双(正丁基环戊二烯基)二氯化锆催化1-丁烯齐聚的研究

本文系统研究了双(正丁基环戊二烯基)二氯化锆与甲基铝氧烷催化剂体系催化1-丁烯的齐聚反应,详细考察了反应温度、Al与Zr的摩尔比、催化剂的用量及反应时间对1-丁烯聚合反应的影响。研究结果表明,反应的最佳条件为:聚合温度60℃、Al与Zr摩尔比为1500、催化剂中双(正丁基环戊二烯基)二氯化锆的用量为6mg、反应时间1.5h。     

茂金属催化剂催化1-己烯齐聚反应的研究

以茂金属配合物双(四甲基环戊二烯基)二氯化锆为主催化剂,1-己烯为反应物,甲基铝氧烷(MAO)为助催化剂,考察了反应条件对茂金属催化剂催化1-己烯齐聚反应活性的影响。结果表明,茂金属催化剂1-己烯齐聚反应活性和产物收率均随反应温度的升高和反应体系中铝锆比(Al/Zr)的增加而增加。通过降低反应体系中1-己烯的加入量可以使1-己烯齐聚反应在较低的Al/Zr(200∶1)和较低的反应温度(40℃)下具有较高的齐聚反应活性和产物收率。茂金属催化剂双(四甲基环戊二烯基)二氯化锆具有较高的1-己烯齐聚反应活性,其反应活性可达106g/[mol(Zr)·h]以上。     

金属茂均相催化剂用于乙烯聚合的研究

研究金属茂均相催化剂中过渡金属的性质对乙烯聚合的影响。以丁烯基取代的二茂二氯化锆（ＣｐＢｕ）２ＺｒＣｌ２和丁烯基取代的二茂二氯化锆（ＣｐＢｕ）２ＨｆＣｌ２与甲基铝氧烷组成的均相催化剂体系，对乙烯聚合进行了较详细的比较研究。     

盐酸乐卡地平的合成

以肉桂酸、氯化亚砜、甲胺等为原料经傅克烷烃化、酰氯化、酰胺化,再用KBH4/ZnC l2体系还原酰胺得到中间体N-甲基-3,3-二苯基丙胺Ⅴ;以2-甲基烯丙基氯为原料,经水合得到中间体1-氯-2-甲基-2-丙醇Ⅵ;再由Ⅴ、Ⅵ合成关键中间体侧链醇2,N-二甲基-N-(3,3-二苯基丙基)-1-氨基-2-丙醇Ⅶ,最后和母核1,4-二氢-2,6-二甲基-4-(3-硝基苯基)-5-甲氧羰基-3-吡啶羧酸(DHPCOOH)对接得到乐卡地平Ⅷ,6步反应总得率23.2%,各中间体及产物结构经MS以及1HNMR确证。     

芳氧亚胺锆络合物的合成及其催化乙烯聚合

以3-枯基-5-甲氧基水杨醛和2,6-二甲基环己胺为原料,经缩合反应合成了水杨醛亚胺配体(Ⅰ),利用四氯化锆-四氢呋喃络合物和配体反应制备了相应的芳氧基亚胺二氯化锆络合物(Ⅱ),用MS、~1HNMR和~(13)CNMR表征了配体及络合物的结构,并评价了络合物Ⅱ催化乙烯聚合的性能。在甲基铝氧烷(MAO)助催化下,Ⅱ成功地催化了乙烯聚合反应。在50℃、0.9MPa乙烯压力下,Ⅱ在甲苯中的催化活性为53.5kg聚乙烯(PE)/(mmol×Zr×h),所得聚合物为超高相对分子质量(简称分子量)聚乙烯,黏均分子量达3.3×10~6 g/mol。当以正己烷为溶剂时,聚乙烯黏均分子量提高至4.1×10~6 g/mol。     

氯碱下游产品建设投资分析（续完）

介绍了20种氯碱下游产品——氯甲苯、氯乙酸、环氧氯丙烷、氯化苄、环氧丙烷、聚偏氯乙烯树脂、氯化聚氯乙烯树脂、氯化聚乙烯、甲基氯硅烷、三氯氢硅、氯化法钛白粉、三氯化磷、4,4’-二苯基甲烷二异氰酸酯、1,4-丁二醇、苯胺、环己酮、气相法白炭黑、甲基异丁基酮、对氨基苯酚、水合肼的市场前景、技术来源与建设投资。     

