嵌段共聚物sPS-b-Poly(S-co-E)的合成与表征

用主催化剂茂基三苄氧基钛和茂基三呋喃甲氧基钛与助催化剂甲基铝氧烷(MAO)组成的催化体系研究了先预聚苯乙烯(S)再引入乙烯(E)进行的嵌段共聚合反应,发现总的催化效率随苯乙烯预聚合时间的延长而增加.对嵌段共聚合产物用丁酮、四氢呋喃和氯仿进行顺序萃取分离,得到四氢呋喃中的可溶级分即嵌段共聚物sPS-b-Poly(S-co-E),占总嵌段共聚合产物的30%～50%,其中乙烯链节的含量占总嵌段共聚物的9%～14%.对嵌段共聚物用DSC、WAXD、FTIR、13CNMR和偏光显微等方法进行了表征.     

水杨酸或阿司匹林二茂钛(Ⅳ)配合物的抗氧化作用

在无水苯中以二氯二环戊二烯基钛与乙酰水杨酸钠或水杨酸钠合成出二环戊二烯基二阿司匹林钛(Ⅳ)或二环戊二烯基二水杨酸钛(Ⅳ)配合物,通过元素分析,IR,^1HNMR,XPS等研究了它们的化学组成与结构,证实配合物的组成式为cp~2Ti(Asp)~2和cp~2Ti(Sal)~2(cp=η^5-C~5H~5,Asp=阿司匹林酸根,Sal＝水杨酸根),Asp及Sal均以羧基氧原子以单齿形式与Ti(Ⅳ)配位。通过测定cp~2Ti(Asp)~2,cp~2Ti(Sal)~2,cp~2TiCl~2,阿司匹林(HAsp),水杨酸(HSal),Ti(OH)~2·(Asp)~2及Ti(OH)~2(Sal)~2等七种化合物对超氧阴离子自由基(O~2^-^.)和羟自由基(OH^.)的清除率,发现金属Ti(Ⅳ)只有与茂基及Asp或Sal形成混合配体金属有机配合物时,对上述两种自由基的清除才能产生“协同作用”。     

茂钛催化剂的苯乙烯间规聚合

比较了几种庞钛化合物/甲基铝氧烷/三甲基铝均相催化剂的苯乙烯间规聚合,认为茂基三正丙氧基钛[CpTi(O－n－Pr)₃]是苯乙烯间规聚合的良好催化剂[催化效率：ω_ps·ω_Ti^-1=4×10⁴g·g^-1]．探索了催化剂浓度、单体浓度、聚合温度和时间对苯乙烯聚合的影响．聚合反应产物用佛丁酮萃取,沸丁酮不可溶级分大于95％,经¹³CNMR分析该级分为间规聚苯乙烯．     

小果博落回对照物质及其核磁共振氢谱指纹图的创建

采用规范化的程序获取6个不同来源小果博落回样品的对照物质(CSPD)及其^1H NMR图谱;从小果博落回CSPD中分得6个单体成分,其结构分别被鉴定为二氢血根碱(1)、二氢白屈菜红碱(2)、6-甲氧基二氢血根碱(3)、6-甲氧基二氢白屈菜红碱(4)、齐墩果酸(5)和原阿片碱(6)。通过各单体化合物的^1H NMR图谱与CSPD的^1H NMR图谱的对比研究,实现了小果博落回的^1H NMR指纹图的解析。研究结果表明：6个不同来源的小果博落回样品,其^1H NMR指纹图有很好的重现性和高度的特征性,并主要显示以上生物碱类成分的特征共振信号,可做为其基源鉴定的参考。     

β-二酮-茂基二氯化钛/MAO催化体系用于苯乙烯间规聚合

制备了 β 二酮类配体 [O ,O]的茂基二氯化钛配合物CpTi(dbm)Cl2 .实验证明 ,这类配合物在助催化剂甲基铝氧烷MAO作用下 ,可催化苯乙烯间规聚合 .显示较高的活性 (10 7× 10 5gPS molTi·h) .所得聚合物具有较高的间规度 .CpTi(dbm)Cl2 MAO体系催化活性随铝 钛比的增加呈上升而后衰减 ,当铝 钛比为 5 0 0左右时活性最高 ;聚合温度较高时会导致催化活性下降 .对聚合物进行了1 3C NMR表征     

含氮亲核试剂在2-甲磺酰基-5-(3,4,5-三甲氧基苯基)-1,3,4-恶二唑环上取代反应的研究

本文报道了制备2-甲磺酰基-5-(3,4,5-三甲氧基苯基)-1,3,4-恶二唑和其进一步与多种亲核试剂反应. 2-巯基-5-(3,4,5-三甲氧基苯基)-1,3,4-恶二唑经过甲基化, 而后用KMnO~4氧化得到2-甲磺酰基-5-(3,4,5-三甲氧基苯基)-1,3,4-恶二唑衍生物. 其结构由元素分析,IR, ^1H NMR 和MS确定.化合物4对大肠杆菌和枯草芽孢杆菌有较强的抑制性能.     

