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     

Phase transitions and mechanical properties of nitrocellulose plasticized by glycidyl azide polymer and nitroglycerine

Films of nitrocellulose (NC), glycidyl azide polymer (GAP), and nitroglycerine (NG) have been evaluated using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, dynamic mechanical analysis (DMA), and tensile testing. The SEM micrographs demonstrate that, even at low GAP concentration, a portion of GAP will coalesce into spherical domains due to a saturation effect. This is related to the inability of higher molecular weight GAP to effectively situate itself between NC polymer chains. The addition of a small fraction of lower molecular weight NG completely changes this behavior. DMA confirms that two transitions are present and can be attributed to a plasticizer rich phase (β), a polymer rich phase (α) and that NC plasticized with GAP is in accordance with the Gordon-Taylor equation. Tensile results show that the addition of a small fraction of NG to a NC/GAP based-formulation increases elongation at break to values similar to that of the NC/NG base formulation. The combination of these two plasticizers, GAP and NG, allows for the plasticization of NC at significantly lower environmental and human toxicity levels.     

硝酸酯增塑的叠氮胶粘剂研究进展

论述了国内外叠氮缩水甘油聚醚(GAP)胶粘剂的研究现状及存在的差距,评估了GAP胶粘剂预聚物的物理性能、热性能、危险性及其与推进剂组分的相容性;最后介绍了制备硝酸酯增塑GAP胶粘剂的实验室放大条件和工艺流程,并对其今后的发展方向进行了展望。     

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     

Rheological and thermal properties of glycidyl azide polyol‐based energetic thermoplastic polyurethane elastomers

The purpose of this study was to investigate the effects of polyol on glycidyl azide polyol (GAP)‐based energetic thermoplastic polyurethane elastomers (ETPEs). Briefly, a series of GAP/polyol‐based ETPEs (GAP/polyol ETPEs) with different copolyol ratios and hard segment contents were synthesized using GAP‐diol with common polyol and 4,4‐methylenebis(phenylisocyanate)‐extended 1,5‐pentanediol as soft and hard segments, respectively, by solution polymerization in dimethylformamide. The three types of polyols used were poly(tetramethylene ether) glycol (PTMG), polycarbonate‐diol (PCL‐diol) and polycaprolactone‐diol (PCD‐diol). The synthesized GAP/polyol ETPEs were identified and characterized using Fourier transform infrared and ¹H NMR spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and rheometric mechanical spectrometry. For GAP/PCL ETPEs with lower hard segment content, DSC results showed that the GAP segment failed to interact with either the PCL segment or PCL melting. In addition, the results of DMA showed that the presence of PCL segments in ETPEs improved the storage modulus below the melting temperature of the PCL block. Further, the crystalline PCL segments were attributed to reinforcing the ETPEs in a manner similar to that of the hard domain. As the hard segment content increased in the GAP/polyol ETPEs, both GAP/PTMG ETPEs and GAP/PCL ETPEs exhibited microphase separation transitions, while rheological experiments demonstrated a sudden decrease in complex viscosity in neighboring microphase separation transitions. © 2012 Society of Chemical Industry     

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     

Synthesis,spectral and DSC analysis of glycidyl azide polymers containing different initiating diol units

Glycidyl azide polymers (GAPs), containing different diol units, were prepared by treating the corresponding poly(epichlorohydrin)s (PECHs) with sodium azide in DMF solvent at 110°C for 8–10 h. The poly(epichlorohydrin)s containing different diol units were synthesized by the polymerization of epichlorohydrin using borontrifluoride etherate as initiator in the presence of a small amount of low molecular weight diols. The formation of these PECHs was confirmed by IR spectroscopy. The nature of terminal hydroxyl group present in the polymer chain was confirmed by proton NMR spectroscopy. The structure of GAPs containing different initiating diol units was confirmed by UV, IR, and proton NMR spectral analysis. Thermal properties of the GAPs were evaluated using differential scanning calorimetry; the stabilities and glass‐transition temperatures of the GAPs varied according to the initiating diol unit present in the polymer chains. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2157–2163, 2004     

Network regulation and properties optimization of glycidyl azide polymer-based materials as a candidate of solid propellant binder via alternating the functionality of propargyl-terminated polyether

