键合剂对RDX/HTPB推进剂界面粘结效能的影响

应用接触角测定仪测试了几种键合剂对ＲＤＸ／ＨＴＰＢ界面粘结效能的影响。选择了两种键合剂制备了ＲＤＸ／ＨＴＰＢ推进剂，测定了推进主 单轴拉伸力学性能和单拉伸破坏能。结果表明，键合改善ＲＤＸ／ＨＴＰＢ推进剂力学性能的主要原因在于它们改善了ＲＤＸ颗粒与ＨＴＰＢ粘结剂基体间的界面粘结效能。     

HTPB复合固体推进剂材料声发射的特性

阐述了声发射原理及应用,指出ＡＥ技术适应于研究ＨＴＰＢ复合固体推进剂动态损伤过程。在声发射实验结果分析的基础上,得出了ＨＴＰＢ 合固体推进剂材料声发射特性。     

端羟基聚丁二烯液体橡胶老化性能研究

研究了不同防老剂种类及用量，不同环境温度条件下，端羟基聚丁二烯（ＨＴＰＢ）液体橡胶粘度变化规律。结果表明，加入防老剂，尤其是２２４６可以显著改善ＨＴＰＢ的老化性能，且防老剂２２４６最佳用量为０．２％￣０．５％，室温下，ＨＴＰＢ不加防老剂的贮存期长达１年。     

浇注型端羟基聚丁二烯聚氨酯弹性体的合成及性能研究

采用不同分子量的端羟基聚丁二烯（ＨＴＰＢ）和甲苯二异氰酸酯为主要原料合成预聚物，以Ｎ，Ｎ－Ｍ（２－羟丙基）苯胺为扩链剂制备了浇注型聚氨酯弹性体，并着重研究了预聚体中游离异氰酸酯基含量、扩链剂用量、ＨＴＰＢ分子量以及不同分子量ＨＴＰＢ并用和扩链剂并用对弹性体力学性能的影响，还对弹性体的结构与形态进行了初步分析和探讨。结果表明，预聚体中游离异氰酸酯基含量为９．０％时，拉伸强度最大，且综合性能最佳；扩链系数为０．８９时，拉伸强度、定伸应力、硬度出现最大值；ＨＴＰＢ分子量增大，弹性体力学性能有下降趋势，不同分子量ＨＴＰＢ并用时分子量大的ＨＴＰＢ增多，力学性能下降；当ＨＴＰＢＭｎ＝３１００，游离异氰酸酯基含量为９．０％，扩链系数为０．８９时，弹性体综合性能最佳。电子显微镜照片显示ＨＴＰＢ型聚氨酯有微相分离，且软硬键段分布不规整。     

超微细 Cu_2O 对 RDX/AP/HTPB 推进剂组分热分解特性影响的研究

通过氧化还原法在微乳液中合成了超微细的Ｃｕ２Ｏ（０．２μｍ）,并用ＤＴＡ研究了超细Ｃｕ２Ｏ、市购化学纯Ｃｕ２Ｏ（３μｍ）、ＹＢ、ＱＣ及它们的不同组合对ＲＤＸ／ＡＰ／ＨＴＰＢ推进剂组分热分解特性的影响。实验结果表明：超细Ｃｕ２Ｏ能大幅度降低ＡＰ和ＲＤＸ／ＡＰ（质量比１∶２）混合体系的分解活化能,其催化作用与市购Ｃｕ２Ｏ相比有较大的增强。与ＹＢ组合对ＡＰ和ＲＤＸ／ＡＰ混合体系的催化有明显的协同效应,对ＲＤＸ也有一定的催化作用。     

端异氰酸酯基聚丁二烯液体橡胶

兰州石油化工公司化工研究院液体橡胶室继推出端羟基聚丁二烯 (ＨＴＰＢ Ｌ)及聚丁二烯 丙烯腈 (ＨＴＢＮ Ｌ)液体橡胶工业试产品后 ,又推出了端异氰酸酯基聚丁二烯 (ＩＴＰＢ)及端异氰酸酯基聚丁二烯 丙烯腈 (ＩＴＢＮ)液体橡胶。据报道 ,ＩＴＰＢ是由ＨＴＰＢ与ＴＤＩ在特定条件下合成。ＩＴＰＢ系列 4种中试产品的技术指标为 :相对分子质量分别为 380 0、30 0 0、2 5 0 0及 2 0 0 0 ,ＮＣＯ含量 0 .6、0 .9、1.2及 1.6ｍｍｏｌ/ｇ ,40℃粘度分别低于 30、2 6、2 0及 15Ｐａ·ｓ。它们可用于环氧树脂增韧、电子灌封胶等。由于ＩＴＰＢ粘度…     

