Ethylene polymerization studies with supported cyclopentadienyl,arene, and allyl chromium catalysts

Highly active catalysts for low pressure ethylene polymerization are formed when chromocene, bis (benzene)- or bis (cumene)-chromium or tris- or bis (allyl)-chromium compounds are deposited on high surface area silica-alumina or silica supports. Each catalyst type shows its own unique behavior in preparation, polymerization, activity, isomerization, and response to hydrogen as a chain transfer agent. The arene chromium compounds require an acidic support (silicaalumina) or thermal aging with silica to form a highly active catalyst. At 90°C polymerization temperature arene chromium catalysts produced high molecular weight polyethylene and showed, in contrast to supported chromocene catalysts, a much lower response to hydrogen as a chain transfer agent. An increase in polymerization temperature caused a significant decrease in polymer molecular weight. Addition of cyclopentadiene to supported bis (cumene)-chromium catalyst led to a new catalyst which showed a chain transfer response to hydrogen typical of a supported chromocene catalyst. Polymerization activity with tris- or bis (allyl)-chromium appears to depend on the divalent chromium content in the catalyst. Changes in the silica dehydration temperature of supported allyl chromium catalyst have a significant effect on the resulting polymer molecular weight. High molecular weight polymers were formed with catalysts that were prepared using silica dehydration temperatures below about 400°C. Dimers, trimers, and oligomers of ethylene were usually formed with catalysts that were prepared on silica dehydrated much above 400°C. The order of activity of the different types of catalysts was chromocene/silica > chromocene/silica-alumina > bis (arene)-chromium/silica-alumina ? allyl chromium/silica.     

New Chromium on Silica Gel Catalysts with very high activity for the polymerization of ethylene

Together with the known chromium (II)/silica gel catalyst (Phillips catalyst) for the polymerization of ethylene, two new ones have been investigated. It was found that a chromium(II)-“repoly” catalyst (prepared by short reaction of the chromium(II)/silica gel with ethylene at temperatures between 100 and 225°C) and a chromium(III)/silica gel catalyst have up to hundred times higher activity than the chromium(II) one. Activation energies were calculated as 54.6, 49.6 and 43.8 kJ per mol, respectively. The number of active sites was determined by measuring the integrated absorbance of the C? H and C?O stretching vibrations of the polymer. At low chromium concentration (0.056%) roughly 50% of all chromium was catalytically active in the case of chromium(II) and chromium(III) on silica gel. For the chromium(II)-“repoly” catalyst all chromium atoms can be active. The turnover numbers for the polymerization at 20°C were calculated as 0.1 (chromium(II)), 7.5 (chromium(II)-“repoly”) and 20 (sec^?1 atm^?1) (chromium(III)).     

Supported bis(indenyl)– and bis(fluorenyl)–chromium catalysts for ethylene polymerization

Silica-supported bis(indenyl)– and bis(fluorenyl)–chromium catalysts show good activity in ethylene polymerization. For maximum productivity with the indenyl chromium catalyst, the silica must be dried, with higher dehydration temperatures giving a significant increase in polymerization activity. Less deactivation on thermal aging of the supported bis(indenyl)–chromium catalyst allows ethylene polymerization to proceed for many hours, which provides polyethylenes of low residual chromium content. In contrast to the behavior of supported chromocene catalysts, the indenyl–and fluorenyl–chromium catalysts require a higher hydrogen/ethylene ratio to achieve a specific polymer melt index. Nevertheless, highly saturated polyethylenes are produced with these new catalysts. This result indicates that chain transfer to hydrogen remains the major chain transfer reaction. Addition of cyclopentadiene to a supported indenyl–chromium catalyst provided a catalyst with a much higher transfer response to hydrogen. This result suggests that ligand exchange occurred, producing a supported chromocene catalyst. These overall results are consistent with an active-site model which comprises a supported divalent chromium center attached to an indenyl or fluorenyl ligand during the polymerization process. Polymerization is believed to occur by a coordinated anionic mechanism of the type previously discussed for a supported chromocene catalyst.     

