Synthesis and Characterization of Boron Complex of Calix[4]arene

A new boron complex of calix[4]arene was synthesized by the reaction of calix[4]arene with BMS; and the structure of the product was characterized by IR- (HNMR)-H-1. (CNMR)-C-13, (BNMR)-B-11 and MS spectra.

Mixed Pyridine-phenol Boron Complex Encapsulated in Polymer/Silica Hybrid Sol-gel Matrix

A novel pyridine-phenol boron complex[（dppy）BF] was encapsulated into polymer/silica composite matrix by sol-gel process. UV-Vis absorption spectra show that this process can control the aggregation structure of complex （dppy）BF. The results of photoluminescence of （dppy）BF in sol-gel composite film indicate that both fluorescence intensity and photostability are markedly increased using this method compared with other methods, which increases the practical significance of such composite film.

Determination of Boron Trifluoride in Boron Trifluoride Complex by Fluoride Ion Selective Electrode

A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.

Kinetics of the Reaction Between Boron Trifluoride Methanol Complex and Sodium Methoxide to Produce Enriched ^(10)B Methylborate

The relation of boron trifluoride concentration with conductivity in boron trifluoride methanol solution(BF_3-CH_3OH)was power exponent fitted in low concentration range. The kinetics of the reaction between boron trifluoride methanol complex and sodium methoxide to produce enriched ^(10)B methylborate was proposed based on a detailed mechanism study, and was verified by acid-base titration method and conductivity method. It was found that this reaction is first order reaction and the rate constant is 0.022 min^(-1) at 338 K(65 ℃), the activity energy is 65 k J/mol. In addition, it was found that the conductivity method is more feasible to measure the kinetic curve than acid-base titration method.

Complex Boronized Layer on the Hot-dip Aluminized Steels and Its Surface Performances

Plain carbon steels were dipped in molten aluminum bath at 720°C ±5°C and diffused for 1, 2.5 and 6 hours respectively and then boronized at 950°C for 6 hours. The oxidation, hot-corrosion and abrasion resistance behavior were examined. The experimental results showed the compounds of the aluminized layer, from the surface to the matrix, were composed of Fe2Al5 ( n -phase ) .. Fe3Al ( -phase ) and a phase. The microstructure of aluminized plus complex boronized were similar to that simplex boronized. The XRD analysis results indicated that there existed Fe2B> Fe2AlB2and Fe2Als in this kind of layer. The simplex aluminized layers still remained bright gray appearance when oxidized at 950°C, but complex boronized layer was not able to resist oxidization at the temperature. Both the layers of complex boronized and aluminized had the same anti-oxidization level in the circulative oxidization tests, and also good anti-corrosion ability in molten salt medium. Under dry abrasive conditions, wear resistance of complex boronized layer was superior to the aluminized layer.

Suppression and compensation effect of oxygen on the behavior of heavily boron-doped diamond films

This work investigates the suppression and compensation effect of oxygen on the behaviors and characteristics of heavily boron-doped microwave plasma chemical vapor deposition(MPCVD)diamond films.The suppression effect of oxygen on boron incorporation is observed by an improvement in crystal quality when oxygen is added during the diamond doping process.A relatively low hole concentration is expected and verified by Hall effect measurements due to the compensation effect of oxygen as a deep donor in diamond.A low acceptor concentration,high compensation donor concentration and relatively larger acceptor ionization energy are then induced by the incorporation of oxygen;however,a heavily boron-doped diamond film with high crystal quality can also be expected.The formation of an oxygen–boron complex structure instead of oxygen substitution,as indicated by the results of x-ray photoelectron spectroscopy,is suggested to be more responsible for the observed enhanced compensation effect due to its predicted low formation energy.Meanwhile,density functional theory calculations show that the boron–oxygen complex structure is easily formed in diamond with a formation energy of-0.83 eV.This work provides a comprehensive understanding of oxygen compensation in heavily boron-doped diamond.

二氟化硼配合物类功能材料研究进展

归纳二氟化硼配合物类化合物的设计、合成和应用领域的研究进展,可以揭示当前研究的热点和难点,为未来研究提供方向指引,拓展光电功能的应用领域。二氟化硼配合物类化合物目前主要分为N,N-二齿有机二氟化硼配合物、N,O-二齿有机二氟化硼配合物和O,O-二齿有机二氟化硼配合物3类。本文系统地综述这3类二氟化硼配合物的合成方法和应用,将有助于促进新材料的研究与应用,促进学科交叉合作,具有重要的科学意义和应用前景。

甲醛与环氧氯丙烷交替共聚物制备及其表征

采用自制的三氟化硼-二苯基亚砜复合物催化剂,以三聚甲醛与环氧氯丙烷通过阳离子开环聚合的方法共聚合成出一种新型甲醛与环氧氯丙烷交替共聚物,并探究了不同反应条件对共聚结果的影响。采用了傅里叶红外光谱、核磁共振谱、凝胶渗透色谱等对所得共聚物的结构进行了表征。结果表明,该聚合反应在甲醛与催化剂摩尔比例为50:1、甲醛与环氧氯丙烷摩尔比例为1:1、反应时间为8 h、反应温度为25℃的条件下进行反应产率可达到84.52%。由凝胶渗透色谱结果表明,该条件下共聚物的Mn=3.60×10^(3),分子量分布指数PDI=1.32。傅里叶红外光谱、核磁共振谱分析的结果表明,该共聚物为交替共聚物。