催化剂对复合推进剂凝聚相反应热效应的影响

应用热分析方法研究了ＣｕＯ、Ｃｒ２Ｏ３、Ｃｏ２Ｏ３及其碳酸盐的煅烧产物对ＡＰ／ＨＴＰＢ复合推进剂凝聚相反应热效应的影响。试验表明,绝大多数催化剂使推进剂的分解总热效应增大,使氧化剂ＡＰ与粘结剂ＨＴＰＢ间的界面反应明显增强,煅烧ＣｕＯ与煅烧Ｃｏ２Ｏ３在混合比为１∶２和１∶３（重量）时可有效地增强粘结剂的吸热分解反应     

含铜催化剂对RDX/AP/HTPB推进剂燃烧特性的影响

采用热分析方法，研究了五种新型含铜催化剂对ＡＰ、ＡＰ／ＲＤＸ热分解特性的影响，从中筛选出两种催化效果比较好的催化剂。进一步研究了它们对ＡＰ／ＲＤＸ／ＨＴＰＢ推进剂燃速及燃速压强指数的影响。结果表明：这两种催化剂对提高燃速，降低压强指数有明显效果，经适当组合，可进一步提高燃速，降低压强指数。     

利用溶盐精馏法分离乙醇—水体系的研究

乙醇浓度达到95.57%时,乙醇—水形成共沸体系无法继续分离,必须通过其他途径实现无水乙醇的制备。目前工业上采用共沸精馏、萃取精馏、溶盐精馏等方法制备无水乙醇。本文采用溶盐精馏法,研究无水氯化钙及醋酸钾在乙醇—水体系中的分离作用。     

乙醇/丙醇-水-复合溶剂体系汽液平衡研究

为研究复合萃取溶剂体系下醇-水的汽液平衡,分别选用盐质量浓度为0.2 g/mL的乙二醇+氯化锂、乙二醇+醋酸钾2种复合萃取溶剂,测定了101.3 kPa下不同溶剂体积比(0.5∶1,1∶1,2∶1)时乙醇-水和丙醇-水的汽液平衡数据。分别用W ilson和NRTL热力学模型对所测汽液平衡数据按拟三元体系进行了关联。利用工业规模的实验装置,对测定结果进行了验证。结果表明,复合萃取溶剂能使乙醇-水和丙醇-水体系的共沸点消失,大大改变了体系中醇与水的相对挥发度。关联结果表明,W ilson热力学模型较NRTL热力学模型更适于乙醇/丙醇-水复合萃取溶剂体系。工业规模生产数据验证了所测定数据的可靠性,乙醇产品纯度可达到99.85%。     

羟基硅油改性HTPB型聚氨酯的合成与性能

以端羟基聚丁二烯(HTPB)为软段、异佛尔酮二异氰酸酯(IPDI)和3,3′-二氯-4,4′-二苯基甲烷二胺(MOCA)为硬段、羟基硅油(PDMS-OH)为改性剂和硅烷偶联剂(DB-550)为交联剂,合成了硅氧烷封端的HTPB型聚氨酯(PU)。采用L9(34)正交试验法优选出最佳工艺条件,探讨了PDMS-OH用量对改性PU的力学性能、耐水性能的影响,并对改性PU的耐老化性能进行了测定。结果表明:加入DB-550后,可以降低相分离程度;当R=2.5、w(HO-PDMS)=9%和n(MOCA):n(DB-550)=9:1时,采用直接法合成的改性PU具有优异的力学性能,并且其吸水率较低、耐老化性能较好。     

聚丁二烯聚氨酯-脲密封材料的性能研究

以端羟基聚丁二烯 (HTPB)、二异氰酸酯 (TDI或IPDI)为原料制备预聚体 ,利用多元胺或多元醇作固化剂 ,制成聚氨酯及聚氨酯 脲弹性体。测试了这些材料的力学性能、动态力学性能、粘接性能、耐介质、耐水解及透气性能。结果表明 :HTPB型聚氨酯 脲具有优良的力学性能 ,其耐介质及耐水解性明显优于聚醚型或聚酯型聚氨酯 ,具有很好的密封性能 ,可用作水下密封材料。     