氯碱下游产品建设投资分析(续1)

介绍了20种氯碱下游产品——氯甲苯、氯乙酸、环氧氯丙烷、氯化苄、环氧丙烷、聚偏氯乙烯树脂、氯化聚氯乙烯树脂、氯化聚乙烯、甲基氯硅烷、三氯氢硅、氯化法钛白粉、三氯化磷、4,4‘-二苯基甲烷二异氰酸酯、1,4-丁二醇、苯胺、环己酮、气相法白炭黑、甲基异丁基酮、对氨基苯酚、水合肼的市场前景、技术来源与建设投资。     

三、橡胶工业制品

热收缩型胶料及其模压制品 本专利中的胶料可在温度≤100℃的条件下收缩，适用于制备热收缩胶管。该胶料包括3—10份（以100份橡胶为计算基准）侧链结晶聚合物、软化剂、填料和硫化剂等组分。将三异丁基铝、（1，2’-二甲基亚甲硅基）（2，1’-二甲基亚甲硅基）双（3-三甲基甲硅烷基甲基茚基）二氯化锆和二甲基苯胺四重（五氟苯基）硼酸盐，     

查尔酮氯化加成物-1,3-二苯基-2,3-二氯-1-丙酮分析方法的研究

<正> 查尔酮的卤素加成物是医药和农药的重要中间体。西北大学刘源发等曾对查尔酮的氯化加成物1,3-二苯基-2,3-二氯-1-丙酮(简称PDD)与甲肼反应制备野燕枯的重要中间体1-甲基-3,5-二苯基吡唑及其反应过程作了初步研究。本文仅就PDD的鉴定及其定量分析方法作一初步研究。     

1-苯基-2,4-戊二酮的合成研究

以β-二酮与氨基钠反应,再与氯化二苯基碘反应得到1-苯基-2,4-戊二酮。     

Investigation on Decomposition Kinetic and Thermal Stability of Metallocene Catalysts

Data on thermal stability of metallocene catalysts such as bis(n-butyl cyclopentadienyl) zirconium dichloride and bis(t-butyl cyclopentadienyl) zirconium dichloride is required because of their application in high temperature polymerization process. In the present study, the thermal stability of the bis(n-butyl cyclopentadienyl) zirconium dichloride and bis(t-butyl cyclopentadienyl) zirconium dichloride was determined by differential scanning calorimetry (DSC) and simultaneous thermogravimetry-differential thermal analysis (TG-DTA) techniques. The results of TG analysis revealed that the main thermal degradation for the bis(n-butyl cyclopentadienyl) zirconium dichloride and bis(t-butyl cyclopentadienyl) zirconium dichloride occurs in the temperature ranges of 194–360 °C and 195–350 °C, respectively. On the other hand, TG-DTA analysis indicated that bis(n-butyl cyclopentadienyl) zirconium dichloride melts (about 98.7 °C) before it decomposes. However, the thermal decomposition of the bis(t-butyl cyclopentadienyl) zirconium dichloride was started simultaneously with its melting. Also, the kinetic parameters such as activation energy and frequency factor for both compounds were obtained from the DSC data by non-isothermal methods proposed by Kissinger and Ozawa. Based on the values of activation energy obtained by Kissinger and Ozawa methods, the following order for the thermal stability was noticed: bis(t-butyl cyclopentadienyl) zirconium dichloride >bis(n-butyl cyclopentadienyl) zirconium dichloride. Finally, the values of ΔS^#, ΔH^# and ΔG^# of their decomposition reaction were calculated.     

