希夫碱钛配合物/三异丁基铝催化MMA本体聚合

经希夫碱缩合反应,制得水杨醛亚胺配体(1),其Na盐分别与TiCl4和CpTi-Cl3反应合成了新型希夫碱钛配合物{3,5-di-Br-2-(O)C6H2CHN[2(O)C6H4]}TiCl2(2);{3,5-di-Br-2-(O)C6H2CHN[2(O)C6H4]}[TiCl(C5H5)](3).以GC-MS,1HNMR和元素分析对中间产物及配合物进行了表征.以Al(i-Bu)3为助催化剂,详细考察了聚合时间、温度、Al/Cat和MMA/Cat的摩尔比对催化MMA本体聚合的影响.两个催化体系的聚合转化率均可以达到62%左右.2/Al(i-Bu)3(A)催化体系在聚合条件MMA/Cat(摩尔比)=2 000,Al/Cat(摩尔比)=20,T=60℃,t=15 h下,Mη可以达到3.6×105,相对分子质量分布2.14;3/Al(i-Bu)3(B)催化体系在相同聚合条件下,Mη可以达到4.3×105,相对分子质量分布2.44.红外光谱分析表明,A,B两个催化体系所得的PMMA的间同含量分别为85%和86%左右.     

新型铁系催化剂催化制备高相对分子质量宽/双峰聚乙烯

合成了配合物3([2,6-R2-C6H3N=C(CH3)C5H3N(CH3)C=N(3,5-R2)C6H2-CH2-(3,5-R2)C6H2N=C(CH3)C5H3N(CH3)C=N(2,6-R2)C6H3][FeCl2]2(R=i-C3H7)).经甲基铝氧烷(MAO)或三乙基铝(AlEt3)活化,配合物3对乙烯聚合表现出较高的催化活性,得到高相对分子质量的宽/双峰聚乙烯,且聚乙烯中高相对分子质量部分占优势.此外,所得聚乙烯具有较高的熔点和结晶度.13C NMR核磁共振表征显示,所得聚合物为线性聚乙烯.     

二价二(叔丁基环戊二烯基)钐对4-乙烯基吡啶的催化聚合研究

首次探索了二价(t-C4H9C5H4)2Sm对4-乙烯基吡啶的催化聚合性能,发现二价(t-C4H9C5H4)2Sm可以单组分高效催化4-乙烯基吡啶的聚合,而且聚合物分子量一般在1O×105以上.在20℃至70℃温度范围内,催化聚合活性随单体浓度和聚合温度的提高而提高.     

取代茚基二价稀土配合物催化甲基丙烯酸甲酯的聚合

较系统地研究了取代茚基二价稀土配合物(1—C5H9C9H6)2Sm(THF)作为单组分催化剂，催化MMA的聚合反应。结果表明，催化剂在较宽的温度范围显示出较高的催化活性，在以甲苯为溶剂的催化体系中加入少量的极性溶剂THF，聚合活性有显著的提高，温度降低MMA的转化率增加，所得PMMA的分子量升高，分子量分布变窄，几种取代茚基二价稀土配合物都显示了较高的催化活性，其活性次序为：(1—PhCH2C9H6)2Sm(THF)2＜(1—C5H9C9H6)2Yb(THF)2＜(1—C5H9C9H6)2Sm(THF)＜(1—C2H5C9H6)2Sm(THF)2。中性取代茚基二价稀土配合物所得聚合物主要为间同立构的PMMA，而由离子型的二价稀土配合物KSm(1—C5H9C9H6)3(THF)3所得到的为无规立构PMMA。     

C6H5CH2C5H4NdCl2·3THF的合成及催化聚合活性研究

合成了苄基环戊二烯基二氯化钕配合物(C6H5CH2C5H4NdCl2·3THF).用元素分析、红外光谱分析对其结构进行了表征,该配合物与三乙基铝(AlEt3)组成的催化体系催化丁二烯聚合,单体转化率达85%.     

胍基稀土硼氢化物的催化聚合性能

研究了胍基稀土硼氢化物 [Ph2NC（NCy）2]Ln（BH4）2 [Ph=C6H5, Cy=C6H11, Ln=Er（1）、Yb（2）]、 [（Me3Si）2NC（NCy）2]Ln（BH4）2 [Ln=Er（3）、 Yb（4）] 和 [（Me3Si）2NC（NCy）2]2LnBH4 [Ln=Er（5）, Yb（6）]催化甲基丙烯酸甲酯的聚合性能，其活性顺序为5〉6〉3〉4～1～2，说明胍基配体的供电性越强，配合物的催化活性越高。还研究了1和2催化丙烯腈聚合的性能。实验表明，胍基稀土硼氢化物也是催化丙烯腈聚合的良好催化剂。     

Ai(i-Bu)3-La(AA)3-H2O催化的环氧乙烷聚合作用

详细研究了在Al(i-Bu)3-La(AA)3-H2O的催化下环氧乙烷的均聚反应和与环氧丙烷的共聚反应情况.实验发现在该催化剂的作用下,以甲苯为反应介质,在n[Al(i-Bu)3]∶n[La(AA)3]为16～10,n[Al(i-Bu)3]∶n[H2O]为1∶(1～3),n(单体)∶n[La(AA)3]为1000∶(1～3),n(单体)∶n[Al(i-Bu)3]为100∶(1～3),45℃预聚2h,85～90℃聚合10h的条件下,催化剂的活性高,聚合速率大,所得产物的平均相对分子质量高.以水为溶剂,在30℃测得环氧乙烷均聚物的v=310×104;在m(环氧乙烷)∶m(环氧丙烷)为195∶15时,其共聚物的v=380×104,且产物有较好的水溶性.     

