三臂星形端羟基聚丁二烯的阴离子合成及其表征

以叔丁基二甲基硅氧基丙基锂为引发剂,环己烷为溶剂进行阴离子聚合合成三臂星形端羟基聚丁二烯。采用凝胶渗透色谱(GPC)和1H-NMR方法表征了聚合物相对分子质量及其分布、支化度、平均官能度和主链微观结构。研究结果表明,三臂星形端羟基聚丁二烯的相对分子质量分布指数≤1.1,平均官能度和支化度均接近3。     

端胺基聚丁二烯的合成与表征

采用阴离子聚合法合成了端羟基聚丁二烯,通过端基转化法将羟基转化成胺基,从而合成了端胺基聚丁二烯,通过红外光谱（IR）、核磁共振（1H-NMR）、凝胶渗透色谱（GPC）等对其进行了表征。结果表明,所合成的端胺基聚丁二烯相对分子质量分布较窄（≤1.10）,平均官能度接近2,且微观结构可调;通过羟基值与胺基值的测定表明,端基转化率大于98%。     

端羧基聚丁二烯固化胶的力学性能

以三(2-甲基-1-氮丙啶)氧化膦(MAPO)为固化剂,研究了端羧基聚丁二烯预聚物(CTPB)的官能度与其固化胶力学性能之间的关系,并以纳米三氧化二铝作为填充剂,考察了其用量对CTPB固化胶微观形貌、力学性能及动态力学性能等的影响。结果表明,CTPB官能度与其固化胶扯断伸长率呈明显的正相关,随官能度增大固化胶的扯断伸长率明显升高;纳米三氧化二铝的加入可有效提升CTPB固化胶的力学性能,填充量为40份(质量)时固化胶的拉伸强度及扯断伸长率均有明显增大。CTPB的装药应用结果表明,在扯断伸长率相同的情况下,官能度为1.9的CTPB固化胶的拉伸强度较官能度为1.5者要高1.00 MPa。     

端羟基液体聚丁二烯橡胶微观结构及其力学性能

通过FT—IR,HNMR,CNMR,GPC等方法,对相同牌号HTPB样品A和B的主链微观结构、羟基类型、环氧基团、官能度分布和固化物力学性能进行了对比,2个样品的主链微观结构、羟基类型、环氧基团含量基本一致,而官能度分布存在较大差异,由结果可得,HTPB官能度分布对其力学性能影响较大,二官能度为84．2％的样品A具有较好的力学性能,二官能度为676％的样品B具有相对较差的力学性能。     

线型及星形端羟基聚丁二烯的合成与表征

以叔丁基二甲基硅氧基丙基锂为引发剂,丁二烯为单体,环己烷为溶剂,甲基三氯硅烷为偶联剂,采用活性负离子聚合法合成了线型端羟基聚丁二烯(L-HTPB)和星形端羟基聚丁二烯(S-HTPB),并用凝胶渗透色谱和核磁共振氢谱对其结构进行了表征。结果表明,采用该方法合成的2种聚丁二烯,其1,4-结构摩尔分数均接近90.00%,L-HTPB的平均官能度接近2.00,S-HTPB的平均官能度接近3.00,与分子设计值基本相符。     

以齐聚异戊二烯二锂为引发剂制备端羟基聚丁二烯的研究

本工作研究了锂-萘-四氢呋喃引发体系合成的α,ω-端羟基聚丁二烯的特性,以及聚合反应条件对聚合物微观结构、分子量分布、端羟基平均官能度等的影响。实验结果表明,合成的引发剂平均官能度 f 接近2,聚合度 n 为1—7。用此引发剂合成的聚丁二烯,分子量M_n 认为2—5×10~3,1,2结构含量约为50％;分子量分布较窄。当引发剂浓度为47—119毫摩尔/100克单体时,聚丁二烯中1,2结构含量基本不变,但当引发剂浓度大幅度下降时,则1,2结构含量也随之下降。     