Copolymerization of propene with phenylnorbornene using ansa‐bridged metallocene catalysts

Propene was copolymerized with phenylnorbornene using methylaluminumoxane (MAO)‐activated metallocene dichlorides exhibiting different symmetry: C₂‐Symmetric rac‐ethylenebis(1‐ indenyl)zirconium dichloride ( 1 ), rac‐ dimethylsilylbis(1‐indenyl)zirconium dichloride ( 2 ), rac‐ethylenebis(1‐indenyl)hafnium dichloride ( 6 ), C_s‐symmetric isopropylidene(cyclopentadienyl‐9‐fluorenyl)zirconium dichloride ( 3 ), meso‐ethylenebis(1‐indenyl)zirconium dichloride ( 4 ), and C₁‐symmetric ethylene(1‐ fluorenyl‐1‐phenyl‐2‐indenyl)zirconium dichloride ( 5 ) were chosen to evaluate the influence of the symmetry in copolymerization reactions. Experiments were done as batch polymerizations to produce homogeneous copolymers. By this setup, blend formation was avoided. The copolymers were characterized by NMR, GPC, and DSC. Catalysts 1 and 2 were the most active to copolymerize random, amorphous, copolymers with good activity. C_s‐symmetric, 3 , showed decreased activity compared with 1 and 2 and produced a bimodal copolymer. Catalyst 4 showed even lower activity than that of 3 . The activity of the hafnium complex 6 , which produced a semicrystalline polymer with a high molecular weight (116,000 g/mol) was 320 kg/mol. Catalyst 1 produced the highest comonomer content (42%) in the copolymers measured by NMR. The least active catalyst was 5 (phenyl croup in the bridge), producing only 290 kg copolymer per mole of catalyst. All polymers had elevated glass transition temperatures compared to polypropylene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2743–2752, 2002     

Structure of cyclopentene unit in the copolymer with propylene obtained by stereospecific zirconocene catalysts

Copolymerization of propylene and cyclopentene (CPE) was carried out using as a catalyst isospecific rac-ethylenebis(indenyl)zirconium dichloride (1), rac-dimethylsilylenebis(indenyl)zirconium dichloride (2), rac-dimethylsilylenebis(2-methylindenyl)zirconium dichloride (3), or syndiospecific diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium dichloride (4) with methylaluminoxane as a cocatalyst. Isospecific zirconocene catalysts 1-3 produced copolymers having narrow molecular weight distribution, while syndiospecific catalyst 4 effected propylene homopolymerization. Microstructures of the copolymers were studied by ¹³C NMR and distortionless enhancement of polarization transfer (DEPT) spectroscopy. CPE was found to be incorporated in the copolymer preferentially via 1,2-insertion mechanism in the copolymerization with the catalyst 3. The catalyst 1 and 2 gave copolymers containing CPE units formed by either 1,2-insertion or 1,3-insertion mechanism. The proportion of 1,3-insertion units increased with increasing CPE content in the copolymers. The isomerization reaction from 1,2-insertion to 1,3-insertion CPE units was discussed on the basis of kinetic parameters.     

Influence of polymerization conditions on microstructure of norbornene-ethylene copolymers made using metallocene catalysts and MAO

When characterized with ¹³C-NMR, it was found that norbornene-ethylene copolymers had a more complicated microstructure when dimethylsilyl bis(indenyl) zirconium dichloride was used as the catalyst compared to ethylene bis(indenyl) zirconium dichloride. One could see more block sequences but less alternating sequences. For both catalysts the highest amounts of block sequences were obtained for high norbornene concentrations, medium to high Al/Zr ratios, and low polymerization temperatures. There were also more alternating sequences for high norbornene concentrations and high polymerization temperatures. The isolated norbornene units (separated by more than one ethylene unit) were all exoconfiguration. No unsaturation was seen. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1071–1076, 1997     

Heterogeneous polymerization of ethene with metallocene catalysts. A comparison of poly(organosiloxane) microgels and silica as support materials for MAO‐type cocatalysts

Zirconocene dichloride and bis(n‐butylcyclopentadienyl)zirconium dichloride are used as catalyst precursors for the heterogeneous polymerization of ethene. A methyl‐substituted microgel as support material for heterogeneous cocatalysts on the basis of MAO is compared with different commercially available silica‐supported cocatalysts. The catalyst performances and the properties of the obtained polyethenes show considerable differences. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 613–617, 2001     

Elastomeric properties of ethylene/propylene copolymers prepared by zirconocene/methylaluminoxane catalysts

