1,3–偶极环加成反应在固化含能黏合剂中的应用

从叠氮化物的1,3–偶极环加成反应和腈氧化物的1,3–偶极环加成反应两个方面,综述了它们分别固化含能黏合剂的研究进展。介绍了叠氮黏合剂与多炔基化合物、端炔基黏合剂与多叠氮化合物2种固化反应,以及腈氧化物的固化反应原理及其在低温固化方面的应用情况。指出了未来腈氧化物研究的3个重点方向:固化剂的理论设计、黏合体系与炸药的作用机理、材料间相容性研究。     

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。     

黏合剂固化网络参数对叠氮聚醚推进剂低温性能的影响

系统研究了黏合剂固化网络参数对推进剂低温力学性能的影响。通过调节黏合剂预聚物分子结构,选择合适的固化剂、交联剂、扩链剂、增塑剂等固化网络结构因子,显著改善了PBT(3,3–双(叠氮甲基)氧杂环丁烷与四氢呋喃共聚醚)叠氮聚醚推进剂低温力学性能;–55℃时推进剂最大抗拉强度大于2.00 MPa,最大伸长率大于100.0%,T_g低于–60.00℃。     

新型非异氰酸酯固化体系研究进展

综述了国内外近十年来报道的3类新的非异氰酸酯固化体系:端环氧基-亲核基团固化体系、叠氮基-炔基固化体系和腈氧化物-烯基固化体系的研究进展。总结了预聚物和固化剂的合成方法、固化条件、交联弹性体的力学性能、玻璃化温度、热稳定性等并进行了对比分析。指出腈氧化物-烯基固化体系具有固化温度低,反应活性高,对水分不敏感等优点,应用潜力巨大。建议推进剂用固化体系的重点发展方向为加强弹性体网络结构与物化性能的关系研究、通过结构改性进一步提高弹性体的力学性能以及发展便捷高效的新型固化方法。附参考文献58篇。     

利用1,3偶极环加成反应固化叠氮黏合剂研究进展

基于叠氮基团与亲偶极基团发生1,3–偶极环加成反应形成1,2,3–三唑五元环的原理,以多元亲偶极化合物为固化剂,可以成功地固化叠氮聚合物。介绍了固化剂分子结构、固化剂用量、固化温度对固化速率的影响,交联体的相关性能,以及固化剂在推进剂中的应用情况,对固化剂的使用提出了一些建议与设想。     

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%。     

侧链非离子改性水性环氧固化剂的制备及性能研究

非离子型固化剂是在固化剂中通过嵌段方式引入非离子的聚醚类链段,容易造成固化剂黏度增大,需要较多溶剂稀释以降低黏度。为了解决这一问题,本研究通过含有非离子链段的异氰酸酯半加成物,将亲水型聚乙二醇非离子链段接入到水性环氧固化剂中,得到侧链非离子改性的水性环氧固化剂。本研究分别对侧链非离子改性水性环氧固化剂制备过程中异氰酸酯半加成物的制备工艺、功能单体聚乙二醇单甲醚的用量、水性环氧固化剂的封闭剂进行了讨论。使用所制备的新型水性环氧固化剂研磨颜填料浆,将其与环氧乳液固化,得到了双组份水性环氧涂料,并对其性能进行了表征。     

叠层母排用绝缘胶粘剂的制备及性能研究

以饱和聚酯树脂(SP)为主体树脂,多官能度异氰酸酯为固化剂,成功制备出一种耐高温SP胶粘剂,并将其涂覆在聚酯膜表面,干燥后即得到叠层母排用绝缘胶膜。采用衰减全反射红外光谱(ATR-FTIR)和差示扫描量热(DSC)法研究了SP和多官能度异氰酸酯固化剂的固化反应特性,讨论了固化剂种类对绝缘胶膜剥离强度及高低温冲击性能的影响。结果表明,异氰酸酯固化剂可与SP反应,固化交联后的SP胶粘剂无明显熔点。添加固化剂可以显著提高绝缘胶膜的高温剥离强度、高低温冲击性能,且以芳香族异氰酸酯固化剂交联固化的SP胶粘剂的综合性能优于脂肪族异氰酸酯固化剂固化的SP胶粘剂。     

室温固化耐水聚氨酯黏合剂的研制

采用端羟基聚丁二烯和蓖麻油为聚合物多元醇,二苯基甲烷二异氰酸酯和4,4′-双仲丁氨基二苯基甲烷为固化剂,配以多种助剂和填料,制备了一种室温固化的聚氨酯黏合剂,用于黏结金属和聚氨酯,研究了聚合物多元醇种类、异氰酸酯和固化剂种类以及助剂对黏合剂力学性能和黏结性能的影响。结果表明,制备的黏合剂具有优异的贮存稳定性和耐水性能,在40℃的蒸馏水中浸泡10周,吸水率为0.21%,在40℃的质量分数为4%的NaCl水溶液中浸泡1周,黏结强度保持率为90%。     

