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不同催化剂条件下HTPB/IPDI黏结剂体系的固化过程
作者:
作者单位:

(1. 中北大学化工与环境学院, 山西 太原 030051; 2. 四川科技职工大学, 四川 成都 610101)

作者简介:

马慧(1984-),女,博士研究生,主要从事高分子黏结炸药的研究。e-mail: mahui20032011@163.com 通信联系人: 刘玉存(1961-),男,教授,博导,主要从事含能材料与火炸药的研究。e-mail: lyc2ct@sina.com

通讯作者:

刘玉存(1961-),男,教授,博导,主要从事含能材料与火炸药的研究。e-mail: lyc2ct@sina.com

基金项目:

国家自然科学基金委员会和中国工程物理研究院联合基金资助(U1330131)


Study on the Curing Process of HTPB/IPDI Binder System under Different Catalysts Conditions
Author:
Affiliation:

(1. Chemical Engineering and Environment College, North University of China, Taiyuan 030051, China; 2. Science and Technology University of Sichuan Staff, Chengdu 610101, China)

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    摘要:

    为了解不同催化剂[二月桂酸二丁基锡(DBTDL)、乙酰丙酮铁(FeAA)、辛酸亚锡(TECH)、三亚乙烯二胺(DABCO)、三苯基铋(TPB)、纳米氧化锌(nano-ZnO)]条件下HTPB/IPDI黏结剂体系的固化过程, 采用黏度法研究了45 ℃时, 不同催化剂作用下, 端羟基聚丁二烯(HTPB)/异佛尔酮二异氰酸酯(IPDI)体系的黏度-时间关系, 并探讨了固化反应速率的变化。结果表明, 45 ℃时, 无催化剂和不同催化剂作用下HTPB/IPDI体系的流变反应速率常数分别为: kblank=0.002, kDBTDL=0.045, kFeAA=0.0439, kTECH=0.0335, kDABCO=0.0051, kTPB=0.0036, knano-ZnO=0.0034。不同催化剂对HTPB/IPDI体系固化反应速率常数的影响效果为: DBTDL>FeAA>TECH>DABCO>TPB>nano-ZnO。在HTPB/IPDI体系中, 使用DBTDL, FeAA, TECH, DABCO, TPB, nano-ZnO作为催化剂时, 黏结剂体系的适用期分别为0.3, 0.7, 1.9, 6.7, 16, 18 h。通过固化过程中浆料适用期和反应速率常数k的变化情况分析, 认为TPB更适合作为HTPB/IPDI体系的固化催化剂。黏度对数随时间的增长趋势均呈现出前期快后期慢, 向图线右下方偏离的两阶段现象。造成这一现象的主要原因是由于IPDI中NCO基团反应活性的明显差异导致: IPDI中的伯NCO基受到环己烷环和甲基的位阻效应, 其反应活性明显低于环上的仲NCO基的反应活性。

    Abstract:

    To understand the curing process of hydroxy-terminated polybutadiene(HTPB)/isophorone diisocyanate(IPDI) binder system under the conditions of different catalysts [dibutyltin dilaurate(DBTDL), ferric acetylacetonate(FeAA), tin (ii) ethyethylhexanoate(TECH), diazabicyclooctane(DABCO), triphenylbismuth(TPB) and nano zinc oxide (nano-ZnO)], the relationship of viscosity vs. time for HTPB/IPDI system under the action of different catalysts at 45 ℃ was studied by viscosity method, and the changes in curing reaction rate were discussed. Results show that the rheological reaction rate constant for HTPB/IPDI system without catalyst and under the action of different catalysts at 45 ℃ is determined as kblank=0.002, kDBTDL=0.045, kFeAA=0.0439, kTECH=0.0335, kDABCO=0.0051, kTPB=0.0036 and knano-ZnO=0.0034. The effect of different catalysts on the curing reaction rate of HTPB/IPDI binder system decreases in the order of DBTDL > FeAA > TECH > DABCO > TPB > nano-ZnO. In the HTPB/IPDI system, when DBTDL, FeAA, TECH, DABCO, TPB and nano-ZnO are used as catalyst, the pot-life of the binder system is 0.3, 0.7, 1.9, 6.7, 16, 18 h, respectively. Through the change situation analyses of the pot life and the reacon rate constant k for sulrry during the curing process, considering that TPB is more suitable to be used as the curing catalyst of HTPB/IPDI system. The trend of the logarithm of viscosity increases with time reveals the phenomenon of two defined stages, fast early stage and slow later period, and deviation from the bottom right of graph line. The main reason for this phenomenon is due to the obvious reactive differences of NCO groups in IPDI. Science the steric effect of the methyl group and the cyclohexane ring, the reactivity of prim NCO group is significantly lower than the secondary NCO group.

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引用本文

马慧,刘玉存,柴涛,等.不同催化剂条件下HTPB/IPDI黏结剂体系的固化过程[J].含能材料, 2017, 25(5):360-365. DOI:10.11943/j. issn.1006-9941.2017.05.002.
MA Hui, LIU Yu-cun, CAI Tao, et al. Study on the Curing Process of HTPB/IPDI Binder System under Different Catalysts Conditions[J]. Chinese Journal of Energetic Materials, 2017, 25(5):360-365. DOI:10.11943/j. issn.1006-9941.2017.05.002.

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  • 收稿日期: 2016-10-18
  • 最后修改日期: 2016-12-15
  • 录用日期: 2017-01-13
  • 在线发布日期: 2017-05-27
  • 出版日期: 2017-05-31