丁基改性的甲基铝氧烷助催化乙烯聚合

采用丁基改性的甲基铝氧烷(MMAO-Bu)与茂金属或后过渡金属配合物组成催化体系并催化乙烯聚合或齐聚。考察了MMAO-Bu的助催化活性及其对聚乙烯分子量和齐聚产物分布的影响。结果表明,适宜组成的MMAO-Bu可表现出比MAO更高的助催化活性;在MMAO-Bu的助催化作用下,所得聚乙烯具有较宽的分子量分布,而齐聚产物分布向高碳数的方向移动。     

含氟双亚胺非茂金属锆配合物催化α-烯烃配位聚合研究

以3,5-二叔丁基水杨醛和邻氟苯胺为原料,合成了3,5-二叔丁基水杨醛缩2-氟苯胺配体,在四氢呋喃溶剂中与Zr Cl4配位反应,制得了1种新型含氟双亚胺过渡金属锆配合物,采用核磁共振仪、元素分析等手段对所合成的化合物进行了表征,并在甲基铝氧烷(MAO)为助催化剂、甲苯为溶剂的条件下,对其催化乙烯聚合进行了探究。结果表明,3,5-二叔丁基水杨醛与2-氟苯胺形成一种新型含氟亚胺配体,与锆的氯化物能够形成双亚胺锆配合物,锆配合物与MAO催化体系对甲苯溶剂中的乙烯均相催化聚合,具有极高的催化活性,并能够制得高黏均分子量的聚乙烯(PE)产品。催化乙烯聚合的优化反应条件为:助催化剂中Al与主催化剂中Zr的摩尔比4 500,聚合反应温度40℃。     

负载型茂金属催化剂用于乙烯淤浆聚合的研究

在烯烃催化聚合领域,茂金属催化剂显示出比传统Ziegler-Natta催化剂更高的活性。以苯甲酸催化三甲基铝（TMA）受控水解生成甲基铝氧烷（MAO）,经热解过程后合成了一种不溶形式的固体聚甲基铝氧烷（sMAO）。以合成的sMAO为载体负载茂金属催化剂,并将该催化剂应用于乙烯淤浆聚合反应中,系统探究了聚合条件对催化行为的影响,同时对聚乙烯产品mPE的粒度、堆密度、分子量及分布和熔体流动速率等基本理化性能进行了分析表征。实验结果表明,制备的催化剂颗粒形态较好,粒子分布均匀,在5 L釜中催化淤浆反应,乙烯/1-己烯共聚活性最高可达15 302.6 g·g^-1,并得到了相对分子质量分布均匀的中、高密度聚乙烯产品。     

双核茂金属催化剂催化乙烯／1-己烯共聚合

合成了[CpTiCl2]2 {μ,μ-[(Me2Si)2 (η5-C5H3)2]}双核茂金属化合物,用1H NMR和IR分析进行了表征.合成的化合物经硅胶作载体负载,以MAO作助催化剂,催化乙烯/1-己烯共聚合.考察了茂金属用量,茂金属与硅胶/MAO处理温度,MAO的用量对负载催化剂的影响,以及1-己烯用量对聚合产物的影响.反应温度65℃,在1-己烯浓度为0.25 mol·L-1条件下共聚活性可达4.01×106 gPE/mol Ti·h,催化所得聚乙烯的相对分子质量分布为7.32,1-己烯插入率8.45%.     

双核茂金属催化剂催化乙烯／1-己烯共聚合

制备[CpTiCl2]2{μ,μ-[(Me2Si)2(η5-C5H3)2]}双核茂金属化合物,用1H NMR和IR分析进行了表征.合成的化合物经硅胶作载体负载,以MAO作助催化剂,催化乙烯/1-己烯共聚合.考察了茂金属用量,茂金属与硅胶/MAO处理温度,MAO的用量对负载催化剂的影响,以及己1烯-用量对聚合产物的影响.反应温度65℃,在1-己烯浓度为0.25mol/L条件下共聚活性可达4.01× 106gPE/molTi·h,催化所得聚乙烯的相对分子质量分布为7.32,己1烯-插入率8.45.     

