Propylene polymerization in a semibatch slurry reactor over supported TiCl4/MgCl2/ethyl benzoate/triethyl aluminum catalyst. I. Catalytic behavior

High activity TiCl₄/MgCl₂/ethyl benzoate (EB)/triethyl aluminum (TEA) catalysts for the polymerization of propylene were synthesized and characterized for particle size distribution and crystallinity. Polymerization was carried out in a semibatch, constant pressure slurry reactor. A correction for interfacial mass transfer was found to be necessary to relate the monomer feed rate to the instantaneous rate of polymerization. Without such a correction serious misinterpretation of rate data could result. Optimum productivity was observed with respect to the Al/Ti ratio. Similar behavior was observed with polymerization temperature. Isotacticity increased with polymerization tamperature and decreased with Al/Ti ratio. The addition of a small amount of 2,2,6,6-tetramethylpiperidine increased the percentage of isotactic polypropylene to 98% without significantly affecting productivity.     

Ethylene and Propylene Polymerization Using In Situ Supported Me2Si(Ind)2ZrCl2 Catalyst: Experimental and Theoretical Study

Summary: Me₂Si(Ind)₂ZrCl₂ was in situ immobilized onto SMAO and used for ethylene and propylene polymerization in the presence of TEA or TIBA as cocatalyst. The catalytic system Me₂Si(Ind)₂ZrCl₂/SMAO exhibited different behavior depending on the amount and nature of the alkylaluminum employed and on the monomer type. The catalyst activity was nearly 0.4 kg polymer · g cat^?1 · h^?1 with both cocatalysts for propylene polymerization. Similar activities were observed for ethylene polymerization in the presence of TIBA. When ethylene was polymerized using TEA at an Al/Zr molar ratio of 250, the activity was 10 times higher. Polyethylenes made by in situ supported or homogeneous catalyst systems had practically the same melting point (T_m). On the other hand, poly(propylenes) made using in situ supported catalyst systems had a slightly lower T_m than poly(propylenes) made using homogeneous catalyst systems. The nature and amount of the alkylaluminum also influenced the molar mass. The poly(propylene) molar mass was higher when TIBA was the cocatalyst. The opposite behavior was observed for the polyethylenes. Concerning the alkylaluminum concentration, the molar mass of the polymers decreased as the amount of TEA increased. In the presence of TIBA, the polyethylene's molar mass was almost the same, independent of the alkylaluminum concentration, and the poly(propylene) molar mass increased with increasing amounts of cocatalyst. The deconvolution of the GPC curves showed 2 peaks for the homogeneous system and 3 peaks for the heterogeneous in situ supported system. The only exception was observed when TEA was used at an Al/Zr molar ratio of 500, where the best fit was obtained with 2 peaks. Based on the GPC deconvolution results and on the theoretical modeling, a proposal for the active site structure was made.

Molar mass distribution deconvolution of polyethylene prepared with the system Me₂Si(Ind)₂ZrCl₂/SMAO/TIBA with 500 mol/mol of alkylaluminum as cocatalyst.     

Cocatalyst‐originated aluminum residues in fibrous,very high molar mass polyethylene

In this work, fibrous very high molar mass polyethylene was prepared by Cp₂TiCl₂, which was supported on methylaluminoxane (MAO) pretreated mesoporous silica fiber. After the polymerization, an “ordinary” washing procedure was not sufficient to remove the aluminum residues of the cocatalyst MAO from the polymerization product. When hydrochloric acid was used in the termination of the polymerization, the aluminum existed as [Al(H₂O)₆]Cl₃, the presence of which causes additional signals to DSC and XRD grams of the polyethylene. These signals have previously been interpreted to be attributed to the extended chain crystal structure of the polyethylene. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1812–1815, 2004     

Polymerization of lactides and lactones. III. Ring-opening polymerization of DL-lactide by the (η3-C3H5)2Sm(μ2-Cl)2(μ3-Cl)2Mg(tmed)(μ2-Cl)Mg(tmed) complex

Ring-opening polymerization of DL -lactide (LA) has been initiated with the (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(η₂-Cl)Mg(tmed) complex both in bulk and solution. The effects of reaction conditions, such as reaction time, reaction temperature, and monomer/initiator molar ratio on the polymerization has been discussed. The results showed that (η³-C₃H₅)₂Sm(μ₂-Cl)₂(μ₃-Cl)₂Mg(tmed)(μ₂-Cl)Mg(tmed) was more effective for the polymerization of LA, and high molecular weight of polylactide was obtained by this initiator. The solvent affected the polymerization significantly. The polymerization mechanism was in agreement with the coordination mechanism. The polymer was characterized by FTIR, ¹H-NMR, and DSC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2857–2862, 1999     