A kind of glycidyl azide polymer (GAP)-based composite has been fabricated using propargyl-terminated ethylene oxide-tetrahydrofuran copolymer (PPET) with two (p-) and three (t-) alkyne functionalities via Huisgen reaction. Independent upon the PPET functionality, both crosslink densities and mechanical properties for two GAP/PPET systems showed a positive-interrelation changes of initial increase and subsequent decrease with an increase of azide/alkyne molar ratios. At equivalent of azide/alkyne molar ratios, the composites containing t-PPET with higher alkyne functionality exhibited better mechanical properties, while those with two alkyne functionality presented lower glass transition. Under the regulation of alkyne functionality as 3 and azide/alkyne molar ratio as 3:1, the tensile strength, Young's modulus and breaking elongation could simultaneously reach the maximum values of 1.38 MPa, 4.07 MPa, and 122.5%, which was ascribed to optimal participation of azide/alkyne reaction into network construction. Overall, this study provides an additional optimization route for network-structured binders in solid propellant system. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48016.     

GAP/PET双软段含能聚氨酯弹性体的性能

为改善聚叠氮缩水甘油醚(GAP)的性能,选用环氧乙烷/四氢呋喃共聚醚(PET),以三羟甲基丙烷(TMP)为交联剂、异佛尔酮二异氰酸酯(IPDI)为固化剂,制备了GAP/PET/TMP/IPDI双软段含能聚氨酯弹性体,采用FTIR、DSC、XRD等手段对弹性体进行了表征。实验结果表明:在催化剂含量为0.1%时,两种软段与IPDI的反应速率变化有一定差异,但能够共同形成交联网络结构;PET软段的引入使得弹性体拉伸强度提高0.9MPa,延伸率提高156%;弹性体显示出两个软段的Tg,并随两类软段含量的不同而变化。所制弹性体为非晶聚合物,183℃开始分解。     

Molecular-beam mass-spectrometric study of the flame structure of composite propellants based on nitramines and glycidyl azide polymer at a pressure of 1 MPa

A study was performed of the chemical and thermal structure of flames of model composite propellants based on cyclic nitramines (RDX and HMX) and an active binder (glycidyl azide polymer) at a pressure of 1 MPa. Propellant burning rates were measured. The chemical structure of the flame was studied using molecular-beam mass spectrometry, which previously has not been employed at high pressures. Eleven species (H₂, H₂O, HCN, N₂, CO, CH₂O, NO, N₂O, CO₂, NO₂, and nitramine vapor) were identified, and their concentration profiles, including the composition near the burning surface were measured. Two chemical-reaction zones were observed. It was shown that flames of nitramine/glycidyl azide polymer propellants are dominated by the same reactions as in flames of pure nitramines. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 6, pp. 48–57, November–December, 2006.     

Kinetics of the copolymerization of alkylene oxides with glycidyl methacrylate

In the present study, the kinetics of copolymerization reaction of propylene oxide (PO) and butylene oxide (BO) with glycidyl methacrylate (GMA) in the presence of BF₃ · O(C₂H₅)₂ catalyst were investigated. The kinetic parameters and activation energy of the copolymerization reaction were calculated. The amounts of reacting PO, BO, and GMA during copolymerization were determined by chromatographic method, because the same copolymerization conditions were carried out for them. It was determined that the copolymerization rate of PO (r₀) and BO (r₀) was higher than that of GMA, but activation energy (E) of GMA was higher than that of PO and BO. The rate of reaction, the rate constant, and activation energy were calculated from the amount of copolymer obtained with respect to time. The structures of synthesized copolymers were determined by the spectral and chemical analysis methods. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

微量热法研究GAP与BPS固化反应

为了解叠氮黏合剂/非异氰酸酯固化体系的反应动力学和固化终点,通过非等温与等温微量热法,利用Kissinger方程和Crane方程研究了聚叠氮缩水甘油醚(GAP)与非异氰酸酯固化剂-丁二酸二丙炔醇酯(BPS)黏结体系的固化过程。结果表明,—C≡C—与—N₃摩尔比为1时,GAP/BPS黏结体系固化反应放热量最大;固化反应的表观活化能为80.33kJ/mol,指前因子为10^8.42s^-1,反应级数为0.94,固化反应热为-1357.69J/g;拟合计算出了黏结体系的特征温度,凝胶温度为313.87K,固化温度为316.18K,后固化温度为338.55K;GAP/BPS黏结体系固化反应中存在自催化现象;拟合出黏结体系完全固化时间与温度之间的函数关系为y=4.13×10¹⁰e^-0.06441x+5.029。     