Burning‐rate enhancement of a high‐energy rocket composite solid propellant based on ferrocene‐grafted hydroxyl‐terminated polybutadiene binder

Four different samples of ferrocene‐grafted hydroxyl‐terminated polybutadiene (Fc‐HTPB), containing 0.20, 0.52, 0.90, and 1.50 wt % iron, were synthesized by the Friedel–Crafts alkylation of ferrocene with hydroxyl‐terminated polybutadiene (HTPB) in the presence of AlCl₃ as a (Lewis acid) catalyst. The effects of the reaction conditions on the extent of ferrocene substitution were investigated. The Fc‐HTPBs were characterized by IR, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectra. The iron content and number of hydroxyl groups were estimated, and the properties, including thermal degradation, viscosity, and propellant burning rates (BRs), were also studied. The thermogravimetric data indicated two major weight loss stages around 395 and 500°C. These two weight losses were due to the depolymerization and decomposition of the cyclized product, respectively, with increasing temperature. The Fc‐HTPB was cured with toluene diisocyanate and isophorone diisocyanate separately with butanediol–trimethylolpropane crosslinker to study their mechanical properties. Better mechanical properties were obtained for the gumstock of Fc‐HTPB polyurethanes with higher NCO/OH ratios. The BRs of the ammonium perchlorate (AP)‐based propellant compositions having these Fc‐HTPBs (without dilution) as a binder were much higher (8.66 mm/s) than those achieved with the HTPB/AP propellant (5.4 mm/s). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Diffusion and sorption of benzene vapor through polybutadiene‐, polybutadiene/styrene‐, and polybutadiene/acrylonitrile‐based polyurethanes

A series of polyurethane (PU) films made from toluene diisocyanate (TDI), 1,4‐butanediol (BDO), and hydroxyl‐terminated polybutadiene (HTPB), hydroxyl terminated polybutadiene/styrene (HTBS), or hydroxyl terminated polybutadiene/acrylonitrile (HTBN) was synthesized by solution polymerization. The absorption of benzene vapor was found mainly in the soft phase. The equilibrium adsorption (M_∞) was reduced with increasing hard segment content for all the PUs. The values of M_∞ were in the sequence of HTBN‐PUs > HTBS‐PUs > HTPB‐PUs, which could be explained by the different interaction parameters between soft segments and benzene. The HTBN‐PU film showed the lowest degree of phase segregation and had more hard segments intermixed in the soft phase, restricting the movement of soft segments, and therefore resulted to non‐Fickian behavior, while the HTPB‐PU is antithetical. FTIR and atomic force microscopy were utilized to identify the hydrogen bonding behavior and morphology change of the PU films before and after the absorption of benzene vapor. The tensile strength of the HTBN‐PUs showed a greater decrease than that of HTBS‐PUs and HTPB‐PUs after absorbing benzene vapor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2984–2991, 2004     

阴离子端羟基聚丁二烯的表征及其固化物的力学性能

简述了以硅烷保护羟基的烷基锂为引发剂,环己烷为溶剂合成丁羟胶的聚合方法;通过IR、^1H—NMR和GPC等方法研究了阴离子端羟基聚丁二烯主链结构、分子质量分布、官能度及其分布;对其固化物力学性能进行了评价。研究结果表明,阴离子端羟基聚丁二烯的1,4-结构含量高达约90％、分子质量分布指数≤1．05、官能度接近2,其固化物具有优异的力学性能。     

CaCO3填充型聚丁二烯聚氨酯弹性体的研究

以端羟基聚丁二烯、液化改性二异氰酸(MDI)为原料，用或不用丁二醇作扩链剂，加入CaCO3，用机械搅拌或超声分散法合成填充型聚丁二烯聚氮酯(HTPB-PU)弹性体。并对填充型HTPB-PU弹性体的力学性能、热性能以及水解性能进行了研究，同时用扫描电镜研究了弹性体的应力断裂的断口形态。结果发现，随填料加入量的增多，弹性体的强度增大；填料加入量相同时，纳米CaCO3填充型HTPB-PU弹性体的力学性能和抗水解性能均优于普通CaCO3填充型；采用超声波分散相同时，HTPB-PU弹性体中的CaCO3分散得比采用机械搅拌分散时均匀得多；弹性体中存在明显的两相分离。     