点火药的研究进展与展望

作为武器系统的重要组成部分,点火系统的性能直接影响到武器的发射效率和作战效果,因而点火药的性能尤为重要。以硼/硝酸钾为代表的非金属类点火药的研究已经较为深入,但该点火药面临着点火温度过高、硼粉老化及吸湿等问题。以金属粉作为可燃剂的金属类点火药具有高能量密度、良好的机械性能和独特的能量释放特性,但燃烧速率较慢。因此,研究人员进行了大量实验研究,制备出具有层状或核壳结构的反应材料,可以大大增加氧化剂和金属燃料之间的接触面积,并缩短传质距离,从而提高反应效率。近年来,含能配合物类点火药的研究成为本领域的研究热点,研究表明以含能配合物作为燃料,设计点火药配方,能够显著实现点火药的性能调控性能。

三氟化硼-苯甲醚络合物的管式裂解工艺研究

以三氟化硼-苯甲醚络合物为原料,采用管式裂解工艺,考察了裂解温度、停留时间以及预热温度对裂解反应的影响。采用气质联用仪定性分析了裂解后产物中的杂质,采用气相色谱外标法定量分析了各主要杂质的含量。通过研究获得了较优的管式裂解工艺参数,其中预热温度为40℃,裂解温度为185℃,停留时间为120 s,裂解率最高达到98.06%。

Carbothermic reduction characteristics of ludwigite and boron–iron magnetic separation

Ludwigite is a kind of complex iron ore containing boron, iron, and magnesium, and it is the most promising boron resource in China. Selective reduction of iron oxide is the key step for the comprehensive utilization of ludwigite. In the present work, the reduction mechanism of ludwigite was investigated. The thermogravimetry and differential scanning calorimetry analysis and isothermal reduction of ludwigite/coal composite pellet were performed. Ludwigite yielded a lower reduction starting temperature and a higher final reduction degree compared with the traditional iron concentrates. Higher specific surface area and more fine cracks might be the main reasons for the better reducibility of ludwigite. Reducing temperature highly affected the reaction fraction and microstructure of the reduced pellets, which are closely related to the separation degree of boron and iron. Increasing reducing temperature benefited the boron and iron magnetic separation. Optimum magnetic separation results could be obtained when the pellet was reduced at 1300°C. The separated boron-rich non-magnetic concentrate presented poor crystalline structure, and its extraction efficiency for boron reached 64.3%. The obtained experimental results can provide reference for the determination of the comprehensive utilization flow sheet of ludwigite.

Effect of oxygen on regulation of properties of moderately boron-doped diamond films

Regulation of oxygen on properties of moderately boron-doped diamond films is fully investigated.Results show that,with adding a small amount of oxygen(oxygen-to-carbon ratio<5.0%),the crystal quality of diamond is improved,and a suppression effect of residual nitrogen is observed.With increasing ratio of O/C from 2.5%to 20.0%,the hole concentration is firstly increased then reduced.This change of hole concentration is also explained.Moreover,the results of Hall effect measurement with temperatures from 300 K to 825 K show that,with adding a small amount of oxygen,boron and oxygen complex structures(especially B_(3)O and B_(4)O)are formed and exhibit as shallow donor in diamond,which results in increase of donor concentration.With further increase of ratio of O/C,the inhibitory behaviors of oxygen on boron leads to decrease of acceptor concentration(the optical emission spectroscopy has shown that it is decreased with ratio of O/C more than 10.0%).This work demonstrates that oxygen-doping induced increasement of the crystalline and surface quality could be restored by the co-doping with oxygen.The technique could achieve boron-doped diamond films with both high quality and acceptable hole concentration,which is applicable to electronic level of usage.

二甲基姜黄素的合成工艺优化

目的:对现有的二甲基姜黄素的合成路线进行工艺优化。方法:以乙酰丙酮作为起始原料,反应分两步进行,首先制得乙酰丙酮的硼络合物,然后与藜芦醛反应得到二甲基姜黄素,并对第二步的反应条件及后处理进行优化。结果:第二步反应制备二甲基姜黄素时,以N,N-二甲基乙酰胺(DMA)作为溶剂,反应温度为80℃,淬灭反应使用的酸用量为正丁胺的1.5当量,结晶补加水的体积为溶剂的2倍时,转化率最高。粗品收率95.1%,纯度98.6%,重结晶后总收率92.3%,纯度99.2%。结论:该路线原料廉价易得,反应条件温和,适合工业化生产。