Kinetics of phase separation in polyurethane/polystyrene semi-1 interpenetrating polymer networks. 1. Light transmission studies

The phase separation of different in-situ semi-1 interpenetrating polymer networks (IPNs) based on polyurethane and polystyrene has been followed by light transmission. The effect of the presence ab initio of small amounts of homopolystyrene in the initial reaction mixture on the phase separation process has also been examined. If gelation of the polyurethane occurs before the onset of phase separation, the latter is impeded or strongly limited, and transparent semi-1 IPNs are obtained. In the opposite case, phase separation is macroscopic and the material is turbid.     

Catalytic mechanisms of triphenyl bismuth,dibutyltin dilaurate,and their combination in polyurethane-forming reaction

The catalytic mechanisms of triphenyl bismuth (TPB), dibutyltin dilaurate (DBTDL) and their combination have been studied in a model polyurethane reaction system consisting of copolyether (tetrahydrofuran–ethyleneoxide) and N-100; NMR spectroscopy was used to detect the associations between reactants and catalysts. A relatively stable complex was shown to be formed between hydroxyl and isocyanate; the catalysts showed different effects on the isocyanate–hydroxyl complex, therefore resulting in different curing characteristics. The formation of hydrogen bonding between the complexed hydroxyl and other hydroxyl or the resulting urethane provided an “auto-catalysis” to urethane formation. DBTDL destroyed the isocyanate–hydroxyl complex before catalyzing the reaction through the formation of a ternary complex, whereas TPB was able to activate the isocyanate–hydroxyl complex directly to form urethane. The reaction catalyzed by the combination of TPB and DBTDL gained advantages from the multiple catalytic entities, i.e., TPB, DBTDL, and a TPB–DBTDL complex. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1217–1225, 1997     

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     

Influence of retention system and curing on paper wet strength improvement by a copolymer containing glycidyl groups

The copolymer (PGS) synthesized by polymerization of glycidyl methacrylate with styrene had a significant effect on paper wet strength. Factors such as retention aids, curing temperature, and curing time were investigated. The results showed that among four kinds of partially aminated poly N‐vinylformamide (APNVF), APNVF‐4 that had the highest charge density was the most effective for strengthening paper. The effectiveness of the retention systems increased with their wet functionality in the order APNVF‐4 > C‐PAM ≈ PAAm > PEI > PDADMAC. The curing temperature and curing time had little influence on paper dry strength, but they influenced paper wet strength greatly. The FTIR studies on model reactions showed that glycidyl groups could react with amino groups and carboxyl groups under common curing conditions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2791–2797, 2001     

Relationships between polymerization activating systems and viscoelastic properties of the subsequent polyurethane/poly(tert-butyl acrylate) interpenetrating polymer networks

To date, most interpenetrating polymer networks (IPNs) are developed for slow processes such as casting or coating. For industrial manufacturing, fast-reactive polymer processing is often required. Simply increasing the amount of catalyst and/or free-radical initiator shows some limitations. Also, increasing too much temperature may cause degradation or side reactions. For polyurethane/polyacrylate IPNs, more or less simultaneous formation of the two networks, with over 97% conversion was obtained after 4 to 6 min at 110°C, using appropriate catalyst/initiator combinations. Depending on the relative kinetics of network formation, either one, two, or multiple transitions were found for a given composition. Kinetics of formation and phase behavior have been investigated by Fourier transform infrared spectroscopy and dynamic mechanical analysis. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 951–958, 1997     

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%。     

Influence of a metallic filler on polyurethane formation

The addition of metallic fillers is recognized to impart improvement of acoustic properties to polyurethane-based materials used for marine applications. The system under consideration was obtained by the reaction of a triisocyanateterminated prepolymer with 1,4-butanediol, in the presence of various concentrations of lead powder. With increasing lead content, gelation time is reduced and an Einstein-type law does not apply. The kinetics of the reaction were determined by Fourier transform infrared spectroscopy. Deviation from the classic second order is observed for the filled systems, and the higher the lead content, the more important the deviation is, showing undoubtedly the catalytic effect of the metallic powder.