Propylene metathesis over Re2O7/Al2O3-B2O3 catalysts

A series of alumina aluminum borate (AAB) with various Al/B molar ratios were prepared by the coprecipitation method. The supported rhenium oxide catalysts with various contents of Re₂O₇ were also prepared by the impregnation method with perrhenic acid. The catalytic activity and stability of Re₂O₇/AAB catalysts for the reaction of propylene metathesis were tested in a fixed-bed microreactor. It was found that Re₂O₇/AAB is more active, stable and regenerable than Re₂O₇/Al₂O₃ for propylene metathesis. The optimum Al/B molar ratio was found to be in the range of 4–10.     

Novel bis(acetylacetonate)palladium/boron trifluoride etherate catalyst system for the polymerization of norbornene

The boron trifluoride etherate, BF₃OEt₂, was used as an activator towards bis(acetylacetonate)palladium precursor in the polymerization of norbornene. The catalyst system Pd(Acac)₂/BF₃OEt₂ was highly active in the polymerization of norbornene. Catalytic activity up to 20,220 kg/(mol Pd · h) and intrinsic viscosities up to 2.64 dL/g were observed, respectively. Catalytic activity, polymer yield and polymer molecular weight could be controlled by varying the reaction parameters. The molar mass distribution indicates a single-site, highly homogeneous character of the active catalyst species. NMR spectroscopy study of the polymer showed exclusively 2,7-enchained repeating units of polymer backbone.     

Effects of aluminum alkyls on ethylene/1‐hexene polymerization with supported metallocene/MAO catalysts in the gas phase

The effects of aluminum alkyls on the gas‐phase ethylene homopolymerization and ethylene/1‐hexene copolymerization over polymer‐supported metallocene/methylaluminoxane [(n‐BuCp)₂ZrCl₂/MAO] catalysts were investigated. Results with triisobutyl aluminum (TIBA), triethyl aluminum (TEA), and tri‐n‐octyl aluminum (TNOA) showed that both the type and the amount of aluminum alkyl influenced the polymerization activity profiles and to a lesser extent the polymer molar masses. The response to aluminum alkyls depended on the morphology and the Al : Zr ratio of the catalyst. Addition of TIBA and TEA to supported catalysts with Al : Zr >200 reduced the initial activity but at times resulted in higher average activities due to broadening of the kinetic profiles, i.e., alkyls can be used to control the shape of the activity profiles. A catalyst with Al : Zr = 110 exhibited relatively low activity when the amount of TIBA added was <0.4 mmol, but the activity increased fivefold by increasing the TIBA amount to 0.6 mmol. The effectiveness of the aluminum alkyls in inhibiting the initial polymerization activity is in the following order: TEA > TIBA >> TNOA. A 2‐L semibatch reactor, typically run at 80°C and 1.4 MPa ethylene pressure for 1 to 5 h was used for the gas‐phase polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3549–3560, 2004     

Simultaneous absorption of carbon dioxide,sulfur dioxide and nitrogen dioxide into aqueous 2-amino-2-methy-1-propanol

The absorption mechanism of three acidic gases in alkali solution, such as the system of carbon dioxide, sulfur dioxide, and nitrogen dioxide in 2-amino-2-methyl-1-propanol (AMP), was used to predict the simultaneous absorption rates using the film theory. Diffusivity, Henry constant and mass transfer coefficient of each gas were used to obtain the theoretical enhancement factor of each component. The theoretical molar fluxe of each gas was obtained by an approximate solution of mass balances with reaction regions of the first order reaction of CO₂ and instantaneous reactions of SO₂ and NO₂ in CO₂-SO₂-NO₂-AMP system. From the comparison between the theoretical total fluxes of these gases and the measured ones, the solubility and the reaction rate between each gas and AMP influenced its molar flux.     