阴极电泳涂料涂膜固化温度的研究

围绕阴极电泳涂料的涂膜固化温度展开研究,详细介绍了阴极电泳涂料的制备过程和反应机理,研究表明,不同封闭型异氰酸酯固化剂对阴极电泳涂料涂膜固化温度和贮存稳定性产生影响。使用HDI、TMP和甲乙酮肟为主要原料制备了一种封闭型异氰酸酯固化剂。使用该封闭型异氰酸酯固化剂制备的阴极电泳涂料具有比较低的涂膜固化温度和较好的贮存稳定性。     

A Study on the Triazole Crosslinked Polymeric Binder Based on Glycidyl Azide Polymer and Dipolarophile Curing Agents

Instead of using urethane curing systems, which have long been used as solid propellants, a triazole curing system has been introduced into a new binder recipe in which azide groups in the polymer react with triple bonds of a dipolarophile curing agent. Commercially available glycidyl azide polymers (GAP) were used and an aliphatic curing agent, bispropargyl succinate (BPS), as well as an aromatic curing agent, 1,4‐bis(1‐hydroxypropargyl)benzene (BHPB), were synthesized as dipolarophile curing agent. Together with networks prepared under the triazole curing system, the networks under dual curing systems, which consist of an isocyanate curing agent and a dipolarophile curing agent, were prepared. Through swelling experiments, solubility parameters and crosslinking densities of the triazole crosslinked networks were determined by using Gee’s theory and Flory–Rhener theory. The mechanical properties of the triazole crosslinked networks were also investigated with different contents of the dipolarophile curing agent, along with the type of dipolarophile curing agent. The networks prepared under the triazole curing system did not show good mechanical properties. However, GAP‐based networks prepared under a dual curing system showed excellent mechanical properties with only a small amount of dipolarophile curing agent used. The effects of BPS and BHPB on the mechanical properties of the networks were much more distinguishable in networks prepared under a dual curing system rather than a single curing system.     

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.     

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.     

叠氮类含能粘合剂研究进展

粘合剂含能化是火炸药未来的发展方向,叠氮类粘合剂是含能粘合剂中的典型代表。该文主要从热塑性含能粘合剂和热固性含能粘合剂两方面综述了近5年叠氮类粘合剂研究进展,并对该类粘合剂的发展趋势和应用前景进行了展望。     

1,2,3‐triazole crosslinked polymers as binders for solid rocket propellants

In this study, 1,2,3‐triazole crosslinked polymers were synthesized as a new binder for solid rocket propellant systems by reacting the azide groups of the polymer with the ethynyl groups of a dipolarophile curing agent. All the mixtures were cured in an oven at 52°C for 7 days, and the curing reactivity of the products was analyzed using a Fourier transform‐infrared spectrometer. The carbonyl group adjacent to the triple bond, which acts as an electron‐withdrawing group, considerably accelerated the 1,3‐dipolar cycloaddition reaction between the azide and ethynyl functional groups, affording rubbery materials. The modulus of the polymers increased whereas the elongation at the break decreased with increasing ratio of the crosslinker to the prepolymer, resulting in highly crosslinked polymers. The molecular weights between the crosslinking points and interaction parameters of the 1,2,3‐triazole crosslinked polymers were determined from the swelling data, Flory–Rehner equation, and Mooney–Rivlin equation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40594.     

Structure and mechanical properties of novel composites based on glycidyl azide polymer and propargyl‐terminated polybutadiene as potential binder of solid propellant

Instead of the traditional isocyanate curing system as the binder of solid propellant, a triazole curing system has been developed by the reaction of azide group and alkynyl group due to a predominant advantage of avoiding to the interference of humidity. In this work, the propargyl‐terminated polybutadiene (PTPB) was blended with glycidyl azide polymers (GAPs) to produce new composites under the catalysis of cuprous chloride at ambient temperature. The triazole‐crosslinked network structure was regulated by changing the molar ratio of azide group in GAP versus alkynyl group in PTPB, and hence various crosslinked densities together with the composition changes of GAP versus PTPB cooperatively determined the mechanical properties of the resultant composites. Furthermore, the formed triazole‐crosslinked network derived from the azide group in GAP and alkynyl group in PTPB resulted in the slight increase of glass transition temperatures and a‐transition temperatures, and improved the miscibility between GAP and PTPB. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40007.     

非异氰酸酯聚氨酯涂料的制备及性能研究

将2,3-环碳酸甘油酯甲基丙烯酸酯(PCMA)与丙烯酸酯类单体共聚生成的聚合物作为主要成膜物,以二乙烯三胺为固化剂,制备了非异氰酸酯聚氨酯涂膜(NIPU).通过门-IR对涂膜结构进行分析,证明了聚氨酯特殊基团氨基甲酸酯的合成;并通过对漆膜综合性能的研究,确定了共聚实验配方及固化合成NIPU的最佳工艺.配制的清漆漆膜综合性能优良,同时其制备过程中不以有毒、高湿敏性的异氰酸酯为原料,安全、环保.     

工程起重机用水性自干防腐底漆的制备

介绍了一种应用于工程起重机的水性自干防腐底漆,重点阐述了该涂料的制备方法、施工工艺以及探讨了分散剂、防锈颜料、颜基比、固化剂用量对涂膜性能的影响,并与现有溶剂型产品进行对比,涂膜性能达到或超过现有溶剂型涂料涂膜性能,产品施工性良好,满足企业安全生产的需求.