Ethylene/propylene copolymers (EPM) have been prepared by a liquid propylene suspension process, using homogeneous catalysts based on nonbridged zirconocenes and methylaluminoxane (MAO). When bis(η⁵-cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂), bis(η⁵-cyclopentadienyl) dimethyl zirconium (Cp₂ZrMe₂) and bis(η⁵-cyclopentadienyl), dibenzyl zirconium (Cp₂ZrBz₂) were used as catalyst components, EPM having low average molecular weight (MW) were in general obtained in low yield. On the contrary, a very large improvement of productivity and MW was observed when bis(η⁵-indenyl)zirconium dichloride (Ind₂ZrCl₂) and bis(η⁵-indenyl) dimethyl zirconium (Ind₂ZrMe₂) as well as bis(η⁵-tetrahydroindenyl)zirconium dichloride [(IndH₄)₂ZrCI₂] were employed in combination with MAO. In particular, this last catalytic system allowed one to obtain EPM with a narrower distribution of MW in addition to the above characteristics. Better performances, in terms of rheological and elastomeric properties, were also found for the crude and vulcanized samples prepared by (IndH₄)₂ZrCl₂/MAO catalyst.     

Correlation between configuration/conformation of zirconocenes on the stereoselectivity of the propylene polymerization reaction

Summary The catalytic performance (activity and polymer properties) of metallocenes with different symmetries in combination with methylaluminoxane (MAO) in the polymerization of propylene has been investigated at different temperatures, under standardized reaction conditions. The zirconocene rac-ethylene (⁵-1-indenyl) zirconium (IV) dichloride, with C₂ symmetry, produces isotatic polypropylene and isopropylidene(⁵-cyclopentadienyl (⁵-9-fluorenyl) zirconium (IV) dichloride, with C _S symmetry, syndiotactic polypropylene. The degree of the tacticity of these polymers increases with decreasing polymerization temperature. Only atactic polypropylene was formed with the unbridged zirconocenes bis(⁵-cyclopentadienyl) zirconium (IV) dichloride and bis(⁵-indenyl zirconium (IV) dichloride at any temperature investigated (10–60°C).     

Influence of process parameters on ethylene-norbornene copolymers made by using [2,2′-methylenebis(1,3-dimethylcyclopentadienyl)]-zirconium dichloride and MAO

Ethylene-norbornene copolymerization was investigated by using metallocene catalysts, [2,2′-methylenebis( 1,3-dimethylcyclopentadienyl)]zirconium dichloride(2,2′-CH₂ (1,3-Me₂Cp)₂ZrCl₂, Catalyst A) and racemicethylenebis( indenly)zirconium dichloride (rac-Et(Ind)₂ ZrCl₂, Catalyst B), in the presence of methylaluminoxane as a cocatalyst. The influences of different process parameters such as polymerization temperature and ethylene pressure were studied by using a 56 wt% norbornene solution in toluene. The results show that Catalyst A has a higher activity in copolymerization than Catalyst B. Catalyst A also has a superior norbornene insertion performance to Catalyst B, resulting in polymers with higher glass transition temperatures, by approximately 70 ‡C, at similar polymerization conditions, indicative of a great commercial potential of Catalyst A.     

Heterogeneous catalyst mixtures for the polymerization of ethylene

Heterogeneous cocatalysts, catalysts, and catalyst mixtures for the polymerization of ethylene were prepared applying “fumed silica” and mesoporous MCM-41 support materials and zirconocene dichloride, titanocene dichloride, and a bis(arylimino)pyridine iron complex as catalyst precursors. The catalyst mixtures produced polyethylenes which exhibit the properties of two single polymers. Polyethylenes with the desired bimodal molecular weight distributions could be obtained with a series of ternary Zr/Ti/Fe catalysts. The ability of the zirconium and titanium species to copolymerize short-chain 1-olefins produced by the iron centers (“in situ” copolymerization) is useful for the production of copolymers from only one monomer (ethylene).     

二氯二环戊二烯基锆合成方法的改进

双环戊二烯在180°C解聚为环戊二烯,冰水浴条件下环戊二烯与钠砂反应得到环戊二烯基钠,再在二甲苯为溶剂、低温下环戊二烯基钠与四氯化锆按理论摩尔比2∶1反应3h时得到二氯二环戊二烯基锆,整个过程始终要用氮气保护。产率可以达到70%。