冲击波处理的结晶MgO的化学分析正电子谱研究

冲击波处理的结晶ＭｇＯ的化学分析正电子谱研究＊张菊郑小明（杭州大学催化研究所，杭州３１００２８）常志向（抚顺石油化工研究院，抚顺１１３００１）关键词冲击波，化学分析正电子谱，结晶氧化镁，丁烯，脱氢冲击波是在介质中以超音速传播的压力脉冲．气体中的冲击波...     

ASSESSMENT OF CRITICAL AGGREGATE CONCENTRATION （CAgC） BY UV． A NEW METHOEOLOGY

ＡＳＳＥＳＳＭＥＮＴ　ＯＦ　ＣＲＩＴＩＣＡＬ　ＡＧＧＲＥＧＡＴＥ　ＣＯＮＣＥＮＴＲＡＴＩＯＮ　（ＣＡｇＣ）　ＢＹ　ＵＶ．　Ａ　ＮＥＷ　ＭＥＴＨＯＥＯＬＯＧＹＡＳＳＥＳＳＭＥＮＴＯＦＣＲＩＴＩＣＡＬＡＧＧＲＥＧＡＴＥＣＯＮＣＥＮＴＲＡＴＩＯＮ（ＣＡｇＣ...     

ELECTRON TRANSFER BETWEEN Eu~(3+) AND Ce~(3+) IN SrMgF_4 MATRIX

ＥＬＥＣＴＲＯＮ　ＴＲＡＮＳＦＥＲ　ＢＥＴＷＥＥＮ　Ｅｕ~（３＋）　ＡＮＤ　Ｃｅ~（３＋）　ＩＮ　ＳｒＭｇＦ_４　ＭＡＴＲＩＸＥＬＥＣＴＲＯＮＴＲＡＮＳＦＥＲＢＥＴＷＥＥＮＥｕ~（３＋）ＡＮＤＣｅ~（３＋）ＩＮＳｒＭｇＦ_４ＭＡＴＲＩＸ￥ＹｉｎｇＷＵ；Ｃｈ...     

THE NON－TEMPLATE SYNTHESIS OF MACROCYCLIC SCHIFF BASE DERIVED FROM THIOPHENE，AND ITS Ag（Ⅰ），Hg（Ⅱ） COMPLEXES

ＴＨＥ　ＮＯＮ－ＴＥＭＰＬＡＴＥ　ＳＹＮＴＨＥＳＩＳ　ＯＦ　ＭＡＣＲＯＣＹＣＬＩＣ　ＳＣＨＩＦＦ　ＢＡＳＥ　ＤＥＲＩＶＥＤ　ＦＲＯＭ　ＴＨＩＯＰＨＥＮＥ，ＡＮＤ　ＩＴＳ　Ａｇ（Ⅰ），Ｈｇ（Ⅱ）　ＣＯＭＰＬＥＸＥＳＴＨＥＮＯＮ－ＴＥＭＰＬＡＴＥＳＹＮＴ...     

冲击波处理的结晶MgO催化乙烷氧化脱氢反应

ＸＲＤ和ＥＳＲ技术研究表明，结晶ＭｇＯ经冲击波处理后晶格发生畸变，晶粒界面微扭曲值明显增大，从而提高了晶体缺陷浓度，并可能形成Ｆ心；晶体的平均晶粒减小，且表现出晶体破碎程度的各向异性。在不同反应温度、空速及时间的条件下考察冲击处理前后的ＭｇＯ催化剂对乙烷氧化脱氢反应的影响，发现用经冲击波处理的ＭｇＯ作催化剂，乙烷的转化率、乙烯的选择性均有一定程度的提高，初步讨论了可能的结构模型和催化机理。     

聚环氧乙烷为支链的两亲共聚物的表征及性能

用端基带有甲基丙烯酸酯的聚环氧乙烷大分子单体（ＰＥＯ—ＭＡ）分别与小分子单体苯乙烯（Ｓ）、甲基丙烯酸甲酯（ＭＭＡ）、丙烯酸甲酯（ＭＡ）溶液自由基共聚合得到了三种具有不同主链结构的以聚环氧乙烷（ＰＥＯ）为支链的两亲接枝嵌段共聚物（分别简写为：ＰＳ─ｇ─ＰＥＯ，ＰＭＭＡ─ｇ─ＰＥＯ，ＰＭＡ─ｇ─ＰＥＯ）．用ＧＰＣ、ＩＲ、１Ｈ─ＮＭＲ、ＷＡＸＤ和ＤＳＣ对其结构进行了表征．研究了接校共聚物的结晶性能、乳化性能以及在Ｗｉｌｌｉａｍｓｏｎ反应中相转移催化作用．结果表明，不同主链结构有不同的结晶度，并随支链ＰＥＯ含量的增加，分子量的增大而提高；其乳化体积和相转移催化反应的转化率均随着共聚物浓度的增加、支链ＰＥＯ含量的增人而增大，随支链ＰＥＯ分子量的提高而减小．     

