烯烃配位聚合二十年

聚烯烃树脂是消费量最大的合成树脂种类,性能优异,用途广泛。二十多年来,烯烃配位聚合技术取得了突飞猛进的发展,在催化剂、聚合方法、聚合工艺方面都有重大突破。本文综述了二十多年来烯烃配位聚合的研究发展情况,包括Ziegler-Natta催化剂,茂金属催化剂,非茂金属催化剂,配位聚合机理,功能化聚烯烃的制备,原位共聚制备LLDPE,原位聚合制备纳米复合材料,活性配位聚合以及Spherizone工艺等方面的成就。     

High-velocity stretching of polyolefin tapes

Stretched polyolefin films and tapes are used in many packaging applications, such as BigBags. Stretching is elongation of polymer tapes in one direction, resulting in improved mechanical properties. Both, amorphous and crystalline polymers are in principle stretchable but linear, unbranched macromolecules are highly stretchable. Hence, the stretchability of e.g. branched low density polyethylene (PE-LD) is lower than of high-density polyethylene (PE-HD). Basic requirements for stretching of thermoplastics are known, but correlations between material parameters and stretching behaviour are scarce. Moreover, stretching of polymers is usually studied with tensile tests at stretching velocities much lower (1–500 mm/min) than in industrial processes (400–1000 mm/s), while results from high-velocity stretching tests or on production machines have not been published as of yet. We investigated high-velocity (800 mm/s) stretching of PE-LD, PE-HD and isotactic polypropylene films and tapes and which stretching parameters resulted in maximum mechanical properties. It was found that sample geometry, temperature, and the degree of stretching have a significant influence on the properties of stretched tapes, e.g. higher stretching temperature resulted in higher mechanical properties and orientation of crystallites. Furthermore, about 80% of the maximum stretching degree resulted in maximum mechanical properties.     

Acetamidine complexes as catalysts for ethylene polymerization

The reaction of (2,6-diisopropyl-phenyl)-acetimidoyl chloride or (2,6-dimethyl-phenyl)-acetimidoyl chloride with 2,6-dimethylaniline in the presence of triethylamine yields a mixture of isomers N′-(2,6-diisopropyl-phenyl)-N-[1-(2,6-diisopropyl-phenylimino)-ethyl]-N-(2,6-dimethyl)-acetamidine (1a) and N-(2,6-diisopropyl-phenyl)-N-[1-(2,6-diisopropyl-phenylimino)-ethyl]-N′-(2,6-dimethyl)-acetamidine (1b), and N,N′-bis-(2,6-dimethyl-phenyl)-N-[1-(2,6-dimethyl-phenylimino)ethyl)]-acetamidine (2), respectively. The addition of isomers (1a + 1b) to nickel (II) dibromide 2-methoxyethyl ether, (NiBr₂[O(C₂H₄OMe)₂]) gives a mixture of new nickel complexes, [NiBr₂{N′-(2,6-diisopropyl-phenyl)-N-[1-(2,6-diisopropyl-phenylimino)-ethyl]-N-(2,6-dimethyl)-acetamidine}] (3a) and [NiBr₂{N-(2,6-diisopropyl-phenyl)-N-[1-(2,6-diisopropyl-phenylimino)-ethyl]-N′-(2,6-dimethyl)-acetamidine}] (3b). Similarly, ligand 2 reacts with nickel (II) dibromide 2-methoxyethyl ether to afford the complex [NiBr₂{N,N´-bis-(2,6-dimethyl-phenyl)-N-[1-(2,6-dimethyl-phenylimino)ethyl)]-acetamidine}] (4). The structures of the ligands and nickel complexes have been determined by single crystal X-ray diffraction.The addition of MAO to these complexes generates catalytically active species for the homopolymerization of ethylene. The polymer products are high molecular weight (80-169 K). At temperatures of up to 60 °C both catalysts are a single site giving a monomodal molecular weight distribution. However, at 70 °C the mixture (3a + 3b) shows a bimodal molecular weight distribution.     

