端羟基聚丁二烯(HTPB)的~(13)C-NMR研究

<正> 以过氧化氢催化丁二烯聚合而得到的端羟基聚丁二烯(HTPB)在工业上具有广泛的用途,当它们发生交联时,即能形成结构体,用作推进剂、涂料和其它材料的基体,HTPB的质量对其最终产物的力学性能起着决定性的作用。然而人们已经发现,在某些情况下,使用相同牌号的HTPB,甚至用常规的分析方法进行鉴定认为是相同的HTPB,其交联体     

STUDY ON SEQUENCE STRUCTURE OF ACRYLAMIDE-ACRYLATE COPOLYMERS BY ~(13)C-NMR METHOD

Triad sequence distributions in a series of P(AM/AA) with different AA% were calculated from copolymerization reactivity ratio r_1 and r_2 based on first order Markov statistic model, and the calculated data compared with observed ones from ~(13)C-NMR spectra showed good agreement with each other. The sequence distribution in P(AM/AA) obtained under our experimental conditions fits in with first order Markov statistic model. A significant sequence structure difference was observed between P(AM/AA) and alkaline hydrolyzed polyaerylamide, ABA triad (acrylate unit center), AAA and AAB triads (aerylamide unit center) dominated in hydrolyzed ones.     

MEASUREMENT OF NUMBER AVERAGE MOLECULAR WEIGHT OF STYRENE OLIGOMER BY 13C-NMR METHOD

~(13)C-NMR ~1H-decoupled spectra of styrene polymers were assigned by comparison with modelcompounds, then used in measurements of number average molecular weights. The higher limit of an exactdetermination of the end group signal is less than a molecular weight of 10~4. For polymer samples withM_n<10~3, the results obtained from ~(13)C-NMR spectra of saturated carbon region are in excellent agreementwith the values determined by ~1H-NMR, SEC, and VPO methods, while the results from ~(13)C-NMR spectra ofphenyl C-1 carbon region are somewhat higher than the values determined by other methods.     

示踪原子法测定Ag/AgNO3-NH3体系的交换电流

The exchange currents of Ag/AgNO_3-NH_3 electrode systems were measured by using radiotrcer method.The magnitude of exchange currents was obtained to be of the order 10~(-7) A. cm~(-2) in solutions with various concentrations of Ag~+(Ⅰ). The data show that the exchange currents decrease with reduction in Ag~+ (Ⅰ) concen- trations.However the difference of exchange currents is not significant.It is in coincidance with the assumption that in very low overpotential region the surface diffusion of adatom is the rate determining step.The experimental conditions that must be fulfilled in order to ensure successful application of this method were also discussed.     

A NEW METHOD ON THE CHEMICAL SYNTHESIS OF DOPED POLYPYRROLE INITIATED BY CuCl_2-C_2H_5OH SYSTEM

Our objectives were to develop a new chemical method for the polymerization of pyrrole. CuCl_2 dissolved in C_2H_5OH solvent is primarily used for the initiation polymerization of pyrrole. The polymers with different yield and conductivity were obtained by raring the initial concentration of Cu~(2+). The initial concentrations of Cu~(2+) varied from 1.2 ×10~(-4) mole to 6.48 ×10~(-3) mole Cu~(2+) with 2.16 ×10~(-2) mole pyrrole. The polypyrrole obtained was characterized with elemental analyzer, XPS, IR spectroscopy, Four-point probe and SEM.     

KINETIC STUDY OF GAS-PHASE POLYMERIZATION OF PROPENE BY THE INHIBITION METHOD USING CARBON MONOXIDE

The inhibition method using CO to determine the active center concentration C~* in olefin poly-merization and the kinetics of gas-phase polymerization of propene were studied. The reliabilityof the method when used in gas-phase polymerization of propene is proved and the influencing fac-tor of the method is found to be the "repeating inhibition" of CO to the active centers. The C~*, the rate constant k_P and the activation energy were determined from the experimentalresults. We concluded that the C~* decreases with polymerization time and coincides with the decayrate of the polymerization.     