Relationship between carbon dioxide transport,free volume and morphology of polyolefin‐based polyurethanes

A series of polyurethane (PU) films, produced from toluene diisocyanate, 1,4‐butane diol and either hydroxyl‐terminated polybutadiene (HTPB), hydroxyl‐terminated polybutadiene/acrylonitrile (HTBN) or hydroxyl‐terminated polybutadiene/styrene (HTBS), was synthesized by solution polymerization. Differential scanning calorimetry (DSC), Fourier‐transform infrared (FT‐IR) spectroscopy, and positron annihilation lifetime (PAL) spectroscopy were used to investigate the morphologies and free volumes of these polyolefin‐based polyurethanes. The free volumes were closely related to the morphologies of such PUs. HTBN‐based PUs showed the lowest degree of phase separation, the smallest fraction of free volume and smallest hole radius among the three types of polyolefin‐based PUs, while the HTPB‐based PUs displaying the largest values. The diffusion and permeation coefficients decreased with decreasing degree of phase separation and increasing content of hard segments. The transport data were in relation to the free volume and fitted the Fujita free‐volume model. Copyright © 2004 Society of Chemical Industry     

Anionic waterborne polyurethane dispersions based on hydroxyl‐terminated polybutadiene and poly(propylene glycol): Synthesis and characterization

Nonpolluting systems based on anionic polyurethane aqueous dispersions were obtained. The prepolymer based on hydroxyl‐terminated polybutadiene (HTPB), isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), and dimethylolpropionic acid (DMPA) were synthesized in bulk. After neutralization with triethylamine (TEA), the anionomer prepolymer was dispersed in water, followed by a chain‐extension reaction with ethylenediamine (EDA). The prepolymers were characterized by Fourier transform infrared spectrometry (FTIR) and the average particle size of the aqueous dispersions was determined by laser light scattering (LLS). The mechanical behavior of polyurethane‐cast films and the adhesive properties of the aqueous dispersions as coatings for wood were evaluated. It was observed that an increase in the HTPB content provoked an increase in the viscosity and in the particle size of the dispersions. The tensile strength and the modulus values of the films and the adhesiveness of the coatings in wood were also increased by increasing the HTPB content. On the other hand, the elongation of the polyurethane‐cast films and the tackness of the surface coatings decreased as the HTPB was increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 566–572, 2001     

Characterization of hydroxyl-terminated polybutadiene

A comparison between the molecular structure of conventional and low molecular weight hydroxyl terminated polybutadienes (HTPBs) is presented. The conventional HTPB samples were R45M, R45HT (Atochem). Liquiflex P and H (Petroflex, Brazil), and the low molecular weight ones were R20LM (Atochem) and two laboratory synthesized materials. The structural differences found were attributed to dissimilarities in fabrication processes for each type of HTPB. Some mechanistic pathways for the polymerization are suggested.     

Properties and pervaporation separation of hydroxyl‐terminated polybutadiene‐based polyurethane/poly(methyl metharcylate) interpenetrating networks membranes

Hydroxyl‐terminated polybutadiene (HTPB), 4,4′‐dicyclohexyl methane diiscyanate (H₁₂MDI), and 1,4‐butane diol are used to synthesize polyurethane (PU) solutions by two‐stage process. Interpenetrating networks (IPNs) of HTPB‐based PU and poly(methyl methacrylate) (PMMA) with HTPB/MMA (wt/wt % ratio) = 2.0, 1.5, 1.0, 1.5, 0.8, and 0.6, which are designated as IPN1 to IPN5, respectively, are synthesized by sequential polymerization technique. Thermal properties, tensile strength, and contact angle of membranes increase with the increase of MMA content, while the elongation of membranes show the reverse trend. Characterization of membranes are investigated by C?C/C?O absorption ratio and infrared absorption frequency shiftment. These PU and IPN membranes are used for the separation of ethanol/water and isopropanol/water solution by pervaporation test. IPN3 membrane possesses the largest pervaporation permeability and the separation factor. The pervaporation results of ethanol/water feed has the same trend as that of isopropyl alcohol (IPA)/water solution. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007