Bis(alkylphenylaminopyridinato) titanium dichlorides as ethylene polymerization catalysts

Four titanium complexes derived from 2-(2-ethylanilino)-, 2-(3,5-dimethylanilino)pyridine, 2-(4-n-butylanilino)- and 2-(2-t-butylanilino)pyridine were synthesized and characterized by spectroscopic methods. These complexes were used to catalyze the polymerization of ethylene in the presence of MAO as cocatalyst. The effect of the complex structures on the polymerization behavior was studied. All the alkylphenylaminopyridinato titanium complexes used in this study yielded higher molar masses than the unsubstituted bis(phenylaminopyridinato) titanium dichloride complex. Correspondingly, activities were lower and molar mass distributions were broader than those in the case of the unsubstituted bis(phenylaminopyridinato) titanium catalyst. The fluxional behavior of alkylphenylaminopyridinato titanium catalysts is probably the reason for the broad molar mass distributions. This might be due to the electron-donating effect from the alkyl substituent because the alkyl substituent enhances the active site isomerization rate.     

A New Zirconocene Complex and Its Catalytic Properties for Olefin Polymerization

As metallocene olefin polymerization catalysts,unbridged metallocenecomplexeshave re-ceived much attention because they are relatively easy to be synthesized and can produce notonly polyethylene butalso oligo-or polypropylenes with differentstereoregularities and prop-erties depending on their structures[1 ,2 ] .It has been known that a rather small structuralchange for a metallocene compound may cause a remarkable effect on its catalytic properties,such as catalytic activity,polymer molecule w…     

Neodymium Ziegler-Natta catalysts: Evaluation of catalyst ageing effect on 1,3-butadiene polymerization

Catalysts constituted by neodymium versatate, diisobutylaluminium hydride and t-butyl chloride were used in this work. After their synthesis, they were aged at 40 °C for 48 h. Afterwards, they were maintained at 10 °C for more 5, 15, 40, 80, 160 and 250 days and finally the aged catalysts were evaluated in butadiene polymerization. The polybutadienes were characterized by size exclusion chromatography (SEC) to determine the molecular weight characteristics and by infrared spectroscopy (FTIR) to determine the microstructure. The aim of this work is to evaluate the effect of ageing time on 1,4 polymerization of butadiene. The results showed that the stereoselectivity of the active sites was not affected by the ageing conditions. However, the catalyst activity increased for long times of ageing.     

Versatile Production of Multivariate,Hyperdimensional End Group and Main Chain Functionalized Polyolefins

The (stereoselective) living coordinative copolymerization of 1-alkenes with 4-aryl-1,6-heptadienes, in both the absence and presence of multiple equivalents of a reversible chain transfer agent, is established as a highly versatile strategy for production of multivariate hyperdimensional functionalized semi-crystalline or amorphous polyolefins that optionally possess either mono- or difunctionalized (telechelic) end-groups in combination with a programmable level of incorporation of orthogonal functional groups within the main-chain. The non-conjugated diene comonomers are readily obtained from a diverse range of aryl carboxaldehyde precursors through a one-step bis-allylation process. These results serve to provide a new platform for exploring the science and technology of a vast new landscape of functionalized classes of polyolefins that are now accessible in practical and scalable quantities.     