不饱和取代环戊二烯基钛衍生物的合成和反应

利用不同方法合成了烯丙基、环戊烯-[2]-基、甲基(或乙基)环戊烯-[2]-基、环已烯-[2]-基和环已基等不饱和取代茂基茂基二卤化钛。烯丙基茂基钛衍生物中的环上烯丙基呈现正常的亲电加成反应,它们与HBr,Br_2,ICl和IBr反应生成对应的卤代衍生物。     

DL-PhEtSiIndCpYbCl的合成及表征

以苯基三氯硅烷为原料,先后与乙基溴化镁、茚基锂、茂基锂反应,制备了苯基乙基茚基茂基硅烷(PhEtSiIndCp)。以此为配体与正丁基锂BuLi反应生成二锂盐,再与YbCl3反应,生成苯基乙基硅基桥联茚基茂基镱一氯化物(PhEtsiIndcpYbcl),其结构经^1HNMR,IR,Ms及元素分析表征。     

二茂铁氨基化合物的合成

二茂铁与邻甲氧基苯甲酰氯反应生成邻甲氧基苯甲酰基二茂铁,再与一系列芳胺反应合成亚胺,最终还原为二茂铁氨基化合物,其结构均经元素分析、^1H NMR确证。     

单茂钛催化剂用于苯乙烯-乙烯嵌段共聚物的合成与表征

乙烯（Ｅ）与苯乙烯（Ｓ）的嵌段共聚合用自制的两种催化剂———茂基三呋喃甲氧基钛［ＣｐＴｉ（ＯＣＨ２Ｏ）３］和茂基三苄氧基钛［ＣｐＴｉ（ＯＣＨ２Ｐｈ）３］进行了研究．考察了促进剂三甲基铝（ＴＭＡ）及乙烯的预聚合时间对聚合结果的影响，发现不同的催化体系有不同的［ＴＭＡ］最佳值以及随着乙烯预聚合时间的延长总的催化效率降低．对嵌段共聚合产物用丁酮、四氢呋喃和氯仿连续萃取分离，得到四氢呋喃中的可溶级分即嵌段共聚物ＰＥ ｂ ｓＰＳ，它占总嵌段共聚合产物的４０ｗｔ％～６０ｗｔ％．对嵌段共聚物用ＤＳＣ、ＷＡＸＤ、ＦＴＩＲ和１３Ｃ ＮＭＲ等方法进行了表征．     

Bis(η-cyclopentadienyl)titanium(II) in the gas phase:: Mass spectrometric and computational study of the structure and reactivity

Bis(η⁵-cyclopentadienyl)titanium(II), titanocene, was generated in the gas phase by a thermolysis of the titanocene complex with bis(trimethylsilyl)acetylene. This elusive compound was characterized by means of mass spectrometric methods. Density functional theory (DFT) calculations indicated that the triplet ground state titanocene is kinetically stable towards the unimolecular isomerizations. Based on a DFT calculated energetics, a mechanism of the formation of a titanocene dimer, was proposed, which was based on a formation of bis(η⁵-cyclopentadienyl)titanium hydride as a key intermediate.     

[η^5-Bz~5C~5(CO)~nM]~2的合成

本文通过η^5-Bz~5C~5MNa与氧化偶联试剂Fe~2(SO~4)~3/HOAC/H~2O的反应合成了含η^5-五苄基环戊二烯基配体的两个金属-金属单键化合物[η^5-Bz~5C~5(CO)~3M]~2 (1: M=Mo; 2: M=W) , 产率分别为45%和19% . 1 在沸腾的甲苯中可进一步脱碳而以98%的产率生成金属-金属叁键化合物[η^5-Bz~5C~5(CO)~2Mo]~2 (3).1～3的结构均经碳氢分析, IR, ^1H NMR 和MS鉴定. 3的结构尚被单晶X射线衍射分析确证 .     

Synthesis and characterization of bis(cyclopentadienyl)bis(hexafluoroantimonato) titanium(IV)

Reaction of titanocene dichloride with two equivalents of silver hexafluoroantimonate in sulphur dioxide quantitatively yields Cp₂Ti(SbF₆)₂ (Cp = η⁵-C₅H₅) and AgCl. The titanocene bishexafluoroantimonate was recrystallized from SO₂ and characterized by chemical analysis, ¹H NMR, IR and mass spectroscopy.     

