Highly Efficient and Thermal Robust Cobalt Complexes for 1,3-Butadiene Polymerization

A family of highly bulky bis(salicylaldiminate)Co(Ⅱ)complexes bearing cavity-like conformations are disclosed herein.Due to their unique bulky nature around the cobalt atoms that are reflected from space-filling models and the buried volume percentages,obviously longer bond distances of Co―N and Co―O are revealed from those complexes.Moreover,because of these well-protected active species,the cobalt complexes are able to catalyze 1,3-butadiene polymerization in high yields at extreme low catalyst concentrations,revealing a ultra high catalytic efficiency.At a ratio of 50000,all the complexes can afford polybutadiene with yields higher than 90%.Furthermore,the highly steric bulkiness of the ligand can also significantly enhance the thermostability of the active species.At temperature of 80-120°C,the complexes are able to successfully maintain high activities,giving polymer yields up to 90%.

Neodymium Organic Sulfonate Complexes: Tunable Electronegativity/Steric Hindrance and Application in Controlled Cis-1,4-polymerization of Butadiene

Rare earth catalysts possessing characteristics of cation-anion ion pair show advantages of adjusting electronegativity and steric hindrance of metal active sites, which can control the catalytic performance and stereoselectivity better than those of traditional metallocene and Ziegler-Natta catalysts in diene polymerization. In this work, a series of neodymium organic sulfonate complexes,Nd(CF_3SO_3)_3·x H_2O·y L(x, y: the coordination number; L refers to an organic electron donating ligand, such as acetylacetone(acac), isooctyl alcohol(IAOH), tributyl phosphate(TBP), etc.), have been synthesized to form the cationic active species in the presence of alkylaluminum such as Al(i-Bu)_3, AlEt_3, and Al(i-Bu)_2H, which display high activities and distinguishing cis-1,4 selectivities(up to99.9%) for the polymerization of butadiene. The microstructures, yield, molecular weight, and molecular weight distribution of the resulting polymer are well controlled by adjusting electronegativity/steric hindrance of the complexes. In addition, the kinetics, active species, and the possible process of polymerization are also discussed in this article.

Synthesis and Catalytic Activities of Polymer-Supported Neodymium Complexes——Polymers Containing Thiol and Sulphoxide

The neodymium complexes with crosslinked polystyrene containing -CH2SH and -CH2SOCH3 groups, P-CH2SH . NdCl3 and P-CH2SOCH3. NdCl3, were prepared. P-CH2SH . NdCl3 shows no catalytic activity for butadiene polymerization, while P-CH2SOCH3. NdCl3 can catalyze the polymerization of butadiene. The content of cis-1,4-polybutadiene is more than 95%.

POLYMERIZATION OF ETHYLENE WITH UNSYMMETRIC 2,6-BIS(IMINO)PYRIDINE IRON(Ⅱ)COMPLEX

An unsymmetric 2,6-bis(imino)pyridine iron(II) complex 1' was synthesized. The relationship between catalyststructure and its activity in ethylene polymerization is discussed. The kinetic behavior of ethylene polymerization and theeffects of polymerization conditions such as temperature, aluminum/iron molar ratio on the activity of catalyst and thecharacteristics of polyethylene were reported. The unsymmetric catalyst 1' has a good catalytic performance of 3.47×10~6 gPE·mol^(-1)·Fe·h^(-1) at 40℃ with aluminum/iron molar ratio = 2500. A dependence of catalyst activity on themethylaluminoxane (MAO) concentration and reaction temperature was found. The molecular weight (MW) of polyethylenewith broad dispersity is about 10~4-10~5 g/mol. The melting temperature and branching of polyethylenes vary with changingreaction temperature and aluminum/iron molar ratio.

Preparation and Characterization of Polymer－Supported Rare Earth Complexes

he polymers containing different ligand groups of atoms(mainly O,N,and S)and their rare earth complexes were prepared,characterized and classified based on the type of metal-ligand bonding. The catalytic activities of the complexes are briefly discussed.The polymer- supported rare earth complexes shwed much greater activities than the correspond- ing complexes with a low molecular weight.

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation(CWAO)is one of the most promising technologies for pollution abatement.Developing catalysts with high activity and stability is crucial for the application of the CWAO process.The Mn/Ce com-plex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation.The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis.The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller(BET)analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry(ICP-AES).The results show that the catalysts have high catalytic activities even at a low temperature(80°C)and low oxygen partial pressure(0.5 MPa)in a batch reactor.The metallic ion leaching is comparatively low(Mn<6.577 mg/L and Ce<0.6910 mg/L,respectively)in the CWAO process.The phenol,COD_(Cr),and TOC removal efficiencies in the solution exceed 98.5%using the optimal catalyst(named CSP).The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater.