Chromocene-based catalysts for ethylene polymerization: Thermal removal of the cyclopentadienyl ligand

Thermal aging of a chromocene catalyst, (C₅H₅)₂Cr/SiO₂, in an inert atmosphere leads to a modified catalyst which shows poor response to hydrogen as a transfer agent. Polyethylenes prepared at a polymerization temperature of 90°C with this modified catalyst have a low melt index and high vinyl unsaturation level. By thermogravimetry the weight loss of the catalyst, relative to dehydrated silica, was equivalent to loss of one cyclopentadienyl ligand per chromium site. Pyrolytic gas chromatography showed cyclopentadiene was liberated in the thermal process. These overall studies provide strong evidence that loss of a cyclopentadienyl ligand in supported chromium catalysts has a profound effect on overall polymerization behavior.     

Comparison of silyl chromate and chromium oxide based olefin polymerization catalysts

A comparison of the ethylene polymerization performance conducted with an oxo and a triphenylsilyl chromate catalyst on silica was performed. The oxo catalyst has higher activity and better comonomer response. The silylchromate catalyst has a much longer induction time and made a much broader molecular weight distribution polymer compared to the oxo analogue. Performance similar to silylchromate on silica was observed when triphenylsilanol (TPS) was added to the oxo chromium catalyst. The oxo catalyst was converted to the silyl chromate catalyst by ligand substitution. Analysis of the catalyst components when TPS was added to the oxo chrome analogue showed that bis triphenylsilyl chromate can form and be removed from the support.     

二(叔丁基环戊二烯基)钕甲基配合物催化ε-己内酯开环聚合

二（叔丁基环戊二烯基）钕甲基配合物催化ε 己内酯开环聚合罗云杰姚英明沈琪（苏州大学化学化工学院苏州２１５００６）关键词开环聚合，ε 己内酯，茂基稀土甲基配合物聚ε 己内酯（Ｐｏｌｙｃａｐｒｏｌａｃｔｏｎｅ，ＰＣＬ）是一种生物降解材料，有良好的相...     

烯烃配位聚合催化剂的研究进展

较全面地综述了配位聚合催化剂和聚合机理的研究进展:高效Ziegler-Natta催化剂催化丙烯、乙烯等烯烃高效聚合,可合成多种高性能聚烯烃,等规聚丙烯的等规度大于98.5%,不同结构和性能的聚乙烯包括线性低密度聚乙烯(LLDPE)、超低密度聚乙烯(VLDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)、双/宽峰分布聚乙烯、超高分子量聚乙烯(UHMWPE)和超低密度双/宽峰分布聚乙烯等;茂金属催化剂催化苯乙烯、乙烯、丙烯、1-丁烯等烯烃的均聚合和共聚合,并概括了其聚合机理;非茂金属催化剂合成多组分、多立体结构嵌段的聚烯烃,极性聚烯烃及超支化聚烯烃等,介绍了链行走和链穿梭机理。展望了配位聚合的发展趋势,认为聚合过程的环境友好、产品使用过程的环境友好、聚烯烃的高性能化和功能化是从事配位聚合工作的全体人员努力的方向。     

On the polymerization mechanism of the Chromium(III) and Chromium(II)-B Silica Gel Catalysts