不同聚合方法端羟基聚丁二烯复配物的制备及其固化物的力学性能

采用端羟基聚丁二烯(HTPB)与负离子法HTPB(A-HTPB)复配的方法制备了不同平均官能度(f)及其分布的HTPB,研究了f对固化物胶片和铝粉填充固化胶片力学性能的影响。结果表明,对于A-HTPB/HTPB固化胶片,随着A-HTPB用量的增加,当A-HTPB用量不大于25份,即f值不小于2.28时,其拉伸强度基本不变,但扯断伸长率逐渐增加;当A-HTPB用量大于25份,即f值小于2.28时,其拉伸强度虽然有所降低,但扯断伸长率增加幅度较大。对于铝粉填充A-HTPB/HTPB固化胶片,当A-HTPB用量为40份,即f值为2.22时,拉伸强度下降和扯断伸长率上升的幅度均较大,与A-HTPB/HTPB固化胶片的力学性能相近,说明f值是影响A-HTPB/HTPB固化胶片力学性能的重要因素。     

端羟基聚丁二烯官能度对推进剂力学性能的影响研究

通过凝胶渗透色谱（GPC）测定端羟基聚丁二烯（HTPB）样品的平均相对分子质量,化学滴定测定样品羟值,根据相对分子质量和羟值计算得到产品的平均官能度。通过假设交联密度和交联点间相对分子质量分别与推进剂抗拉强度和延伸率成正比,建立简单的官能度数学模型,阐述了平均官能度对推进剂力学性能的影响,同时官能度变化可很好地解释HTPB推进剂固化“活性”的差异。     

GPC法测定HTPB的官能度分布

端羟基聚丁二烯(HTPB)是一种重要的预聚物。据报道,HTPB的分子量(Mi)、分子量分布、官能度(f)和官能度分布对其物理和加工性能均有很大的影响。因此,对HTPB官能度分布的研究,具有十分重要的意义。 HTPB在聚合过程中,由于无法控制链的转移而产生了不同的官能度。预聚物的官能度被定义为预聚物的数均分子量(Mn)     

端环氧基超支化聚酯的合成及应用

本文以季戊四醇为心核结构、2,2-二羟甲基丁酸为重复单元、对苯甲磺酸为催化剂,合成了端羟基超支化聚酯;然后,采用环氧氯丙烷对超支化聚酯的端羟基进行环氧官能化,合成端环氧基超支化聚酯,采用GPC、13CNMR及1H-NMR图谱对结构进行表征。采用端环氧基超支化聚酯做增韧剂,研究其对双酚A环氧树脂力学性能的影响,探讨了端环氧基超支化聚酯对环氧树脂固化体系力学性能及韧性的影响。     

Functionality distribution and crosslink density of hydroxyl-terminated polybutadiene

A novel approach is proposed for estimating the average molecular weight between crosslinks (M?_c) from the functionality distribution of hydroxyl-terminated polybutadiene ( HTPB ). The functionality distribution of four free-radically polymerised HTPB prepolymers of varying hydroxyl content and molecular weight was determined by a combination of preparative and analytical gel permeation chromatography. The gumstock properties of the samples cured with stoichiometric amounts of toluene diisocyanate were not correlatable with the relative amounts of difunctional chain extender and multifunctional crosslinker present, unlike the case of HTPB with similar hydroxyl content and molecular weight. However, the mechanical properties and sol content could be correlated with the average molecular weight between crosslink sites, M?_c, of the cured polymer. The M?_c values derived by our method compare well with those of classical methods, and the observed differences are attributed to segmental entanglement. These M?_c values give consistently good correlation with all the gumstock properties, confirming the validity of our approach and the soundness of the techniques developed for the determination of the functionality distribution of HTPB .     

Structure-property relationship of HTPB-based propellants. II. Formulation tailoring for better mechanical properties

There has been a constant endeavor to improve the mechanical properties of hydroxylterminated polybutadiene (HTPB) -based composite solid propellants. A systematic study has been conducted on different batches of HTPB resins with varying molecular weights and hydroxyl values. Propellant formulation experiments were conducted wherein the ratio of chain extender to crosslinker was systematically varied, with a view to achieve the maximum possible strain capability and moderately high tensile strength, keeping all other parameters constant. The influence of increasing hydroxyl content from trimethylolpropane at the expense of hydroxyl content from butanediol, on the mechanical properties of the finished propellant, has been depicted on 3-dimensional graphs. The isoproperty lines, plotted as a triangular chart with the percentage hydroxyl contents from the three constituents, can be used to arrive at the suitable formulation for a specified application depending upon the OH value of the resin. HTPB resins with high molecular weight, low functionality, and low hydroxyl value require higher levels of trifunctional curing agent and higher NCO / OH ratios to obtain outstanding mechanical properties, especially elastic properties, compared to low molecular weight, high functionality resins. The impact of hard and soft segment domain structure on the mechanical behavior of the cured systems is more pronounced in the low molecular weight resin formulations due to the higher hard segment content compared to those attainable in high molecular weight resin formulations. © 1993 John Wiley & Sons, Inc.     