Dynamic 1H NMR spectroscopy of η2-ethylene transition metal complexes

The low-temperature ¹H NMR spectra of bis(ethylene)trimethylphosphinenickel (1), η⁵-cyclopentadienyl(ethylene)methylnickel (2a), bis(ethylene)-η⁵-cyclopentadienylcobalt (2b), [bis(1-ethyl-2,4,6-triphenylphosphorinyl)nickel]P,P′-nickel(ethylene) (3) and η⁵-cyclopentadienyl(ethylene)hydrido(triphenylphosphine)ruthenium (4) exhibit {AA′B′B} (1) {ABB′A} (2a and 2b), {ABA′B′} (3) or {ABCD} (4) spin patterns, respectively, for the complexed ethylene. A full line shape analysis including all the proton couplings was performed for the ethylene rotation in 1, 2a and 2b. In addition to olefin rotation, a reversible intramolecular β-H-elimination was confirmed for 4 by magnetization transfer experiments.     

The preparation of a substituted titanocene-supported polymer and its application in catalytic reactions

A series of polymer-supported RCpCpTiCl₂ (Cp = η⁵  C₅H₅; RCp=η⁵  RC₅H₄) has been prepared and reduced by i-C₃H₇MgBr in situ, then used as catalysts in hydrogenation of styrene, isomerization of 1,5-cyclooctadiene and 1,5-hexadiene, and reduction of carbonyl compounds. In some cases, the introduction of a polymer ligand on the Cp ring restricts the aggregation of active sites and the formation of the inactive dimer of the titanocene species, and results in an increase of activity. Regeneration of polymer-supported titanocene catalysts was performed and the results are presented and briefly discussed.     

2-(1-(Arylimino)propyl)quinolin-8-olate half-titanocene dichlorides: synthesis, characterization and ethylene (co-)polymerization behaviour

A series of 2-(1-(arylimino)propyl)quinolin-8-olate half-titanocene dichlorides, Cp'TiCl(2)L (Cp' = η(5)-C(5)H(5) or η(5)-C(5)Me(5), L = 2-(1-(2,6-R(1)-4-R(2)-phenylimino)propyl)quinolin-8-olate), was synthesized via the stoichiometric reaction of Cp'TiCl(3) with the corresponding potassium 2-(1-(2,6-R(1)-4-R(2)-phenylimino)propyl)quinolin-8-olate salt. All titanium compounds were characterized by elemental analysis, (1)H NMR and (13)C NMR spectroscopy; the molecular structures of two representative compounds were determined by single crystal X-ray diffraction. On activation with methylaluminoxane (MAO), all half-titanocene compounds showed high activity in ethylene polymerization, and furthermore, performed with good to high activities in the co-polymerization of ethylene with either 1-hexene or 1-octene affording polyethylenes with high co-monomer incorporation. Less bulky ortho-substituents (R(1)) on the phenylimino groups were found to enhance the catalytic activities of their titanium compounds. In general, the titanium pro-catalysts containing η(5)-C(5)Me(5) (C7-C12) exhibited higher activities than did their analogues bearing η(5)-C(5)H(5) (C1-C6). Some of the resultant polyolefins were ultrahigh molecular weight polyethylene.     

Raman spectroscopic evidence for bent metallocene fragments [M(Cp)2]2+

Raman spectroscopy was used as a very simple and convenient tool for the detection of bent metallocene fragments [M(Cp)₂]²⁺ (Cp = η⁵‐cyclopentadienyl ring; M = early transition metal) both in solid state and in solution. The rules were formulated and tested on the group of titanium complexes containing one or two η⁵‐bonded cyclopentadienyl rings, as well as on a series of model α‐amino acid complexes of antitumour active titanocene and vanadocene dichlorides. Copyright © 2005 John Wiley & Sons, Ltd.     

VISIBLE LIGHT PHOTOPOLYMERIZATION OF METHYL METHACRYLATE COINITIATED WITH TITANOCENE AND KETOCOUMARIN DYE*

The photosensitive system which can initiate methyl methacrylate with visible light was composedof compound 1 bis(η-5-cyclopentadienyl)-bis[2,6-difluoro-3-(1-H-pyrrolyl)phenyl]titanium (titanocene) andcompound 2 [(3,3'-carbonylbis(7-diethylamino coumarin)] (ketocoumarin dye). The high photosensitiveinitiating efficiency of this photosensitive system could be very promising for efficient system for laser (Ar~+488 nm) to plate and photocuring for thick coating and ink. The variation of UV-visible spectrum ofcompound 2 during irradiation indicates that photolysis of compound 2 is through its triplet state and it canbe quenched by O_2. The much quicker photobleaching of the photosensitive system suggests that there existscertain quick electron transfer reaction between compounds 1 and 2.     

Hydroalumination of olefins catalyzed by immobilized titanium compounds

SiO₂-supported titanium chloride ($\text{1}$) and polystyrene-supported titanocene dichloride ($\text{2}$) and ($\text{3}$) were synthesized. These heterogenized titanium compounds are excellent catalysts for hydroalumination of olefins.     

大位阻取代环戊二烯基钛、锆衍生物

通过6,6-二烷基富烯与芳基锂及四氯化钛、锆反应,合成了十九个具有明显立体电子效应的双(取代环戊二烯基)钛、锆衍生物,研究了它们的立体结构和~1H NMR谱.