Influence on the Properties of Propellants

Currently formulated propellants comprise RDX and polymeric binders, such as hydroxy‐terminated polybutadiene (HTPB) and cellulose‐acetate butyrate (CAB) as well as the energetic substances glycidyl azide polymer (GAP) and nitrocellulose (NC). Propellants based on GAP are often brittle if they are formulated with a high content of cyclotrimethylene trinitramine (RDX) and due to the usually insufficient mechanical properties of GAP. On the other hand formulations based on RDX and NC may exceed the tolerable burning temperature with increasing RDX concentration. Therefore, in this study propellants with a high force and with relatively low burning temperature has been formulated by using a compound of NC and GAP as energetic binder. According to thermodynamic calculations GAP/NC composite propellants can be formulated with up to 15 percent more specific energy than seminitramines at the same burning temperature. By choosing appropriate polymerization conditions chemical stable compositions can be produced. ARC experiments give evidence that at temperatures from 120°C to 160°C the binder decomposes similar to NC. At higher temperatures the behaviour switches from NC type to GAP type decomposition. In comparison to GAP bound propellants the compressive strength of propellants bound by the GAP/NC compound can be significantly increased by up to 420 percent at room temperature. Although the examined seminitramine propellants bound with NC show a compressive strength which is about 10 percent higher at room temperature, the GAP/NC compositions are quite superior at elevated temperature.     

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.     

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.     

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.     

含1,1–二氨基–2,2–二硝基乙烯推进剂的能量特性参数计算研究

利用国军标方法及CAD系统软件,在标准条件(pc∶p0=70∶1)下,计算了含1,1-二氨基-2,2-二硝基乙烯(FOX-7)的各类推进剂的能量特性参数,分析了氧化剂(AP、RDX、CL-20)及黏合剂(HTPB、PET、GAP、PBAMO)等成分对FOX-7推进剂能量特性的影响。结果表明,将AP加入HTPB/FOX-7推进剂配方中取代FOX-7可有效改善氧条件,有利于推进剂能量的提高。在黏合剂含量较低(质量分数<8%)的推进剂体系中,使用惰性黏合剂有利于提高推进剂的能量;而在黏合剂含量较高(质量分数>10%)的推进剂体系中,使用含能黏合剂提高推进剂能量的幅度优于惰性黏合剂,且GAP优于PBAMO。用FOX-7取代NEPE推进剂中的AP,推进剂最大理论比冲可达2 567 N.s/kg。由GAP/FOX-7/RDX组成的无烟推进剂,在很宽的范围内都可以达到2 400 N.s/kg以上的理论比冲值。     

Combustion of GAP Based Energetic Pyrolants

Glycidyl azide polymer (GAP) is a high energy material used as a fuel component and binder of propellants and gas generators. High temperature products are formed by the scission of the chemical bond N₃ when GAP is decomposed. The major decomposition products are N₂, CO, and C. Though GAP contains no oxidizer fragments in its products, an addition of metal particles increases the energy of GAP. A mixture of GAP and metal particles forms a high energy metal based GAP pyrolant, i.e. GAP/metal pyrolant. The metals examined are Al, Mg, B, Ti, and Zr. The results indicate that the thermal decomposition and burning rate are dependent on the type of metals mixed.     

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.     

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     

高纯硼粒子的包覆及其在高能富燃料推进剂中的应用（续完）

3．3用高热值金属作包覆剂 3．3．1用金属钛作包覆剂 早在1984年M．K．King等人就研究了用金属Ti或Zr包覆硼粒子的工艺,他们还研究了这种包拨的硼粒子的点火性能。结果表明：只有当环境温度达到包覆金属的点火温度时,才会发生硼粒子的点火反应;外层金属的燃烧通过反应性气体的扩散过程及其在粒子表面碰撞来控制。