丙烯酸十八酯在Nd(P204)3-Al(i-Bu)3催化剂体系中聚合的研究

研究了丙烯酸十八酯(OA)在Nd(P204)3-Al(i-Bu)3催化剂体系中的聚合反应,反应的最佳条件是:以苯为溶剂,［Al］／［Nd］=9(摩尔比),［OA］／［Nd］=162(摩尔比),60 ℃反应6 h,聚合转化率大于90%,所得聚合物的分子量为1.0×105～1.5×105。聚合反应速率与单体浓度、催化剂浓度均呈一级关系,聚合反应的表观活化能为32.5 kJ／mol。     

混合配体钕催化体系聚合异戊二烯

以二(二(2-乙基己基)磷酸)异辛酸钕盐(Nd(P_(204))_2EHA)/氢化二异丁基铝(AlH(i-Bu)_2)/二甲基二氯硅烷(Me_2SiCl_2)为催化剂进行异戊二烯聚合。考察了[Al]/[Nd]、[Cl]/[Nd]比、聚合温度和时间对聚合的影响。该催化剂在[Al]/[Nd]为10时,可高活性催化异戊二烯聚合。所得聚合物具有高相对分子质量(Mn~10~5)、窄相对分子质量分布(Mw/Mn2. 0)、高顺-1,4立构规整性(97. 5%)。催化活性随[Al]/[Nd]在8. 0~15和[Cl]/[Nd]在1. 0~3. 0范围内的增加而提高,反应温度的升高可显著加快聚合速率。聚合物窄的相对分子质量分布和凝胶渗透色谱的单峰曲线,表明该催化体系具有单一活性中心的特点;聚合物的立构规整性基本不受反应条件的影响,顺-1,4结构含量为97. 0%~97. 5%,表明催化剂有高的立体定向性。     

MoCl_2(C_7H_(15)Coo)_2-(i-Bu)_2Alo-■体系催化丁二烯聚合的研究

本工作研究了MoCl_2(C_7H_(15)COO)_2-(i-Bu)_2AlO-催化体系在加氢汽油中对丁二烯聚合的催化行为,考察了多种聚合条件对丁二烯的转进率、聚合速度、聚合产物的分子量及微观结构的影响。结果表明,本体系的催化活性很高,适宜的主、助催化剂配比较宽,除聚合温度对聚合物的微观结构稍有影响外,其他各种聚合条件几乎不影响单体的插入方式。聚合物的1,2-链节含量在85％以上,且几乎不含有顺式1,4-链节。     

溶液型磷酸酯钕催化体系合成Cis-1,4-聚异戊橡胶

以溶液型磷酸酯钕盐Nd(P204)3(简称Nd)为主催化剂,在有少量单体异戊二烯(IP)存在下的三异丁基铝(Al(i-Bu)3,简称Al)及二乙基氯化铝(AlEt2Cl,简称Cl)催化体系催化异戊二烯(IP)聚合。通过在磷酸酯钕中加入丙二醇制备出溶液型主催化剂,这种方法解决了磷酸酯钕的非均相问题,同时,此方法无需皂化反应,减少了废水排放。考察了此催化剂组分的陈化方式、聚合温度及时间等对异戊二烯聚合的影响。结果表明,催化剂陈化方式为IP+Al+Nd+Cl,[IP]/[Nd]为10,[Al]/[Nd]为10,[Cl]/[Nd]为2,在10℃陈化3h的条件下,得到的聚异戊二烯橡胶顺式-1,4-结构含量在98%以上,相对分子质量分布小于2.5。     

添加剂MoCl_n(OC_8H_(17)_(4-n)-(i-Bu)_2AlOP_a体系催化丁二烯聚合的影响

研究了含有N、O、卤素等给电子试剂作为MoCl_n(OC_8H_(17))_(4-n)-(i-Bu)_2AlOPh体系第三组分,对丁二烯聚合活性、聚合物的分子量及其分布、微观结构等的影响。发现烯丙基卤可以大幅度调节聚合物的分子量,对分子量分布也有一定的调节作用。三种烯丙基卤对分子量的调节效果是:烯丙基溴>烯丙基碘>烯丙基氯。卤代二乙基铝的影响效果与烯丙基卤不同,在本体系中起链终止作用。     