Cr/MCM-41催化剂上的乙烯聚合行为

以纯硅ＭＣＭ４１为载体，负载Ｐｈｉｌｉｐｓ烯烃聚合催化剂活性组分Ｃｒ．ＸＲＤ及ＴＥＭ表征结果表明，所得到的Ｃｒ／ＭＣＭ４１催化剂具有良好的晶体结构和较理想的长程有序一维孔道．ＦＴＩＲ和Ｒａｍａｎ光谱表征结果表明，Ｃｒ／ＭＣＭ４１上不仅可发生乙烯聚合过程，而且形成的聚乙烯以结晶和无定形两种形态存在．乙烯聚合活性不仅与反应参数有关，而且与Ｃｒ的负载量密切相关．用于乙烯聚合后，Ｃｒ／ＭＣＭ４１催化剂仍保持其特征的晶体结构和一维孔道结构．     

Chemical catalysed recycling of polypropylene over a spent FCC catalyst and various commercial cracking catalysts using TGA

Thermogravimetric analysis (TGA) has been used as a tool to characterise the activity, regenerability and deactivation behaviour of spent FCC commercial catalyst (FCC-s1) in the degradation of polypropylene. The FCC-s1 catalysts and amorphous silica–alumina (SAHA) significantly reduced the activation energy as compared with thermal process, and zeolites (ZSM-5 and HUSY) further reduced the activation energy. However, silicalite catalysts gave very minimal effect on PP degradation at a temperature similar to that of thermal cracking. Analysis of the TGA results allowed a relationship between catalyst activity and coke content to be derived. The activity of FCC-s1 catalysts was found to fall exponentially with coke content, and it could be recover most its initial value. The results represent an interesting alternative to have significant impact on the economics of a catalytic polymer degradation process employing post-use FCC commercial catalysts of zero market value.     

Methylene‐Bridged Metallocenes with 2,2′‐Methylenebis[1H‐inden‐1‐yl] Ligands: Synthesis,Characterization, and Polymerization Catalysis of a Synthetically Simple Class of C2‐ and C2v‐Symmetric ansa‐Metallocenes

The acid‐catalyzed reaction between formaldehyde and 1H‐indene, 3‐alkyl‐ and 3‐aryl‐1H‐indenes, and six‐membered‐ring substituted 1H‐indenes, with the 1H‐indene/CH₂O ratio of 2 : 1, at temperatures above 60° in hydrocarbon solvents, yields 2,2′‐methylenebis[1H‐indenes] 1 – 8 in 50–100% yield. These 2,2′‐methylenebis[1H‐indenes] are easily deprotonated by 2 equiv. of BuLi or MeLi to yield the corresponding dilithium salts, which are efficiently converted into ansa‐metallocenes of Zr and Hf. The unsubstituted dichloro{(1,1′,2,2′,3,3′,3a,3′a,7a,7′a‐η)‐2,2′‐methylenebis[1H‐inden‐1‐yl]}zirconium ([ZrCl₂( 1′ )]) is the least soluble in organic solvents. Substitution of the 1H‐indenyl moieties by hydrocarbyl substituents increases the hydrocarbon solubility of the complexes, and the presence of a substituent larger than a Me group at the 1,1′ positions of the ligand imparts a high diastereoselectivity to the metallation step, since only the racemic isomers are obtained. Methylene‐bridged ‘ansa‐zirconocenes’ show a noticeable open arrangement of the bis[1H‐inden‐1‐yl] moiety, as measured by the angle between the planes defined by the two π‐ligands (the ‘bite angle’). In particular, of the ‘zirconocenes’ structurally characterized so far, the dichloro{(1,1′,2,2′,3,3′,3a,3′a,7a,7′a‐η)‐2,2′‐methylenebis[4,7‐dimethyl‐1H‐inden‐1‐yl]}zirconium ([ZrCl₂( 5′ )] is the most open. The mixture [ZrCl₂( 1′ )]/methylalumoxane (MAO) is inactive in the polymerization of both ethylene and propylene, while the metallocenes with substituted indenyl ligands polymerize propylene to atactic polypropylene of a molecular mass that depends on the size of the alkyl or aryl groups at the 1,1′ positions of the ligand. Ethene is polymerized by rac‐dichloro{(1,1′,2,2′,3,3′,3a,3′a,7a,7′a‐η)‐2,2′‐methylenebis[1‐methyl‐1H‐inden‐1‐yl]}zirconium ([ZrCl₂( 2′ )])/MAO to polyethylene waxes (average degree of polymerization ca. 100), which are terminated almost exclusively by ethenyl end groups. Polyethylene with a high molecular mass could be obtained by increasing the size of the 1‐alkyl substituent.     