负载茂金属催化剂催化乙烯气相聚合

研究了负载茂金属催化剂(n-BuNeCp)_2ZrCl_2/SiO_2的乙烯气相聚合行为及其催化聚合产品的性能。三乙基铝加入聚合体系后可降低负载茂金属催化剂的初始活性,有利于聚合过程中的温度控制。气相聚合产品聚乙烯的重均分子量为(1 42～2.28)×10~5,相对分子质量分布为2.6～3.1,熔点在135℃以上,结晶度约为60%,聚乙烯产物颗粒形态以球形为主.堆密度大于0.35 g/cm~3。     

Ziegler-Natta/茂金属复合催化剂制备双峰聚乙烯

通过把茂金属催化剂负载在Ziegler-Natta催化剂上制备了ZM复合催化剂,在单一聚合反应器内研究了ZM催化剂用于乙烯聚合制备双峰聚乙烯的性能。考察了催化剂中茂金属化合物的含量、聚合过程中反应温度、助催化剂的用量和共聚单体1-己烯的用量对催化剂乙烯聚合性能的影响规律。结果表明：采用ZM催化剂可以在单反应器内催化乙烯聚合得到分子量分布呈双峰的聚乙烯,聚乙烯的分子量分布达到155,聚合活性可达2.52×10⁷ g/molMt·h。     

二茂型稀土金属对乙烯聚合反应的催化性能研究进展

概述了茂金属有机络合物的发展,重点介绍了无助催化剂的非桥二茂稀土金属络合物、桥联二茂稀土金属络合物和加助催化剂的非桥二茂稀土金属络合物三类二茂型稀土金属络合物对乙烯聚合的催化活性的研究进展,说明二茂型有机稀土络合物在催化乙烯聚合反应中有优良活性并极具开发价值。     

茂金属加合物技术首次工业试验

采用中国石油化工股份有限公司茂金属加合物技术制备茂金属加合物,并进行负载化研究;完成了茂金属加合物催化剂催化乙烯聚合以及乙烯与α-烯烃共聚合的淤浆、环管淤浆、气相流化床工艺的中试;在中试的基础上,茂金属加合物催化剂于60kt／a气相流化床聚乙烯生产装置上成功进行了工业试验。探索了茂金属催化剂与Ziegler催化剂的切换技术,研究了催化剂组成和聚合工艺参数对聚乙烯树脂性能的影响。用所得茂金属聚乙烯树脂加工成的薄膜具有较好的透明性,并表现出了优异的落镖冲击强度和撕裂强度。     

中国专利

[N^O]型双齿配体与锆金属配位的烯烃聚合催化剂及其制备方法本发明为一种[N^O]型双齿配体与锆金属配位的烯烃聚合催化剂及其制备方法。该催化剂表达式为ZrL_2Cl_2,其中L表示一种含有可与金属配位的N,O原子的配体。该催化剂不仅具有独特新颖的结构,催化乙烯聚合具有较高的催化活性,并且催化剂制备简单。该催化剂作为A,B组分配合,可用于催化乙烯聚合,制备高相对分子质量聚乙烯产品。公开号CN 101824109公开日2010年9月8日申请人复旦大学     

Insect antifeedant properties of anthranoids from the genusVismia

Vismiones and ferruginins, representatives of a new class of lypophilic anthranoids from the genusVismia were found to inhibit feeding in larvae of species ofSpodoptera, Heliothis, and inLocusta migratoria.     

Direct observation of freeze-thaw instability of latex coatings via high pressure freezing and cryogenic SEM

Despite its industrial importance, the subject of freeze-thaw (F/T) stability of latex coatings has not been studied extensively. There is also a lack of fundamental understanding about the process and the mechanisms through which a coating becomes destabilized. High pressure (2100 bar) freezing fixes the state of water-suspended particles of polymer binder and inorganic pigments without the growth of ice crystals during freezing that produce artifacts in direct imaging scanning electron microscopy (SEM) of fracture surfaces of frozen coatings. We show that by incorporating copolymerizable functional monomers, it is possible to achieve F/T stability in polymer latexes and in low-VOC paints, as judged by the microstructures revealed by the cryogenic SEM technique. Particle coalescence as well as pigment segregation in F/T unstable systems are visualized. In order to achieve F/T stability in paints, latex particles must not flocculate and should provide protection to inorganic pigment and extender particles. Because of the unique capabilities of the cryogenic SEM, we are able to separate the effects of freezing and thawing, and study the influence of the rate of freezing and thawing on F/T stability. Destabilization can be caused by either freezing or thawing. A slow freezing process is more detrimental to F/T stability than a fast freezing process; the latter actually preserves suspension stability during freezing. Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, October 27–29, 2004 in Chicago, IL. Tied for first place in The John A. Gordon Best Paper Competition.     