高拉伸强度高伸长率丁羟弹性体的研究进展

综述了影响丁羟弹性体力学性能的几种关键因素,包括固化参数、固化剂类型、扩链剂类型等,对比了几种提高丁羟弹性体力学性能的方法及其研究进展。提出了通过合成具有不同官能度的窄分子质量分布的丁羟液体橡胶,并进行复配研究,将是制备高拉仲强度、高伸长率丁羟弹性体的研究方向。     

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。     

Properties of hydroxyl-terminated polybutadiene-urethane systems

The properties of liquid hydroxyl-terminated polybutadiene (HTPB) stocks crosslinked with isocyanates of different functionalities were intensively investigated. The stocks were modified by inclusion of small proportions of various low molecular weight diols to increase the urethane concentration. The following studies were carried out: (1) the system functionality was varied at a low and relatively constant urethane concentration; (2) the system functionality was varied with the urethane concentration constant but at a higher level; (3) at a constant crosslink density, the urethane concentration was varied by adding low molecular weight diols; and (4) the structure of the diols used in the previous experiments was varied. A correlation between the per cent functional groups reacted, the average functionality of the system, and the mechanical properties of simple HTPB stocks was attained. Furthermore, a correlation was found between mechanical properties and urethane concentration at constant crosslink density. The properties of the stocks could be varied enormously by addition of low molecular weight diols in relatively small proportions by weight. The structure and concentrations of these diols caused significant variations in the elongation-at-break and tensile strength values.     

Study on a Vinyl Ester/Methyl Methacrylate Based Reactive Acrylic Adhesive Toughened by Hydroxyl Terminated Polybutadiene

The effect of addition of a hydroxyl-terminated liquid polybutadiene (HTPB) rubber on the morphology, adhesive, thermal and mechanical properties of a vinyl ester (VE)/methyl methacrylate (MMA) based reactive acrylic adhesive has been investigated. Phase separation was observed in the cured HTPB-modified acrylic adhesive. Low levels of HTPB enhanced the adhesive properties and the optimum adhesive strength was observed at about 10wt% HTPB. HTPB modification had no significant effect on the thermal properties, but decreased the mechanical strength, which was attributed to the inadequate bonding of the rubber particles. Introduction of a chemical link between HTPB and VE by toluene diisocyanate coupling showed significant improvement in adhesive and mechanical strength.     

端羟基聚丁二烯官能度及分布的测定

用凝胶渗透色谱法（GPC）测定端羟基聚丁二烯（HTPB）官能度分布。将HTPB用3,5-二硝基苯甲酰氯在一定条件下进行衍生化反应,衍生化后的HTPB经GPC的示差／紫外（RI／UV）双检测器进行检测,所得的色谱图经数据处理,得到HTPB的官能度及其分布。     

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     

Synthesis,Characterization and Properties of Nitropolybutadiene as Energetic Plasticizer for NHTPB Binder

The nitration of low molecular weight polybutadiene (PB) by a convenient and inexpensive procedure was investigated. To retain the unique physico‐chemical properties of the plasticizer, it was nitrated to an extent of 10 % double bonds. The product nitropolybutadiene (NPB) was characterized by FT‐IR and ¹H NMR spectroscopy as well as GPC, DSC, and TGA methods. The kinetic parameters for the decomposition of NPB from room temperature to 400 °C were obtained from non‐isothermal DSC. The changes in glass transition temperature (T _g) and inert uncured binder systems were used for determination of its efficiency as plasticizer. NPB was used in cured and unfilled nitro‐hydroxyl terminated polybutadiene (NHTPB) binder. Isothermal thermogravimetric analysis (Iso‐TGA) was employed to determine the migration rate in cured and unfilled HTPB binder systems compared to the dioctyladiphate (DOA) plasticizer. It was found that the exudation of the NPB plasticizer is slower than that of the DOA plasticizer. Thus, the NHTPB/NPB binder system (binder/plasticizer) presents more convenient mechanical properties than HTPB/DOA and is a promising new energetic binder system for polymer bonded explosives.