Fe—Al—α，α’—联吡啶催化体系催化马来酸酐与环氧环已烷开环共聚

用Fe(acac)3-Al(i-Bu)3-α，α’－联吡啶（acac=乙酰丙酮）催化马来酸酐（MA）与环氧环已烷（CHO）开环交替共聚，研究了Fe/Al、Fe/α，α’－联吡啶摩尔比对聚合的影响，用核磁共振技术研究了共聚物的交替度，测得共聚物中马来酸酐含量达33％以上。共聚物分子量用凝胶渗透色谱仪测量，分析表明共聚物分子量分散度很窄。共聚反应动力学研究表明，共聚反应速度与单体浓度呈一级关系，表观活化能为25．4kJ/mol。     

NdBO_3和 Nd(BO_2)_3的标准生成自由能

用 CaF_2单晶和 ZrO_2(+MgO)为固体电解质分别构成原电池:■和 Pt,B_((s)),NdBO_(3(s)),Nd(BO_2)_(3(s))|ZrO_2|Cr_2O_(3(s)),Cr_((s)),Pt联合测了 NdBO_3和 Nd(BO_2)_3的标准生成自由能:ΔG~0_(NdBO_3)=-1757+3.8×10~(-1)TΔG~0_(Nd)(BO_2)_3=-3435+8.8×10~(-1)T由此求出由氧化物生成 NdBO_3及 Nd((BO_2)_3)的反应的标准生成自由能变化:1/2Nd_2O_(3(s))+1/2B_2O_(3■)=NdBO_(3(s))ΔG~0_(NdBO_3)=-242+1.4×10~(-1)T和 1/2Nd_2O_(3(s))+3/2B_2O_(3(s))=Nd(BO_2)_(3■)ΔG~0′_(NdBO_2)3=-693+4.6×10~(-1)T     

Fe-Al-α,α′-联吡啶催化体系催化马来酸酐与环氧环己烷开环共聚

用Fe(acac)3-Al(i-Bu)3-α,α ′-联吡啶(acac=乙酰丙酮)催化马来酸酐(MA)与环氧环己烷(CHO)开环交替共聚,研究了Fe /Al、Fe/α,α′-联吡啶摩尔比对聚合的影响,用核磁共振技术研究了共聚物的交 替度,测得共聚物中马来酸酐含量达33%以上.共聚物分子量用凝胶渗透色谱仪测得,分析 表明共聚物分子量分散度很窄.共聚反应动力学研究表明,共聚反应速度与单体浓度呈一级关系,表观活化能为25.4 kJ/mol.     

Ni(S_xSe_(1-x))_2纳米线阵列催化电极的制备与析氢性能

黄铁矿型过渡金属硫属化合物(MX_2,典型的M=Fe、Co或Ni,X=S或Se)因具有独特的电子结构、低廉的价格、优异的催化活性和稳定性等特点,在电催化剂领域拥有广阔的发展前景。然而其电催化性能与传统Pt系贵金属催化剂相比尚有差距,因此本研究尝试通过掺杂调控催化剂成分的方式进一步改善其催化性能。以S和Se共掺杂Ni基硫属化合物为研究对象,选择碳纤维纸作为导电基底,采用水热法在碳纤维表面生长出Ni_2-(CO_3)(OH)_2纳米线阵列作为前驱体,并以S/Se混合粉作为反应源,利用化学气相沉积法实现S/Se与Ni_2(CO_3)(OH)_2的反应,合成了成分可控的阴离子共掺Ni(S_xSe_(1-x))_2纳米线阵列自支撑一体化催化电极。电催化性能测试表明:在不同成分的Ni(S_xSe_(1-x))_2中,Ni(S_(0.81)Se_(0.19))_2纳米线表现出最佳的催化性能,仅需要93 mV和135 mV的过电位就可以分别驱动10 m A·cm~(-2)和100 mA·cm~(-2)的电流密度,对应的Tafel斜率也低至42.07 mV·dec~(-1)。研究表明,阴离子掺杂能够进一步提高该类催化剂的催化活性,为高效率、低成本碱金属化合物电催化剂的设计和制备提供借鉴思路。     