钴系催化剂催化共轭二烯烃聚合研究进展

综述了钴系催化剂在共轭二烯烃聚合领域的发展,详细总结了使用不同种类钴催化体系和含不同类型配体的钴配合物催化丁二烯、异戊二烯等共轭二烯烃聚合的催化活性和对聚合物微观结构(区域规整度、顺式-1,4-结构、反式-1,4-结构、1,2-结构和3,4-结构)及其立构规整度(间规度、等规度、微观结构序列分布)、聚合物分子量及其分布等的影响,展望了钴系催化剂在催化共轭二烯烃聚合方面的研究方向。

以氯代烃为第三组分的稀土定向聚合催化剂——Ⅰ.催化剂配制及性能的研究

讨论了以氮代烃为第三组分的稀土催化剂聚合丁二烯的活性及其状态。发现Cl/Nd摩尔比在2至3的范围内变化,或采用先加入烷基铝和氮代烃再加入钕盐的配料顺序,其催化剂的活性最高。由某些氮代烃在一定条件下组成的催化剂可在较宽的Cl/Nd摩尔比范围内保持均相状态。

聚合物载体-稀土金属配合物的研究聚（苯乙烯－丙烯酰胺）载体－氯化钕配合物对?

研究了聚（苯乙烯－丙烯酰胺）（ＰＳＡＣ）载体－氯化钕配合物催化丁二烯聚合的规律，考察了ＰＳＡＣ载体及ＰＳＡＣ·ＮｄＣｌ３配合物的组成与催化活性间的关系．ＰＳＡＣ载体的收率不影响配合物的活性，而配合物的活性却随ＰＳＡＣ载体中Ｃ（Ｏ）ＮＨ２功能团含量的高低而改变，含量低时活性高．

多核Nd-Al双金属配合物对丁二烯的聚合 Ⅳ.烷基铝种类的影响

利用多核Ｎｄ－Ａｌ双金属配合物可单独引发双烯烃聚合的特点，考察了烷基铝种类对丁二烯加聚过程的影响，并与一般混合稀土催化体系进行了比较．烷基铝对活性体催化活性的影响与其用量有关，低ｎ（Ａｌ）／ｎ（Ｎｄ）值时，活性次序为：ＡｌＭｅ３，ＡｌＥｔ３，ＨＡｌＢｕｉ２＞Ａｌ（Ｃ８Ｈ１７）３＞ＡｌＢｕｉ３；高ｎ（Ａｌ）／ｎ（Ｎｄ）值时，活性次序相反：ＡｌＭｅ３，ＡｌＥｔ３，ＨＡｌＢｕｉ２＜Ａｌ（Ｃ８Ｈ１７）３＜ＡｌＢｕｉ３．烷基铝链转移作用强弱次序为：ＨＡｌＢｕｉ２≥ＡｌＥｔ３＞ＡｌＢｕｉ３＞ＡｌＭｅ３＞Ａｌ（Ｃ８Ｈ１７）３．根据聚丁二烯微观结构与其分子量的关系，可将烷基铝对聚丁二烯顺式含量的影响分为３类：（１）ＡｌＥｔ３和Ａｌ（Ｃ８Ｈ１７）３；（２）ＨＡｌ－Ｂｕｉ２和ＡｌＢｕｉ３；（３）ＡｌＭｅ３．所得结果有助于对稀土催化定向聚合过程的深入了解．

聚合物载体－稀土金属络合物催化剂催化双烯烃聚合的特征

对聚合物载体的合成、稀土金属化合物的固定和聚合物载体－稀土金属络合物的性质及其催化双烯烃聚合的特征进行了论述。

二氧化硅负载的聚-4-硫杂-6-二苯膦己基硅氧烷钯(0)配合物的合成与催化性能

聚 -4-硫杂 -6-二苯膦己基硅氧烷与氯化钯作用后经水合肼还原 ,合成了二氧化硅负载的硫 -膦混合双齿钯 ( 0 )配合物 .该配合物可以有效地催化芳 (烯 )基卤化物与烯烃、炔烃、Grignard试剂的交叉偶联反应 ,并可回收多次利用 ,活性基本不变 .

聚合负载三氯化钕配合物的合成及其催化活性—含硫醇和亚砜基团的配合物

合成了含—CH2 SH和—CH2 SOCH3 功能团的交联聚苯乙烯钕配合物P—CH2 SH·NdCl3 和P—CH2 SOCH3·NdCl3。P—CH2 SH·NdCl3 对丁二烯聚合没有催化活性 ,而P—CH2 SOCH3·NdCl3 可使丁二烯高顺式聚合 ,聚丁二烯顺 1,4单元含量在 95 %以上。

载体中元素电负性对稀土催化剂聚合活性的影响

Supported rare earth catalysts were made from Nd(O i Pr) 3 and the chlorides as well as bromides of the elements of ⅠA and ⅡA groups which were used as supporters of the catalyst. In the study on the relationship between the composition of supporters and the polymerization activity of butadiene in the presence of the supported rare earth catalysts, it was found that the electronegativity of ⅠA or ⅡA elements has an obvious effect on the activity of supported catalysts, that is the activity of the supported catalyst increases with the increasing of the electronegativity. This phenomenon is explained in terms of the interaction between the HOMO of the butadiene and the LUMO of the neodymium. This rule also holds in the case when halides of magnesium were used as supporters.