Ethanol and (−)-α-Pinene: Attractant Kairomones for Bark and Ambrosia Beetles in the Southeastern US

In 2002–2004, we examined the flight responses of 49 species of native and exotic bark and ambrosia beetles (Coleoptera: Scolytidae and Platypodidae) to traps baited with ethanol and/or (−)-α-pinene in the southeastern US. Eight field trials were conducted in mature pine stands in Alabama, Florida, Georgia, North Carolina, and South Carolina. Funnel traps baited with ethanol lures (release rate, about 0.6 g/day at 25–28°C) were attractive to ten species of ambrosia beetles (Ambrosiodmus tachygraphus, Anisandrus sayi, Dryoxylon onoharaensum, Monarthrum mali, Xyleborinus saxesenii, Xyleborus affinis, Xyleborus ferrugineus, Xylosandrus compactus, Xylosandrus crassiusculus, and Xylosandrus germanus) and two species of bark beetles (Cryptocarenus heveae and Hypothenemus sp.). Traps baited with (−)-α-pinene lures (release rate, 2–6 g/day at 25–28°C) were attractive to five bark beetle species (Dendroctonus terebrans, Hylastes porculus, Hylastes salebrosus, Hylastes tenuis, and Ips grandicollis) and one platypodid ambrosia beetle species (Myoplatypus flavicornis). Ethanol enhanced responses of some species (Xyleborus pubescens, H. porculus, H. salebrosus, H. tenuis, and Pityophthorus cariniceps) to traps baited with (−)-α-pinene in some locations. (−)-α-Pinene interrupted the response of some ambrosia beetle species to traps baited with ethanol, but only the response of D. onoharaensum was interrupted consistently at most locations. Of 23 species of ambrosia beetles captured in our field trials, nine were exotic and accounted for 70–97% of total catches of ambrosia beetles. Our results provide support for the continued use of separate traps baited with ethanol alone and ethanol with (−)-α-pinene to detect and monitor common bark and ambrosia beetles from the southeastern region of the US.     

Methyl 2,4,6-decatrienoates Attract Stink Bugs and Tachinid Parasitoids

Halyomorpha halys (Stål) (Pentatomidae), called the brown marmorated stink bug (BMSB), is a newly invasive species in the eastern USA that is rapidly spreading from the original point of establishment in Allentown, PA. In its native range, the BMSB is reportedly attracted to methyl (E,E,Z)-2,4,6-decatrienoate, the male-produced pheromone of another pentatomid common in eastern Asia, Plautia stali Scott. In North America, Thyanta spp. are the only pentatomids known to produce methyl 2,4,6-decatrienoate [the (E,Z,Z)-isomer] as part of their pheromones. Methyl 2,4,6-decatrienoates were field-tested in Maryland to monitor the spread of the BMSB and to explore the possibility that Thyanta spp. are an alternate host for parasitic tachinid flies that use stink bug pheromones as host-finding kairomones. Here we report the first captures of adult and nymph BMSBs in traps baited with methyl (E,E,Z)-2,4,6-decatrienoate in central Maryland and present data verifying that the tachinid, Euclytia flava (Townsend), exploits methyl (E,Z,Z)-2,4,6-decatrienoate as a kairomone. We also report the unexpected finding that various isomers of methyl 2,4,6-decatrienoate attract Acrosternum hilare (Say), although this bug apparently does not produce methyl decatrienoates. Other stink bugs and tachinids native to North America were also attracted to methyl 2,4,6-decatrienoates. These data indicate there are Heteroptera in North America in addition to Thyanta spp. that probably use methyl 2,4,6-decatrienoates as pheromones. The evidence that some pentatomids exploit the pheromones of other true bugs as kairomones to find food or to congregate as a passive defense against tachinid parasitism is discussed.     

2007～2008年世界塑料工业进展

收集了2007年7月～2008年6月世界塑料工业的相关资料,介绍了2007～2008年国外塑料工业的发展情况,提供了世界塑料产量、消费量及全球各类树脂的需求量及产能情况.按通用热塑性树脂(聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂)、工程塑料(尼龙、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚)、特种工程塑料(聚苯·硫醚、液晶聚合物、聚醚醚酮)、通用热固性树脂(酚醛、聚氨酯、不饱和聚酯树脂、环氧树脂)不同品种的顺序,对树脂的产量、消费量、供需状况及合成工艺、产品应用开发、树脂品种的延伸及应用的进一步扩展等技术作了详细介绍.     

2005～2006年国外塑料工业进展

收集了2005年7月～2006年6月国外塑料工业的相关资料,介绍了2005—2006年国外塑料工业的发展情况。提供了世界塑料产量、消费量及全球各类树脂生产量以及各国塑料制品的进出口情况。作为对比,介绍了中国塑料的生产情况。按通用热塑性树脂（聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、ABS树脂）、工程塑料（聚酰胺、聚碳酸酯、聚甲醛、热塑性聚酯、聚苯醚）、通用热固性树脂（酚醛、聚氨酯、不饱和树脂、环氧树脂）、特种工程塑料（聚苯硫醚、液晶聚合物、聚醚醚酮）的品种顺序,对树脂的产量、消费量、供需状况及合成工艺、产品开发、树脂品种的延伸及应用的扩展作了详细的介绍。