CHINESE JOURNAL OF ENERGETIC MATERIALS
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高剪切速率下硼与HTPB、PBT和GAP端羟基的反应活性
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1.南京理工大学化工学院;2.上海航天动力技术研究所, 上海 201109

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总装预研重点基金 9140A280204BQ02025总装预研重点基金(9140A280204BQ02025)


Reaction Activity of Terminal Hydroxyl Groups of HTPB, PBT and GAP with Boron at High Shear Rate
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Affiliation:

1.School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094;2.Shanghai Space Propulsion Technology Research Institute, Shanghai 201109

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    摘要:

    含硼富燃料推进剂具有较高的质量热值和体积热值,是固体火箭冲压发动机较理想的燃料之一,而无定形硼与黏合剂中的羟基可发生反应,导致推进剂药浆表观黏度增大快、药浆适用期缩短等问题。计算了分别以端羟基聚丁二烯(HTPB)、3,3-二叠氮甲基氧丁环-四氢呋喃共聚醚(PBT)和聚叠氮缩水甘油醚(GAP)为粘合剂的含硼推进剂的理论体积热值,并采用双螺杆转矩流变仪和红外光谱研究了B/HTPB、B/PBT和B/GAP 体系在高剪切速率混合过程中的流变和红外特性,分析了硼粉表面酸性杂质与粘合剂端羟基的反应活性。结果表明,经过合理配方设计,B/PBT/AP和B/GAP/AP的质量比为50∶20∶30时的体积热值均超过64.00 MJ·dm-3,大于B/HTPB/AP体系的体积热值(61.08 MJ·dm-3)。在剪切速率为355.56 s-1、55 ℃条件下,含25%硼的B/HTPB体系表观黏度快速增加到260 Pa·s,混合110 min发生凝胶现象;含40%硼的B/PBT体系混合7 h黏度仅从3.63 Pa·s上升到10 Pa·s;含55%硼的B/GAP体系混合7 h黏度由5.96 Pa·s下降到0.33 Pa·s。B/HTPB混合体系红外光谱B—O振动吸收峰随着混合时间的增加而逐渐增强,C—O(伯醇)振动吸收峰随着混合时间的增加而逐渐减弱,而B/PBT和B/GAP体系混合420 min后红外光谱B—O振动吸收峰和C—O(伯醇、仲醇)振动吸收峰几乎没有变化。PBT和GAP端羟基与硼粉酸性杂质的反应活性比HTPB的端羟基的活性低很多,这有利于改善含硼推进剂药浆的工艺性能。

    Abstract:

    The boron based fuel-rich propellant is considered as one of the ideal fuel for solid rocket ramjet owning to the high gravimetric and volumetric heating value of boron. However, the amorphous boron powder could react with the terminal hydroxyl groups of the binder, causing increase of apparent viscosity and pot-life of the slurry shortening. The theoretical volumetric heating values of three boron-based propellants were calculated, in which hydroxyl-terminated polybutadiene (HTPB), 3,3-bis (azidomethyl) oxetane and tetrahydrofuran copolyether (PBT) and gycidyl azide polymer (GAP) was used as the binder. The rheological properties and infrared characteristics of B/HTPB, B/PBT and B/GAP at high shear rate were studied by the co-rotating twin screw rheometer and Fourier transform infrared spectrometer, respectively. The reactivity of terminal hydroxyl groups for the three binders was analyzed. At a rational designed composition of 50∶20∶30, the volumetric heating values exceeded 64.00 MJ·dm-3 for B/PBT/AP and B/GAP/AP, which was higher than B/HTPB/AP system (61.08 MJ·dm-3). At shear rate of 355.56 s-1 and 55 ℃, the apparent viscosity for B/HTPB slurry with 25% boron rapidly increased to 260Pa·s and reached gel state after 110 min mixing. After 7 h under same condition, the apparent viscosity increased from 3.63 Pa·s to 10.6 Pa·s for B/PBT with 40% boron, whereas reduced from 5.96 Pa·s to 0.33 Pa·s for B/GAP with 55% boron. For B/HTPB slurry, enhanced B—O vibration absorption and gradually weaken C—O vibration absorption were detected during mixing, which were unchanged for B/PBT and B/GAP slurries. Therefore, considering reacting with the acidic impurities on the surface of boron particles, the reactivity of terminal hydroxyl groups of PBT and GAP were much lower than that of HTPB, which would facilitate processing of boron-based propellant.

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引用本文

张怀龙,王勇,周伟良,等.高剪切速率下硼与HTPB、PBT和GAP端羟基的反应活性[J].含能材料, 2019, 27(7):622-628. DOI:10.11943/CJEM2018279.
ZHANG Huai-long, WANG Yong, ZHOU Wei-liang, et al. Reaction Activity of Terminal Hydroxyl Groups of HTPB, PBT and GAP with Boron at High Shear Rate[J]. Chinese Journal of Energetic Materials, 2019, 27(7):622-628. DOI:10.11943/CJEM2018279.

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历史
  • 收稿日期: 2018-09-29
  • 最后修改日期: 2019-05-14
  • 录用日期: 2019-02-03
  • 在线发布日期: 2019-04-23
  • 出版日期: 2019-07-25