FTIR spectra of the chromium(III)/silica gel catalyst after short polymerization with ethylene show weak bands at 2 685 and 1 447 cm^?1 from the stretching and the deformation vibration of the methylene group, which binds the growing polymer to the active chromium(III) site. The band at 2 685 cm^?1 is reversibly removed by CO adsorption at low temperatures (?145°C). This adsorbed CO shows a broad band at 2 184 cm^?1. From the intensity of CO IR bands on unchanged chromium(III) before and after polymerization it was calculated that 12% of the chromium(III) is catalytically active, which is in good agreement with previous measurements by an entirely different determination method (11%). The chromium(II)-B catalyst showed also a weak band at 2 685 cm^?1 and it is therefore concluded that in this case the chromium(II) is oxidised by the ligating surface silanol group (in cooperation with an ethylene molecule). The band at 2 685 cm^?1 is discussed in relation to that from normal methylene groups at 2 925 and 2 855 cm^?1 and to that from the chromium(II)-A catalyst at 2 750 cm^?1. Evidence for the existence of a mononuclear chromium(II)-A species is found. This one is, in contrast to the dinuclear chromium(II)-A species, not polymerization active.     

Pyrolysis of polyisoprenes. I. Differentiation between natural and synthetic cis-1,4-polyisoprenes

Two methods of differentiating between natural rubber and synthetic cis-1,4-polyisoprenes have been examined. Both techniques depend on the presence of Ziegler-Natta catalyst residues in the synthetic polymers. The major pyrolysis product of cis-1,4-polyisoprenes at 350°C is 1-methyl-4-(1-methylethenyl)cyclohexene. This can undergo disproportionation to yield 1-methyl-4-(1-methylethyl)benzene and methyl-(1-methylethyl)cyclohexenes. It is this disproportionation reaction, catalyzed by Ziegler-Natta catalyst residues or by carbon black, that is responsible for the different product ratios obtained on pyrolysis of natural rubber and Ziegler-Natta catalyzed cis-1,4-polyisoprenes. Lithium alkyl-polymerized polyisoprenes undergo this secondary disproportionation reaction only in the presence of carbon black. Derivative thermogravimetric traces of black-filled sulfur vulcanizates of natural rubber and synthetic polyisoprenes are significantly different because polymerization catalyst residues promote cyclization of the polymer.     

Chromocene catalysts for ethylene polymerization: Scope of the polymerization

Chromocene deposited on silica supports of high surface area forms a highly active catalyst for polymerization of ethylene. Polymerization is believed to occur by a coordinated anionic mechanism previously outlined. The catalyst formation step liberates cyclopentadiene and leads to a new divalent chromium species containing a cyclopentadienyl ligand. The catalyst has a very high chain-transfer response to hydrogen which permits facile preparation of a full range of molecular weights. Catalyst activity increases with an increase in silica dehydration temperature, chromium content on silica, and ethylene reaction pressure. The temperature-activity profile is characterized by a maximum near 60°C, presumably caused by a deactivation mechanism involving silica hydroxyl groups. A value of 72 was estimated for the ethylene–propylene reactivity ratio (r₁). Linear, highly saturated polymers are normally prepared below 100°C. By contrast with other commercial polyethylenes, the chromocene catalyst produces polyethylenes of relatively narrow molecular weight distribution. Above 100°C, unsaturated, branched polymers or oligomers are formed by a simultaneous polymerization–isomerization process.     

单茂金属烯烃聚合催化剂*

本文综述了近年来带有给电子配体的单茂金属化合物应用于烯烃聚合的研究。带有给电子配体的单茂金属化合物是目前烯烃配位聚合催化剂的研究热点之一。作为新型的聚合催化剂,这类催化剂具有合成简单、结构清晰的特点,用于催化烯烃聚合,可得到高聚合活性,同时聚合物可得到高的分子量。用于共聚时,具有很好的共聚能力。通过共聚,可以得到Zieler-Natta催化剂和传统茂金属催化剂不能得到的新共聚物。通过调整催化剂上茂配体和给电子配体的结构,可以方便地调节聚合行为,从而调整聚合物的结构。文中涉及了乙烯、alpha-烯烃的均聚与共聚,乙烯与环烯烃共聚合,苯乙烯聚合等方面的研究。     

Synthesis and characterization of polyethylene/clay–silica nanocomposites: A montmorillonite/silica‐hybrid‐supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT‐Si) supported catalyst, was developed. MT‐Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT‐Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay–silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 941–949, 2004     