基于稀土催化在苯乙烯中合成苯乙烯/异戊二烯/丁二烯三元共聚物

采用钕系稀土催化剂Nd(P204)3/Al(i-Bu)2H/CHCl3,以苯乙烯为溶剂兼做单体,进行苯乙烯(St)/异戊二烯(Ip)/丁二烯(Bd)三元共聚合反应,制备St/Ip/Bd三元集成橡胶(SIBR)。研究了经Ip、Bd陈化的催化剂对聚合活性的影响,重点考察了催化剂各组成用量对共聚合的影响。结果表明,催化剂中只有加入Ip或Bd陈化后才具有聚合活性;随着[Al]、[Cl]、[Nd]用量的增加,SIBR中St组分含量逐渐升高并在一定范围内可实现调控;[Cl]用量变化对SIBR高立体选择性和相对分子质量控制稳定性最好,其Ip、Bd组分1,4-结构含量均在98%以上,重均相对分子质量均控制在2×105左右;[Al]、[Nd]用量增加,SIBR相对分子质量下降、相对分子质量分布变窄;SIBR只有1个Tg,且随着St和Ip组分含量增加而升高;合成了Ip、Bd组分1,4-结构高立体选择性(95%)的无规SIBR。     

Phase diagrams of the ternary liquid systems [Ce(NO3)3(TBP)3]-C10H22-[UO2(NO3)2(TBP)2] and [Ce(NO3)3(TBP)3]-C10H22-[Th(NO3)4(TBP)2] and of the quaternary liquid system [Ce(NO3)3(TBP)3]-C10H22-[UO2(NO3)2(TBP)2]-[Th(NO3)4(TBP)2]

The phase diagrams of the ternary liquid systems [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂(TBP)₂] and [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[Th(NO₃)₄(TBP)₂] and of the quaternary liquid system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂(TBP)₂]-[Th(NO₃)₄(TBP)₂] at T = 298.15 K are constructed. The phase diagrams are characterized by areas of homogeneous solutions and of two-phase liquid systems (systems with phase separation), with one phase (I) enriched in [Ce(NO₃)₃(TBP)₃], [Th(NO₃)₄(TBP)₂], and [UO₂(NO₃)₂(TBP)₂], and the other phase (II), in C₁₀H₂₂. Using the data on the mutual solubility of the components in the systems under consideration and equations of the NRTL model, the parameters of intermolecular interactions and the excess Gibbs energies (G ^ex) were calculated for the binary, ternary, and quaternary systems. Passing from the ternary system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[Th(NO₃)₄(TBP)₂] to the quaternary system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂ (TBP)₂]-[Th(NO₃)₄(TBP)₂] does not appreciably affect the distribution of C₁₀H₂₂ between phases I and II, but leads to the redistribution of [Ce(NO₃)₃(TBP)₃] into phase II and of [Th(NO₃)₄(TBP)₂] into phase I.     

Stabilization of Ferromagnetic Order in La(0.7)Sr(0.3)MnO(3)-SrRuO(3) Superlattices

The study of spatially confined complex oxides is of wide interest, since correlated electrons at interfaces might form exotic phases. Here La(0.7)Sr(0.3)MnO(3)/SrRuO(3) superlattices with coherently grown interfaces were studied by structural techniques, magnetization, and magnetotransport measurements. Magnetization measurements showed that ferromagnetic order in ultrathin La(0.7)Sr(0.3)MnO(3) layers is stabilized in the superlattices down to layer thicknesses of at least two unit cells. This stabilization is destroyed, if the ferromagnetic layers are separated by two unit cell thick SrTiO(3) layers. The resistivity of the superlattices showed metallic behavior and was dominated by the conducting SrRuO(3) layers, the off-diagonal resistivity showed an anomalous Hall effect from both SrRuO(3) and La(0.7)Sr(0.3)MnO(3) layers. This shows that the La(0.7)Sr(0.3)MnO(3) layers are not only ferromagnetic but also highly conducting; probably a conducting hole gas is induced at the interfaces that stabilizes the ferromagnetic order. This result opens up an alternative route for the fabrication of two-dimensional systems with long-range ferromagnetic order.     