后过渡金属配合物催化乙烯齐聚与聚合的研究进展

后过渡金属配合物催化乙烯齐聚和聚合研究 ,不仅拓展了后过渡金属配合物的应用 ,而且为探求烯烃聚合催化剂提供了新机遇 ,成为当前催化研究中的热点课题。本文综述了后过渡金属铁、钴、镍配合物催化乙烯齐聚和聚合的国内外最新研究进展。

（η^6—Arene）Nd（AlCl4）3—AIR3催化丁二烯的聚合

<正> 关于η~6-芳烃过渡金属有机络合物催化烯烃聚合的研究已早有报道.但对于η~6-芳烃稀土络合物催化烯烃聚合的研究至今未见报道.我们在研究了(η~6-C_6H_6)Nd-(AlCl_4)_3-AlR_3催化异成二烯聚合的基础上,又考察了不同芳烃烯土络合物和几种AlR_3组成的催化剂对丁二烯聚合的催化活性. 1.原料及试剂:丁二烯和烷基铝均为聚合级.汽油分别经浓硫酸。

聚合物载体－稀土金属络合物的研究 Ⅻ．聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］载体－三氯化钕络合物－三异丁基铝体系催化丁二烯聚合的活性

研究了聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］（ＰＳＭ）载体－三氯化钕（ＮａＣ１３）络合物－Ａｌ（ｉ－Ｂｕ）３体系催化丁二烯聚合的活性与ＰＳＭ转化率和ＰＳＭ·ＮｄＣｌ３络合物组成的关系。实验结果表明，ＰＳＭ转化率为１８．１％～５３．４％，对ＰＳＭ·ＮｄＣｌ３－Ａｌ（ｉ－Ｂｕ）３体系的活性基本上无影响。低功能团含量的ＰＳＭ·ＮｄＣｌ３络合物的活性优于高功能团含量的ＰＳＭ·ＮｄＣｌ３。该络合物中Ｎｄ含量为４．５×１０（－４）ｍｏｌ／ｇ左右时，体系的催化活性最佳。体系的活性随引入的Ｌｅｗｉｓ酸的种类和用量的不同而改变。

聚合物载体－稀土金属络合物的研究Ⅺ．聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］载体－氯化钕络合物催化体系丁二烯聚合的动力学参数

采用膨胀计法，研究了以Ａｌ（ｉ－Ｂｕ）＿３为助催化剂，聚［苯乙烯－甲基丙烯酸β（甲基亚硫酰基）乙酯］载体－氯化钕络合物为主催化剂的丁二烯聚合动力学。丁二烯均聚时聚合速率对单体浓度和主、助催化剂浓度均呈一级关系，与氯化钕二甲基亚砜络合物－Ａｌ（ｉ－Ｂｕ）＿３体系基本一致，但前者的表现活化能仅为１８．７ｋＪ／ｍｏｌ，后者为４６９．ＫＪ／ｍｏｌ，前者的钕利用率大约是后者的５倍。

钨系齐格勒－纳塔催化剂引发丁二烯－苯乙烯共聚合──Ⅰ．高乙烯基丁苯共聚物的合成

以ＷＣｌ_６（Ｗ）为催化剂，分别与四种烷基铝组成催化体系，以苯乙烯（Ｓｔ）、丁二烯（Ｂｄ）为单体，在６０～７０℃下聚合５ｈ，可获得高乙烯基丁苯共聚物。结果表明，以Ｗ－Ａｌ（ｉ－Ｂｕ）_２Ｃｌ（Ａｌ）组成的催化体系，在Ａｌ／Ｗ＝３．５（摩尔比），陈化３０ｍｉｍ以上时，活性最高，所得丁苯共聚物［η］＝０．２５～０．６５ｄＬ／ｇ，乙烯基含量大于５０％（摩尔），结合Ｓｔ含量为１０％～４０％（摩尔）。

聚合负载三氯化镨配合物的合成、表征及催化活性

合成并表征了聚(苯乙烯(S)-丙烯酸(A))镨配合物(SAAC·Pr).红外光谱表明了它的配位结构.计算了共聚物中单体单元的序列分布.苯乙烯和丙烯酸单元长序列分布随其在共聚物中含量的增加而增加.当丙烯酸长序列分布高时,配合物的催化活性低.苯乙烯和丙烯酸的平均链长分别为 nS=3, nA=1时,配合物的催化活性最高.