Chemiluminescence study on the oxidation of several polyolefins—I. Thermal-induced degradation of additive-free polyolefins

Chemiluminescence (CL) has been applied to evaluate the oxidation susceptibility of various polyolefins: low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and isotactic polypropylene (i-PP). The intensity of CL emission in inert atmosphere could be related to the previous oxidation level. The thermal stability at 170 °C of the hydroperoxides in LDPE seems to be lower than that in LLDPE or HDPE. The kinetic parameters of the oxidation at 170 °C in oxygen, calculated from CL data, suggest the following stability order: HDPE > LLDPE > LDPEi-PP. The intensity of CL emission was related to the CH₃ content as evaluated by Fourier transform infra-red spectroscopy.     

High Melting Point of Linear,Spiral Polyethylene Nanofibers and Polyethylene Microspheres Obtained Through Confined Polymerization by a PPM-Supported Ziegler-Natta Catalyst

In this work, different types of polyethylene (linear, spiral nanofibers and microspheres) were obtained via confined polymerization by a PPM-supported Ziegler-Natta catalyst. Firstly, the Ziegler-Natta catalyst was chemical bonded inside the porous polymer microspheres (PPMs) supports with different pore diameter and supports size through chemical reaction. Then slightly and highly confined polymerization occurred in the PPM-supported Ziegler-Natta catalysts. SEM results illustrated that the slightly confined polymerization was easy to obtain linear and spiral nanofibers, and the nanofibers were observed in polyethylene catalyzed by PPMs-1#/cat and PPMs-2#/cat with low pore diameter (about 23 nm). Furthermore, the highly confined polymerization produced polyethylene microspheres, which obtained through other PPM-supported Ziegler-Natta catalysts with high pore diameter. In addition, high second melting point (T_m2: up to 143.3 °C) is a unique property of the polyethylene obtained by the PPM-supported Ziegler-Natta catalyst after removing the residue through physical treatment. The high T_m2 was ascribed to low surface free energy (σ_e), which was owing to the entanglement of polyethylene polymerized in the PPMs supports with interconnected multi-modal pore structure.     

Morphology Evolution in the Early Stages of Olefin Polymerization

The olefin polymerizations were carried out by using silica supported metallocene/MAO catalysts and MgCl₂ supported Ziegler-Natta catalysts under mild reaction conditions and stopped at very low yield. The surface and cross sectional morphology of the polymer particles were characterized by using scanning electron microscopy (SEM). A homogeneous distribution of (co)catalyst on the support material is a prerequisite condition to get a homogeneous fragmentation and uniform polymer particle morphology. In the present work the catalysts show two different fragmentation behaviors. They can gradually fragment from the outer to the inner surface of the catalyst particle, or instantaneously break up into a large amount of small sub-particles at the beginning of the polymerization. The incorporation of comonomer does not change the general catalyst fragmentation scheme but delays the catalysts break-up progress.     

A chemical study of thermally activated chromic titanate on silica ethylene polymerization catalysts

Thermally activated ethylene polymerization catalysts which contain chromium and titanium on silica differ from those catalysts which contain only chromium on silica. The characteristics of chromium-titanium catalysts vary with the method of incorporating the titanium and the thermal activation procedure. Titanated catalysts of the kind examined in this article have faster initiation and a higher polymerization rate per unit catalyst weight than corresponding catalysts without titanium. High-density polyethylene produced by this type of titanium-chromium catalyst tends to have a higher melt index and a broader molecular weight distribution than polyethylene made with chromium on silica catalysts. Iodometric titration showed that reduction from the initial hexavalent chromium to trivalent occurs when the dry, catalyst starting material is treated with titanium tetraisopropoxide. A study of the reaction between chromium trioxide and titanium tetraisopropoxide in carbon tetrachloride revealed that (1) it is not necessary to have a reaction between surface silanols and titanium tetraisopropoxide for the reduction to occur, and (2) the reaction product has an absorption near 660 nm in the visible range. Comparison of spectra showed that chromium trioxide on silica reduced by isopropyl alcohol has a shifted absorption, i.e., 600 nm. These findings are interpreted to mean that titanium atoms come sufficiently close to chromium atoms to change their electron density in the starting material and remain close neighbors in the activated catalysts. The interpretation is further supported by ESCA data and leads to the proposal that in this case the activated catalysts contain titanium chromate structures.     