含吡啶基β-烯酮亚胺NNO型钇双胺基配合物的合成及其催化异戊二烯聚合研究

通过4-[(2-吡啶基)乙亚胺基]-2-戊烯-2-醇(1)与[(Me3Si)2N]3Y(μ-Cl)Li(THF)3的反应,制备含吡啶基β-烯酮亚胺NNO型钇双胺基配合物(2),采用1 H NMR,13 C NMR,元素分析,X-ray和IR等对该配合物进行了表征,并探索了其在催化异戊二烯聚合中的应用.结果表明,配合物2在催化异戊二烯聚合方面有较好的催化活性和立体选择性.     

几个二价稀土金属配合物的催化甲基丙烯酸甲酯聚合反应活性研究

研究了二价稀土金属配合物(η5:η1-C9H6CH2CH2CH2NMe2)2YbII(1),[{η5:η5:η1-(C9H5CH2SiMe2NC4H8)2}EuI2I(μ-Cl)]2[μ-η3:η5:η1:η3:η5:η1-(C9H5CH2SiMe2NC4H8)2].C7H8.(C6H6)0.5(2),and[η5:η1-C9H6CH2SiMe2NC4H8]2YbII(3)催化甲基丙烯酸甲酯聚合活性.探索了催化剂与MMA单体摩尔比、溶剂的极性、温度对MMA聚合反应的影响.     

脲酶模型化合物合成、表征及对尿素水解的影响

报道了对称六齿配体N,N,N＇,N＇-四(2′-苯并咪唑甲基)乙二胺(EDTB)的两种含镍(I)配合物[Ni(EDTB)](ClO4)2@3H2O和[Ni(EDTB)]C12@2H2O@3C2H5OH的合成、表征及其对尿素水解的影响.根据配合物元素分析、摩尔电导、紫外-可见(UV-Vis)、红外(IR)、ESR谱和循环伏安(CV)等性质与已测X-射线单晶结构的同种配体含铜(I)单核配合物比较,推测此两种配合物中的Ni(I)离子被配体EDTB的4个苯并咪唑(Bzim)氮和2个烷胺氮配位,形成一种畸变八面体几何构型.并用气相色谱法观测了此两种配合物对尿素水解反应的影响,结果表明它们几乎无催化尿素水解的活性,证明配位饱和可以抑制脲酶活性.     

Characterization of Ordovician carbonate reservoirs, southeastern Saskatchewan, Canada

The discovery of the prolific Ordovician Red River reservoirs in 1995 in southeastern Saskatchewan was the catalyst for extensive exploration activity which resulted in the discovery of more than 15 new Red River pools. The best yields of Red River production to date have been from dolomite reservoirs. Understanding the processes of dolomitization is, therefore, crucial for the prediction of the connectivity, spatial distribution and heterogeneity of dolomite reservoirs.The Red River reservoirs in the Midale area consist of 3～4 thin dolomitized zones, with a total thickness of about 20 m, which occur at the top of the Yeoman Formation. Two types of replacement dolomite were recognized in the Red River reservoir: dolomitized burrow infills and dolomitized host matrix. The spatial distribution of dolomite suggests that burrowing organisms played an important role in facilitating the fluid flow in the backfilled sediments. This resulted in penecontemporaneous dolomitization of burrow infills by normal seawater. The dolomite in the host matrix is interpreted as having occurred at shallow burial by evaporitic seawater during precipitation of Lake Almar anhydrite that immediately overlies the Yeoman Formation. However, the low δ18O values of dolomited burrow infills (-5.9‰～ -7.8‰, PDB) and matrix dolomites (-6.6‰～ -8.1‰, avg. -7.4‰ PDB) compared to the estimated values for the late Ordovician marine dolomite could be attributed to modification and alteration of dolomite at higher temperatures during deeper burial, which could also be responsible for its 87Sr/86Sr ratios (0.7084～0.7088) that are higher than suggested for the late Ordovician seawaters (0.7078～0.7080). The trace amounts of saddle dolomite cement in the Red River carbonates are probably related to "cannibalization" of earlier replacement dolomite during the chemical compaction.     