Supported dichlorobis(3-hydroxi-2-methyl-4-pyrone)Ti(IV) catalysts: Evaluation on ethylene polymerization

Dichlorobis(3-hydroxi-2-methyl-4-pyrone)Ti(IV) complex was grafted on different inorganic supports, namely different kinds of SiO₂, MAO-modified silica, MCM-41, Al₂O₃, ZrO₂ and MgO. The resulting supported catalysts were shown to be active in ethylene polymerization using methylaluminoxane (MAO) as cocatalyst, most of them being even more active that the homogeneous complex. The highest catalyst activities were observed for the Ti complex supported on SiO₂ 948 activated at 450 °C, MCM-41 and Al₂O₃.     

Synthesis, characterization, and catalytic activity of divalent organolanthanide complexes with new tetrahydro-2H-pyranyl-functionlized indenyl ligands

Two series of new divalent organolanthanide complexes with the general formula [η⁵:η¹-{1-R-3-(C₅H₉OCH₂)C₉H₅}]₂Ln^II (R = H, Ln = Yb (3); R = Me₃Si, Ln = Yb (4); R = H, Ln = Eu (5); R = Me₃Si, Ln = Eu (6)) were prepared by reactions of 2 equiv. of 1-R-3-(C₅H₉OCH₂)C₉H₆ (R = H (1), R = Me₃Si (2)) with the lanthanide(III) amides [(Me₃Si)₂N]₃Ln(μ-Cl)Li(THF)₃ (Ln = Yb, Eu) via a one-electron reductive elimination process. Recrystallization of 6 from n-hexane afforded [η⁵:η¹-(C₅H₉OCH₂C₉H₅SiMe₃)]₂Eu^II · (C₆H₁₄)_0.5 (7). All compounds were fully characterized by elemental analyses, and spectroscopic methods. The structures of complexes 4 and 7 were additionally determined by single-crystal X-ray analyses. The catalytic activity of the complexes on methyl methacrylate and ε-caprolactone polymerization was studied, and the temperatures, substituents on the indenyl ring, and solvents effects on the catalytic activity of the complexes were examined.     

工业丙烯聚合过程的模型化研究进展

基于我国聚丙烯生产状况,指出我国在聚丙烯合成技术上的研究缺陷.针对国内缺陷并遵循"聚丙烯合成过程模型化"主线,本文从聚丙烯生产工艺、丙烯聚合机理、丙烯聚合动力学以及聚合反应器模型四方面对丙烯聚合过程模型化的近期研究进展进行综述,重点简述我国科研工作者在相关方面的研究进展.     

meso-Me2Si(1-indenyl)2ZrCl2/methylalumoxane catalyzed polymerization of the ethylene to ethyl-branched polyethylene

The meso ansa zirconocene with dimethylsilyl bridge, activated by methylalumoxane, catalyses the ethylene polymerization, producing ethyl-branched polyethylene. With respect to the polymers obtained with the previously investigated meso zirconocenes, we have found higher branching amount and lower molecular weight. The rapid β-H transfer from the growing chain to the coordinated monomer could account for both these features of the polymer. The investigation on the structural parameters of the complex, through X-ray diffraction analysis, and on the electrophilicity of the cationic center, through NMR experiments, suggests, as a possible rationalization of this behavior, the obstruction in the inward site.     