THE GEOMETRY AND ORBITAL INTERACTIONS OF TRIATOMIC CLUSTERS OF Cu, Ag(I)

ＴＨＥＧＥＯＭＥＴＲＹＡＮＤＯＲＢＩＴＡＬＩＮＴＥＲＡＣＴＩＯＮＳＯＦＴＲＩＡＴＯＭＩＣＣＬＵＳＴＥＲＳＯＦＣｕ，Ａｇ（Ｉ）￥ＨａｎＸｉｎｇＬＩＵ（ＡｄｖａｎｃｅｄＭａｔｅｒｉａｌｓＲｅｓｅａｒｃｈＩｎｓｔｉｔｕｔｅ，ＷｕｈａｎＵｎｉｖｅｒｓｉｔｙｏ...     

MORE FACILE SYNTHESES TO THE SEX PHEROMONE COMPONENTS OF THE WINTER MOTH（OPEROPHTERABRUMATAL．（LEPIDOPTERA：GEOMETRIDAE）：（3Z，6Z，9Z）－3，6，9－NONADECATRIENE，（6Z，9Z）－6，9－NONADECADIENE

ＭＯＲＥＦＡＣＩＬＥＳＹＮＴＨＥＳＥＳＴＯＴＨＥＳＥＸＰＨＥＲＯＭＯＮＥＣＯＭＰＯＮＥＮＴＳＯＦＴＨＥＷＩＮＴＥＲＭＯＴＨ（ＯＰＥＲＯＰＨＴＥＲＡＢＲＵＭＡＴＡＬ．（ＬＥＰＩＤＯＰＴＥＲＡ：ＧＥＯＭＥＴＲＩＤＡＥ）：（３Ｚ，６Ｚ，９Ｚ）－３，６，９－...     

SYNTHESIS AND CRYSTAL STRUCTURE OF THE CLUSTER COMPOUND MoS_4Cu_2Ag（Ph_3P）_3Br．H_2O

ＳＹＮＴＨＥＳＩＳ ＡＮＤ ＣＲＹＳＴＡＬ ＳＴＲＵＣＴＵＲＥ ＯＦ ＴＨＥ ＣＬＵＳＴＥＲ ＣＯＭＰＯＵＮＤ ＭｏＳ_４Ｃｕ_２Ａｇ（Ｐｈ_３Ｐ）_３Ｂｒ．Ｈ_２Ｏ￥ＤｅＬｉａｎｇＬＯＮＧ；ＸｉｎＱｕａｎＸＩＮ（ＳｔａｌｅＫｅｙＬａｂｏｒａｔｏｒｙｏｆ?..     

THE GEOMETRY AND ORBITAL INTERACTION OF TRIATOMIC CLUSTERS FOR Cu,Ag,Au(Ⅱ)

ＴＨＥＧＥＯＭＥＴＲＹＡＮＤＯＲＢＩＴＡＬＩＮＴＥＲＡＣＴＩＯＮＯＦＴＲＩＡＴＯＭＩＣＣＬＵＳＴＥＲＳＦＯＲＣｕ，Ａｇ，Ａｕ（Ⅱ）￥ＨａｎＸｉｎｇＬＩＵ（ＡｄｖａｎｃｅｄＭａｔｅｒｉａｌｓＲｅｓｅａｒｃｈＩｎｓｔｉｔｕｔｅ，ＷｕｈａｎＵｎｉｖｅｒｓｉ...     

冲击波处理结晶氧化镁的催化性能研究

冲击波处理结晶氧化镁的催化性能研究１）刘建军徐康２）（中国科学院兰州化学物理研究所兰州７３００００）贺红亮谭华（西南流体物理研究所冲击波物理与爆轰物理实验室成都６１０００３）张菊郑小明（杭州大学催化研究所杭州３１００２８）关键词冲击波氧化镁ＴＰＤＥＳ...     

Effect of ultraviolet irradiation on terpolymerization of sulfur dioxide with two unsaturated compounds

The terpolymerization of sulfur dioxide, butene-1 and acrylonitrile affords terpolymers containing equimolar amounts of sulfur dioxide and butene-1 with various acrylonitrile contents. Ultraviolet irradiation was found to accelerate the polymerization and decrease the acrylonitrile content in the polymer. This fact is interpreted by a mechanism through a copolymerization of sulfur dioxide–butene-1 complex and acrylonitrile, whereby the polymerizability of sulfur dioxide–butene-1 complexed monomer may be accelerated by ultraviolet light. In fact, a binary system of sulfur dioxide and butene-1 was found to be accelerated by ultraviolet irradiation, and it affords a maximum rate at a 1:1 composition of feed monomer. Ultraviolet light of 250–300 mμ wavelength is effective for the initiation and the propagation. This may be ascribed to the ultraviolet absorption of the sulfur dioxide–butene-1 complex. The temperature coefficient was measured in both dark and ultraviolet irradiation reactions. The ultraviolet irradiation enhances the reactivity of sulfur dioxide–butene-1 complexed monomer at low temperature. In the terpolymerization with sulfur dioxide, isoprene, and butadiene, the ratio of isoprene and butadiene in the terpolymer was not altered by ultraviolet irradiation because both monomers from complexes with sulfur dioxide, perhaps having the same temperature coefficient for the polymerization.     