应用X射线无标样相定量法研究V2O5-TiO2体系的表面分散

The standardless simultaneous equation method with regression analysis of multi specimens in quantitative phase determination of XRD was applied for sur- face dispersion studies on V_2O_5-TiO_2 system. The dispersive characteristics of vana- dium oxide in V_2O_5-TiO_2 mixtures and in V_2O_5/TiO_2 catalysts prepared from oxyvanadium oxalate after roasting were compared in this paper.     

pH值对沉淀法制备Cu2(OH)3Cl-CuO超细粉体催化活性的影响

超细粒子因其具有明显的体积效应和表面效应,在催化、功能材料等领域得到了广泛的应用［１～３］,这在一定程度上促进了其制备科学的发展。超细粒子的制备方法较多,通常分为物理法、化学法和综合法三大类。其中化学沉淀法是一种最经济、最常用的制备超细氧化物粉体的方法。目前,采用沉淀法制取ＣｕＯ系列催化剂多以Ｃｕ（ＮＯ３）２ 为原料,而以其它二价铜盐为原料来考察制备条件对所得粉体催化活性影响的研究报道尚少［４,５］。为此,我们以ＣｕＣｌ２ 为原料,采用沉淀法制备ＣｕＯ 催化剂,结果意外地得到了一种对分解Ｈ２Ｏ２ 具有极高催化活性的Ｃｕ２（ＯＨ）３Ｃｌ－ＣｕＯ超细粉体,并发现反应液ｐＨ 值是控制该粉体物相、粒子大小及催化活性的关键。此结果为Ｃｕ 系催化剂的研究、开发,特别是对Ｏ２ 电极催化材料的制备提供了有价值的信息     

ESTIMATION OF REACTIVITY RATIOS OF METHYL ACRYLATE WITH N-ARYLMETHACRYL-AMIDE COPOLYMERS BY ~1H NMR METHOD

The copolymerizations of methyl acrylate (MA) with different N- arylmethacrylamide (N-ArMA) were carried out in benzene solution by free radical initiation. The compositions of the copolymers were deter mined by ~1H NMR method. The monomer reactivity ratios were calculated by the Fineman-Ross (F-R) method. The reactivity ratios and the activity of various N-ArMA with MA were investigated.     

溶剂热法合成无水NaBiO3多晶粉末

Anhydrous NaBiO₃ polycrystal powders have been prepared through a new process in which the alkoxides were used as precursors and the parent ROH as medium. The influences of precursors and medium for products were investigated. The reducibility of Bi(Ⅲ) in solvthermal process and the morphology of NaBiO₃ powders were studied.     

CrO3在γ-Al2O3和SiO2载体表面的分散状态

用X光衍射(XRD)方法研究了CrO_3/SiO_2和CrO_3/γ-Al_2O_3体系。用相定量外推法测定活性组份在载体表面的最大分散量。在干燥气氛中将CrO_3与载体混合, 并在低于CrO_3熔点的温度下烘烤制备样品, 实验得到CrO_3在SiO_2或者γ-Al_2O_3表面的最大分散量都随温度的升高而增大。CrO_3在SiO_2表面的最大分散量由101 ℃的0.27gCrO_3/g SiO_2到170 ℃的0.38g CrO_3/g SiO_2; CrO_3在γ-Al_2O_3表面的最大分散量由120 ℃的0.22g CrO_3/g γ-Al_2O_3到171 ℃的0.42g CrO_3/g γ-Al_2O_3。CrO_3在SiO_2或γ-Al_2O_3表面的最大分散量超过密置单层量, 可由易聚合形成同多酸根来解释。     

储氢材料新合成方法的研究——置换-扩散法合成Mg2Cu

目前,国外普遍采用高温熔炼法制备Mg2Cu,这种方法的优点是工艺比较简单,缺点是产物表面性能较差,吸、放氢速度较慢,且使用前必须经过粉碎。     

A NOVEL METHOD FOR CHARACTERIZING THE WHOLE PROCESS OF POLYMER GELATION*

A novel method was established to investigate the gelation process of polymers. The change of refractive index ofa polymer system during gelation was determined in situ in a prismatic cell. It can give reliable information on the wholegelation process. The apparatus and the execution of this technique are illustrated and the error is also discussed.     