CS-1型和CS-2型高效催化剂的研制、生产和应用

CS-1型和CS-2型高效催化剂已成功应用于国内外许多聚丙烯生产厂。工业应用表明,催化剂具有高效率、高立构定向性、良好的形态和氢调性能,以及PP等规指数可调性,对丙烯原料的适用性强等性能特点。本文简述CS型高效催化剂的开发,工业生产和工业应用情况。     

SYNTHESIS AND CHARACTERIZATION OF POLYPROPYLENE/MONTMORILLONITE NANOCOMPOSITES VIA AN in-situ POLYMERIZATION APPROACH

Polypropylene/montmorillonite (PP/MMT)nanocomposites were prepared by in-situ polymerization using aMMT/MgCl_2/TiCl_4-EB Ziegler-Natta catalyst activated by triethylaluminum(TEA). The enlarged layer spacing of MMT wasconfirmed by X-ray wide angle diffraction (WAXD), demonstrating that MMT were intercalated by the catalyst components.X-ray photoelectron spectrometry (XPS) analysis proved that TiCl_4 was mainly supported on MgCl_2 instead of on the surfaceof MMT The exfoliated structure of MMT layers in the PP matrix of PP/MMT composites was demonstrated by WAXDpatterns and transmission electron microscopy (TEM) observation. The higher glass transition temperature and higher storage modulus of the PP/MMT composites in comparison with pure PP were revealed by dynamic mechanical analysis (DMA).     

Ethylene–styrene thermoplastic copolymers prepared with supported Ziegler–Natta catalysts

The magnesium chloride supported Ziegler–Natta catalysts are able to copolymerize ethylene and styrene in conditions of high activity. Different parameters, including catalyst type, monomer ratio, temperature and Lewis bases, allow variation of the activity and reactivity ratio. The incorporation of styrene in the copolymer remains always rather limited in moles. The products obtained contain less than 20% styrene in weight, and seem very similar in structure to linear low-density polyethylenes (LLDPE) obtained with the same catalyst: the melting temperature is only about 5°C lower than that of pure polyethylene. The polymer can be fractionated by solvents in a similar manner to LLDPE, and contains a styrene-enriched fraction, but homopolystyrene production has never been observed.     

聚烯烃接枝改性设备的开发

介绍了近年来聚烯烃接枝工艺及其设备的开发情况。分别介绍了熔融接枝、溶液接枝、固相接枝、紫外光辐射接枝、等离子体接枝、超临界二氧化碳接枝的工艺及设备的开发情况。     

国外聚烯烃树脂工艺进展及新产品开发

从生产技术和新品种开发方面介绍了国外烯烃树脂最新进展情况，指出茂金属催化剂技术，Ｃａｔａｌｌｏｙ技术，Ｓｐｈｅｒｉｌｅｎｅ技术是人们开发研究的重点，特别是茂金属催化剂技术能按照用户的要求“定制”不同结构的聚合物，茂金属催化剂技术为开发更多的高性能聚烯树脂提供了可能。     

国外聚乙烯催化工艺研究进展

聚乙烯(PE)以其性优、价廉的优势,成为通用合成树脂中产量最大的品种,主要包括低密度聚乙烯(LDPE)、线性低密度聚乙烯(LLDPE)、高密度聚乙烯(HDPE)、中密度聚乙烯(MDPE)、以及一些具有特殊性能的专用料树脂。催化剂是聚烯烃工业的核心,通过调控活性中心和改善聚合工艺,提高了催化剂活性,完善了所得聚烯烃的性能,推动了聚乙烯工业的蓬勃发展。研发特殊性能或优异性能聚烯烃树脂的催化剂,是目前聚烯烃领域关注的焦点。本文对近年来国外聚乙烯催化剂的研究进展进行了综述,重点阐述了目前研究开发中的催化工艺,涵盖了Ziegler-Natta催化剂、铬催化剂、茂金属催化剂、过渡金属催化剂以及制备双峰或宽峰分布聚烯烃的复合催化剂等;对各类新型催化剂的制备方法和工艺特点进行了总结,同时指明了相关工艺的研发公司,以便国内相关研究部门借鉴。