取代基团对吡唑硼-亚铁体系自旋交叉配合物性能的影响

通过不同取代基对吡唑环配体进行修饰,制备了6种基于吡唑硼-亚铁的自旋交叉配合物,研究了取代基对自旋转变性能的影响。实验发现,吡唑硼-亚铁配合物均具有渐变型的自旋转变特性。吸电子取代基可以降低吡唑环的电子云密度,有利于低自旋态稳定,使得自旋转变温度升高;供电子取代基则增加了吡唑环的电子云密度,有利于高自旋态稳定,使得自旋转变温度降低;此外,具有较大空间位阻的取代基会抑制Fe-N键的增长,有利于低自旋态的稳定,使得自旋转变温度升高。本研究表明自旋交叉配合物的自旋转变温度可以通过配体修饰实现有效调控。

硼杂分子带:可控合成与发光功能

硼杂分子带具有独特的电子结构和光电磁性能,然而,受限于硼原子对水氧的敏感性及其削弱芳环的成环活性,硼杂分子带的液相合成仍然极具挑战性。鉴于此,本课题组提出了共轭硼烷可控环合的方法,采用液相光化学和索尔环合反应,制备出一系列硼杂纳米分子带,不仅实现了对边缘结构和共轭长度的控制,而且调控了分子的能带结构,探索了发光性质和电荷传输功能等,从而为有机光功能材料领域提供了新材料体系,为纳米碳分子领域开辟了新研究方向。

压裂返排液中残余硼的去除及返排液的重复利用

在重复利用压裂返排液时,未完全降解的残余硼交联剂会影响后续压裂液的配制,残余硼遇碱时会提前交联羟丙基胍胶,致使体系基液黏度增加,降低泵送速率和压裂效果。采用多羟基化合物与硼络合以消除提前交联的不良影响,并考察了反应条件对络合效率及络合物稳定性的影响。实验结果表明,含有顺式邻位羟基的自制甘露醇(GLC)对硼有很好的络合效果,在GLC与硼酸的摩尔比大于等于2.5、pH约为10时,硼能被完全掩蔽形成稳定的络合物。用络合处理后的返排液直接配制交联冻胶压裂液,未出现提前交联的现象,且其流变性能与原始冻胶压裂液的流变性能相当。该方法能去除利用返排液配制压裂液时出现提前交联的不良影响。整个过程不需分离已存在于返排液中的含硼络合物,可提高处理效率。

酰基吡唑啉酮双席夫碱硼配合物的合成与光谱表征

合成了 3种 [B(PMαFP) 2 en]Ac ,[B(PMαFP) 2 pen]Ac ,[B(PMTHP) 2 en]Ac型硼配合物 (其中(HPMαFP) 2 en为N ,N′ 双 [( 1 苯基 3 甲基 5 氧 4 吡唑啉基 )α 呋喃次甲基 ]乙二亚胺、(HPMαFP) 2 pen为N ,N′ 双 [( 1 苯基 3 甲基 5 氧 4 吡唑啉基 )α 呋喃次甲基 ]邻苯二亚胺、(HPMTHP) 2 en为N ,N′ 双 [( 1 苯基 3 甲基 5 氧 4 吡唑啉基 ) 2 噻吩次甲基 ]乙二亚胺 )。通过元素分析 ,红外光谱 ,电子光谱 ,核磁共振谱 ,摩尔电导等对新配合物的组成。

一种新型希夫碱硼配合物的合成及表征

有机电致发光器件(OLED)已成为平板显示、照明等领域的研究热点。针对已报道的蓝光材料相对短缺,合成了一种新型希夫碱硼配合物蓝光发射材料,其可由N,N′-二(2-羟基-3-甲氧基苯甲醛)缩乙二胺[(HMOB)2en]与醋酸硼B(Ac)3在苯溶剂中反应制得。通过1H NMR,13C NMR和红外光谱确定了其结构,并对其紫外-可见吸收光谱和荧光光谱进行了研究。1H NMR、13C NMR和红外光谱表明该配合物是一种以[B(MOB)2en]Ac分子形式存在的配合物。[B(MOB)2en]Ac的发光与B的引入有关,B的引入增强了分子的刚性、减少了非辐射跃迁能量损失,最终得到一种较强的蓝绿光发光材料。该材料发射的峰值波长为485nm,半峰全宽为87nm,CIE坐标:x=0.2211,y=0.4172,其最佳激发峰波长为378nm。

电池级碳酸锂生产中钙镁硼的络合分离试验研究

采用Bys-201型络合剂在氢氧化锂完成液的碳化过程中分离钙镁硼,考察了碳化温度和时间、CO2气体流速、络合剂用量对钙镁硼络合分离的影响,确定了最优工艺条件。本工艺钙镁硼提取率均可达98%以上,产出的碳酸锂产品质量达到了电池级碳酸锂的国家标准。

高温交联剂合成工艺研究

本文研究高温交联剂有机硼和有机锆的合成工艺。分别进行了以硼砂和硼酸为主要原料合成有机硼的试验研究。确定以硼砂为原料的合成路线最佳工艺条件为加料顺序C，反应温度50～55℃．反应时间30min；以硼酸为原料的合成路线最佳工艺条件为反应温度90～95℃，反应时间30min。通过比较发现，硼酸为原料合成的有机硼的冻胶性能更为优异。合成有机锆最佳工艺条件为氧氯化锆用量3％，反应时间20min。