La2/3Sr1/3Mn1-xCuxO3的磁电阻研究

采用溶胶一凝胶(sol-gel)法制备了La2/3 Sr1/3Mn1-x CuxO3(x=0.00、0.05、0.10、0.20)的多晶样品.利用振动样品磁强计测量了样品在室温下的磁性能;利用X射线衍射确定了粉体的组成;利用扫描电子显微镜观察了颗粒的形貌.在1.8T磁场作用下,当x=0时,在370K,样品的磁电阻几乎成...     

访港随笔(三)

ＡＭＣ又一城 1 1厅影院隶属于美国ＡＭＣ国际娱乐公司的香港ＡＭＣ又一城 1 1厅影院 ,是位于九龙半岛九龙塘达之路的超大型现代综合性商场《又一城》的重要构成之一。这个有着 1 1个影厅、1 853个座席、约 2 2个轮椅位的新建影城 ,以其位居香港第一且具有国际水准的厅数 ,成为一个典型的美国多厅影院香港版 ,值得我们认真研究。ＡＭＣ ,是美国多厅影院公司 (ＡｍｅｒｉｃａｎＭｕｌｔｉ -Ｃｉｎｅｍａ)的缩写。该公司正式成立于1 968年 ,当时拥有 1 2家影院 ,2 2个影厅。其前身是始建于1 92 0年的杜尔伍德影院 ,院线总部一直设在密苏里州的…     

Fluorescence properties of Dy(3+) doped La(3)Ga(5.5)Nb(0.5)O(14) nanocrystals

The effects of Dy(3+) doping concentration and calcinations on the fluorescence properties of La(3)Ga(5.5)Nb(0.5)O(14) (Dy:LGN) nanocrystals were examined for the first time. High quality Dy:LGN nanocrystals were synthesized by the sol-gel method. The room temperature fluorescence spectra were measured; they showed a yellow emission, which can be attributed to the (4)F(9/2)-(6)H(13/2) transition. The relationship between the relative emission intensity and the doping concentration of the specimens, sintered at different temperatures, is consistent with a Gaussian distribution according a fitted and modified formula. The optimum value of the Dy(3+) doping concentration in LGN nanocrystals is in the range 2.0-2.5%. Moreover, in LGN bulk crystal for laser use, the optimum value, calculated through the obtained formula, is presumed in the range 1.5-2.0%. The fluorescent lifetime of a 2.0% Dy:LGN nanocrystal is quite short, only about 8.5?ns.     

Kinetic study of Cu(II) adsorption on nanosized BaTiO(3) and SrTiO(3) photocatalysts

In this study, nanoparticles with perovskite structure (nano-SrTiO(3) and nano-BaTiO(3)) were synthesized via a co-precipitation method, and their photocatalytic and adsorption characteristics were investigated. Both of them exhibited some photocatalytic activity and possessed a high adsorption capacity for copper ions. Further, the pseudo-first-order model was found to be more suitable to fit the experimental data. Moreover, it suggested that the Langmuir model was more adequate in simulating the adsorption isotherm. The maximum adsorption capacity was 370.4 mg/g and 200.0mg/g for nano-SrTiO(3) and nano-BaTiO(3), respectively. The negative apparent free energy confirmed that the Cu(2+) adsorption onto the nano-photocatalysts was a spontaneous process. The underlying mechanism of adsorption of Cu(II) onto nano-perovskites could be due to the ion exchange and surface complexation. From the results, SrTiO(3) and BaTiO(3) nanoparticles may be an effective material for Cu(2+) removal and, together with its photocatalytic activity, may be suitable for environmental remediation applications.     

烧成温度对Pb（Mg_（1／3）Nb_（2／3））O_3－pb（Zn_（1／3

研究了一种满足Ｙ５Ｕ指标要求的ＰＭ计ＰＺＮ－ＰＴ介电陶瓷的恒温老化行为与烧成温度的关系，发现在低温烧结要求的温度范围内（９００∽９５０℃），该材料的老化性能满足有关标准，而过高或过低的烧结温度均导致１０倍时间老化率的增大；利用显微结构结构观察分析了上述结果。