双(三苯基甲硅烷)铬酸酯催化剂及其配制过程中表面化学反应的研究

本文采用红外光谱分析等方法,研究了双(三苯基甲硅烷)铬酸酯的加热、光照和水解反应的一些性质;探讨了双(三苯基甲硅烷)铬酸酯催化剂配制过程的化学变化。当其沉淀在硅胶上时,与硅胶表面羟基反应,生成表面有机铬化合物,铬的价态不变。加入烷基铝后,表面铬化合物还原生成含有Cr-C或Cr-O键的低价表面化合物,其对乙烯聚合具有催化活性。并指出了本催化剂活性组份可能的负载机理。     

Effect of stereoregularity on the thermo-oxidative degradation of poly(propylene)s estimated by chemiluminescence

The effect of stereoregularity on the thermo-oxidative degradation of poly(propylene)s, isotactic (IPP) and syndiotactic (SPP), was compared with that of high density polyethylene (HDPE) by means of chemiluminescence (CL). SPP is extremely stable to thermal oxidation and CL signals appeared much later than in IPP and even later than in HDPE. For example, at 160°C the maximum intensity of CL was measured after only 13 min for IPP, 60 min for HDPE and 260 min for SPP. IR spectroscopic results support the conclusions drawn from CL results.     

Performance of the Cr[CH(SiMe3)2]3/SiO2 catalyst for ethylene polymerization compared with the performance of the Phillips catalyst

The catalysis of a silica‐supported chromium system {Cr[CH(SiMe₃)₂]₃/SiO₂} was compared with a silica‐supported chromium oxide catalyst, the Phillips catalyst (CrO₃/SiO₂). This catalyst was prepared by the calcining of the typical silica support used for the Phillips catalyst at 600 °C and by the support of tris[bis(trimethylsilyl)methyl]chromium(III) {Cr[CH(SiMe₃)₂]₃} on the silica. In the slurry‐phase polymerization, this catalyst conducted the polymerization of ethylene at a high activity without organoaluminum compounds as cocatalysts or scavengers. The activity per Cr was about 6–7 times higher than that of the Phillips catalyst. Upon the introduction of hydrogen to the system, the molecular weight of polyethylene did not change with the Phillips catalyst, but it decreased with the Cr[CH(SiMe₃)₂]₃/SiO₂ catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 413–419, 2003     

The thermo-oxidative degradation of metallocene polyethylenes. Part 1: Long-term thermal oxidation in the solid state

The long-term thermo-oxidative degradation of different metallocene polyethylenes (mPEs) was investigated in the solid state (oven ageing in air at 90 °C). The mPEs differed essentially according to their initial melt index, molar mass distribution, density and ash content. Two Phillips-type HDPEs were also studied for comparison. The rate of oxidation was assessed by carbonyl index measurements. Initial vinyl unsaturation and short chain branch contents were correlated with induction times. The hydroperoxide concentrations of the aged materials and the levels of metal catalyst residues were also evaluated. Outstanding oxidative stability was exhibited for all the mPEs in the solid state relative to the Phillips HDPEs. This was believed to be due to the low concentration of both adventitious metal catalyst residues and initial vinyl unsaturation. Degree of short chain branching also appeared to influence the oxidative stability of the mPEs. Besides inherent properties, the density/crystallinity appeared to be the main factor influencing their oxidative stability. In the case of the Phillips HDPEs, the high level of vinyl unsaturation together with chromium catalyst residues may contribute to their poor oxidative stability.