生化需氧量（BOD5）测定中稀释倍数的简捷确定法

在生化需氧量（BOD5）的测定中，稀释倍数的估计是否适当至关重要。该文根据废水生物处理可行性的判断标准－BOD5／CODcr比值的波动范围，将其分为三个区间，经过数学推导，得出各区间的稀释倍数，即n1=0.57COD/d,n2=1.3COD/d,n3=1.23COD/d，其中d为当天稀释水的溶解氧。这三个稀释倍数可覆盖BOD5整个波动范围。由此，根据化学氧量（CODcr）可以简捷地确定出稀释倍数，从而提高了BOD5测定的有效性和准性。     

A SIMPLE METHOD FOR THE INCORPORATION OF LOW MOLECULAR WEIGHT DYES IN ULTRATHIN FILMS

A simple method for the fabrication of ultrathin films containing low molecular weight dye material is introduced(post-adsorption technique). The chromophore used is 4-nitro-4'-decyloxy azobenzene quaternary ammonium salt (azo-10Q).In classical layer-by-layer (LBL) procedures, where the substrate is dipped alternately into the chromophore solution and thecomplementary polyelectrolyte, the chromophore tends to desorb from the film during subsequent immersion in thepolyanion solution, and there is little or no indication of multilayer growth. The extent of desorption depends somewhat onthe selection of polyelectrolyte, the ionic strength and the pH of solution. An alternative approach is to first prepareconventional LBL films from a pair of oppositely charged polyelectrolytes, and then to soak this film into the chromophoresolution, where adsorption by penetration into the LBL film may take place. In preliminary results, a linear dependence ofUV absorbance on layer number of LBL film thus prepared was found, demonstrating the apparent effectiveness of the post-adsorption technique for the preparation of azo-10Q-containing ultrathin films.     

BaLaB9O16中Ce3+敏化Dy3+发光的机理

在紫外光激发下,研究了BaLaB₉O₁₆中Dy³⁺、Ce³⁺的发光光谱、激发光谱、发光强度及荧光寿命随着组成变化的规律性.结果表明;De³⁺对Dy³⁺的发光有相当强的敏化作用,Ce³⁺→Dy³⁺的能量传递效率可高达93%,能量传递的机理为电偶极-偶极相互作用的共振传递.根据349nm激发下Dy³⁺发光强度与浓度的关系,证明了Dy³⁺发光的自身浓度猝灭机理也为电偶极-偶极相互作用.     

MgB4O7－MgSO4－MgCl2－H2O及次级体系298.15K时稀释热、热容和表观摩尔焓的研究

本文研究了含硼四元水盐体系ＭｇＢ４Ｏ７－ＭｇＳＯ４－ＭｇＣｌ２－Ｈ２Ｏ及次级体系ＭｇＢ４Ｏ７－ＭｇＳＯ４－Ｈ２Ｏ在２９８．１５Ｋ时不同离子强度下的稀释热和热容，产将Ｄｅｂｙｅ－Ｈｕｃｋｅｌ极限公式应用到多元电解质稀溶液中，获得从高子强度到低离子强度Ｉ为１９－０．０００１范围内的相对表观摩尔焓。     

HCl-HClO4-H2O体系中高氯酸活度系数的测定

Mean activity coefficients of perchloric acid in system of HCl-HClO_4-H_2O at a constant total ionic strengths (I=0.7, 0.5, 0.3 and 0.1) have been measured by E.M.F. method from a cell without liquid junctions. The cell consists of a perchloric ion sensitive electode and a glass electrode. Results obtained show that the relationships between the logarithm of the mean activity coefficients of perchloric acid and the concentration of each of the two acids in the above mixtures obey Harned's rule. The respective Harned's coefficients a_(21) have been computed by the least square method.