A computer generator for randomly layered structures

AcomputergeneratorforrandomlylayeredstructuresYUJia shun1,2,HEZhen hua2(1.TheInstituteofGeologicalandNuclearSciences,NewZealand;2.StateKeyLaboratoryofOilandGasReservoirGeologyandExploitation,ChengduUniversityofTechnology,China)Abstract:Analgorithmisintrod…     

海南岛地体及其毗邻陆缘晚中生代—新生代古地磁研究和构造演化

本文叙述了对海南岛及其毗邻大陆边缘白垩纪到第四纪地层岩石进行古地磁研究的全部工作过程。通过分析岩石中剩余磁矢量的磁偏角及磁倾角的变化,提出海南岛白垩纪以来经历的构造演化模式如下:早期伴随顺时针旋转而向南迁移,后期伴随逆时针转动并向北运移。联系该地区及邻区的地质、地球物理资料,对海南岛上述的构造地体运动提出以下认识:北部湾内早期有一拉张作用,主要是该作用使湾内地壳显著伸长减薄,形成北部湾盆地。从而导致了海南岛的早期构造运动,而海南岛后期的构造运动则主要是受南海海底扩张的影响。海南地体运动规律的阐明对于了解北部湾油气盆地的形成演化有重要的理论和实际意义。     

Exciton Seebeck in Molecular Systems

Various applications relevant to the exciton dynamics,such as the organic solar cell,the large-area organic light-emitting diodes and the thermoelectricity,are operating under temperature gradient.The potential abnormal behavior of the exicton dynamics driven by the temperature difference may affect the efficiency and performance of the corresponding devices.In the above situations,the exciton dynamics under temperature difference is mixed with     

Achieving Unusual States of Matter Under High Pressure

The elongation method,originally proposed by Imamura was further developed for many years in our group.As a method towards O(N)with high efficiency and high accuracy for any dimensional systems.This treatment designed for one-dimensional(ID)polymers is now available for three-dimensional(3D)systems,but geometry optimization is now possible only for 1D-systems.As an approach toward post-Hartree-Fock,it was also extended to     

《Chinese Science Bulletin》SUBJECT INDEX TO VOLUME 59(2014)

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An on-line scaling method for improving scalability of a database cluster

The explosive growth of the Internet and database applications has driven database to be more scalable and available, and able to support on-line scaling without interrupting service. To support more client's queries without downtime and degrading the response time, more nodes have to be scaled up while the database is running. This paper presents the overview of scalable and available database that satisfies the above characteristics. And we propose a novel on-line scaling method. Our method improves the existing on-line scaling method for fast response time and higher throughputs. Our proposed method reduces unnecessary network use, i.e. , we decrease the number of data copy by reusing the backup data. Also, our on-line scaling operation can be processed parallel by selecting adequate nodes as new node. Our performance study shows that our method results in significant reduction in data copy time.     

An improved R-tree based on childnode''s probability

R-Tree is a good structure for spatial searching. But in this indexing structure,either the sequence of nodes in the same level or sequence of traveling these nodes when queries are made is random. Since the possibility that the object appears in different MBR which have the same parents node is different, if we make the subnode who has the most possibility be traveled first, the time cost will be decreased in most of the cases. In some case, the possibility of a point belong to a rectangle will shows direct proportion with the size of the rectangle. But this conclusion is based on an assumption that the objects are symmetrically distributing in the area and this assumption is not always coming into existence. Now we found a more direct parameter to scale the possibility and made a little change on the structure of R-tree, to increase the possibility of founding the satisfying answer in the front sub trees. We names this structure probability based arranged R-tree (PBAR-tree).     

Integrating GIS Web services based on mediating architecture

The geographic information service is enabled by the advancements in general Web service technology and the focused efforts of the OGC in defining XML-based Web GIS service. Based on these models, this paper addresses the issue of services chaining,the process of combining or pipelining results from several interoperable GIS Web Services to create a customized solution. This paper presents a mediated chaining architecture in which a specific service takes responsibility for performing the process that describes a service chain. We designed the Spatial Information Process Language (SIPL) for dynamic modeling and describing the service chain, also a prototype of the Spatial Information Process Execution Engine (SIPEE) is implemented for executing processes written in SIPL. Discussion of measures to improve the functionality and performance of such system will be included.     

Tracking data management using topology of moving object database system for moving object constrained trajectory in LBS application

Advances in wireless technologies and positioning technologies and spread of wireless devices, an interest in LBS (Location Based Service) is arising. To provide location based service, tracking data should have been stored in moving object database management system (called MODBMS) with proper policies and managed efficiently. So the methods which acquire the location information at regular time intervals then, store and manage have been studied. In this paper, we suggest tracking data management techniques using topology that is corresponding to the moving path of moving object. In our techniques, we update the MODBMS when moving object arrived at a street intersection or a curved road which is represented as the node in topology and predict the location at past and future with attribute of topology and linear function. In this technique, location data that are corresponding to the node in topology are stored, thus reduce the number of update and amount of data. Also in case predicting the location,because topology are used as well as existing location information, accuracy for prediction is increased than applying linear function or spline function.