Oxidation of butene-1 by palladium chloride in acetic acid

Conclusions The oxidation of butene-1 by palladium chloride in glacial acetic acid leads to the formation of a mixture of complex alkenyl esters: butene-1-ol-3 acetate, butene-1-ol-2 acetate, the acetates of trans- and cis-butene-2-ols-2, and the acetates of trans- and cis-butene-2-ols-1.     

在Fe-Zn-Mg-Cr尖晶石结构催化剂上丁烯-2氧化动力学

用玻璃外循环无梯度反应器研究了在Fe-Zn-Mg-Cr尖晶石结构催化剂上丁烯-2氧化脱氢动力学。丁烯-2氧化脱氢动力学服从三步骤Redox机理。用脉冲法研究了催化剂用丁烯-2还原及还原催化剂用氧再氧化步骤。用脉冲法测定了丁烯-2吸附热。丁烯-2及丁二烯深度氧化动力学服从经验速度方程。用正交设计法估计了动力学方程的参数。丁烯-2氧化脱氢速度比丁烯-1要快。     

Comparative study of the kinetics of non-isothermal melt solidification of random copolymers of butene-1 with either ethylene or propylene

The kinetics of non-isothermal melt solidification of random butene-1/propylene copolymers has been compared with that of random butene-1/ethylene copolymers. Analysis of the distance between neighbored chain segments in the crystal phase revealed inclusion of propylene chain defects into crystals, while ethylene co-units are excluded from crystallization. As a consequence of different acceptance of propylene and ethylene chain defects to participate in crystallization, the kinetics of the transition of the melt into ordered phase is significantly slower in random butene-1/ethylene copolymers. For samples of similar co-unit concentration, the decrease of the crystallization temperature and of the critical cooling rate to suppress ordering/crystallization is higher in random butene-1/ethylene copolymers than in butene-1/propylene copolymers. Due to the required rejection of ethylene co-units at the crystal growth front, ultimately, the maximum crystallinity is lower in butene-1/ethylene copolymers than in butene-1/propylene copolymers of similar amount of co-units.     

Polymerization of butene-2 with isomerization to butene-1

An attempt has been made to prepare a high molecular weight isotactic polybutene-1 from cis- or trans-butene-2. Polymerization of butene-2 did not occur due to the steric effect of the substituents. In the presence of TiCl₃–Al(C₂H₅)₃ catalyst, however, both butene-2 monomers were found to polymerize at a slower rate than butene-1 and to give polymers consisting of the repeating unit of butene-1. From the gas chromatographic determination of the isomer distribution of the butenes recovered after the polymerization, it was found that the butenes isomerized, in the presence of the catalyst system containing TiCl₃, to approach the thermodynamic equilibrium mixture of butene-1, cis-butene-2, and trans-butene-2. It was also found that the rates of polymerization of butene-2 for the catalyst systems used were proportional to the isomerization rates. These results show that butene-2 isomerizes first to butene-1 which has less steric hindrance and then polymerizes as butene-1, through ordinary vinyl polymerization by a coordinated anionic mechanism. This type of polymerization was observed in some other linear β-olefins such as n-pentene-2 and n-hexene-2.     

在Fe-Zn-Mg催化剂上丁烯-1氧化脱氢制丁二烯动力学

用玻璃流动外循环反应器研究了Fe_4.9Zn_0.9Mg_0.1(原子比)催化剂上丁烯-1氧化脱氢动力学,丁烯-1氧化脱氢制丁二烯、丁烯-1及丁二烯深度氧化生成CO₂的动力学用双反应分子强吸附的L-H(LangmuirHinshelwood)机理方程描述。速度方程的参数用非线性最小二乘法估计,得丁二烯生成速度r_D和CO₂生成速度r_co2的动力学方程式。     

茂金属催化剂Cpt2MCl2(Cpt=tBuC5H4，M=Ti、zr、Hf)聚合丁烯-1的研究

探讨了茂金属催化剂Cpt2MCl2(CPt=tBuC5H4,M=Ti,zr,Hf)的合成以及用于聚合丁烯-1的研究,研究了几种不同的茂金属催化剂和不同聚合条件下的催化行为,并通过IR、1H NMR、EI-MS、DSC、粘度法测分子量和正庚烷抽提等测试手段对催化剂和聚合物进行了表征．结果表明,叔丁基取代的茂金属催化剂催化丁烯-1聚合具有较高的催化活性,叔丁基的引入提高了聚合物的等规度和分子量．