Modelling of polymerization kinetics and molar mass development in the nitroxide-mediated polymerization (NMP) of styrene in supercritical carbon dioxide using the PC-SAFT equation of state

A mathematical model for polymerization kinetics and molar mass development in the nitroxide-mediated polymerization (NMP) of vinyl monomers in supercritical carbon dioxide (scCO₂) has been developed. The method of moments is used for molar mass development. The perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state is used to estimate the number of stable phases present at equilibrium in the reaction mixture, critical number average chain length at which polymer particles are formed, and monomer concentration in each phase. Pure and binary PC-SAFT interaction parameters are estimated from liquid–liquid equilibrium (LLE) and liquid–vapour equilibrium (LVE) experimental data at 60 to 129°C. The effect of pressure on monomer conversion and molar mass development in the polymerization of styrene (Sty) using benzoyl peroxide (BPO) and 2,2,6,6-Tetramethylpiperidinyl-1-oxyl (TEMPO) at 120°C and 300–500 bar is studied. It was observed that increasing pressure increases polymerization rate without significantly affecting molar mass development.     

Propylene polymerization with Mg(OEt)2/benzoyl chloride/TiCl4–triethyl aluminum/external donor catalyst systems

Mg(OEt)₂/benzoyl chloride (BC)/TiCl₄ catalyst has been prepared by the chemical reaction method, and the chemical composition and X-ray structure of the catalyst were studied. The effect of various conditions on catalyst activity and isospecificity were also examined. With ¹³C-NMR analysis, it was found that aluminum carbinolate is formed during polymerization by reaction of triethyl aluminum cocatalyst with BC remaining in the prepared catalyst. The formed aluminum carbinolate acts as an additional donor to increase the isotactic index of polypropylene (PP). The morphology of the prepared catalyst and PP was also observed. © 1993 John Wiley & Sons, Inc.     

Mass changes accompanying the pseudocapacitance of hydrous RuO2 under different experimental conditions

Pseudocapacitance reaction of hydrous ruthenium oxide was investigated by cyclic voltammetry combined with electrochemical quartz-crystal nanobalance (EQCN) in sulfuric acid as well as in neutral solutions of Na₂SO₄ and K₂SO₄. The ruthenium oxide electrode was prepared by attaching the ruthenium oxide particles on gold covered quartz electrode. The results show that there are different types of charge taking place simultaneously during the redox reaction of ruthenium oxide electrode. Their contribution to the overall charge depends on the experimental conditions. Depending on the potential and electrolyte used the redox reaction of ruthenium oxide is accompanied either by mass loss or by mass gain. The average molar masses of the species exchanged between the solid phase and the electrolyte solution depend on the potential and scan rate. The effect of Nafion™ top layer was also investigated. It has been found that it does not affect significantly the overall specific capacitance of ruthenium oxide electrode but the apparent molar masses of exchanged species decrease in comparison with the uncovered electrodes.     

Synthesis of (C5H5)2Zr(O2C)CH3 and (C5H5)2Zr(O2C)CH2CH3 for olefin polymerization

Summary (C₅H₅)₂Zr(O₂C)CH₃ and (C₅H₅)₂Zr(O₂C)CH₂CH₃ complexes were synthesized, characterized and activated with MAO for ethylene polymerization. The highest catalytic activity was achieved at Al/Zr molar ratio of 3000 for both systems. The effects of the size of the R group in the carboxylate ligands, the Al/Zr molar ratio and reaction temperature on the catalytic activity and polymer properties were studied and discussed.     

Titanium-magnesium catalysts for propylene polymerization: The effect of donors

The chain transfer reaction with hydrogen at propylene polymerization over Ti-Mg catalysts (TMCs) of composition TiCl₄/D₁/MgCl₂-AlEt₃/D₂ is studied in a wide hydrogen concentration range. A two-step mechanism of this reaction is suggested. This mechanism accounts for the fractional order of the reaction with respect to hydrogen concentration. Constants of chain transfer reaction with hydrogen are determined for TMC with different donors: 1,3-diether or dibutyl phthalate as D₁ and tetraethoxysilane or dicyclopentyldimethoxysilane as D₂. In propylene polymerization over the TMCs, the length of the polymer chain is mainly determined by the ratio of the propylene and hydrogen concentrations because the propagation and chain transfer rate constants are comparable. The rate constant of chain transfer with hydrogen at ethylene polymerization is significantly (more than one order of magnitude) less, and higher hydrogen concentrations are required for attaining the same degree of polymerization. The results of this study might be helpful in simulation of industrial polymerization processes and in control of the polymer molar mass.     

Polymerization of butadiene with Co(acac)3–(i-Bu)3Al–H2O catalyst

The polymerization of butadiene in toluene using Co(acac)₃–(i-Bu)₃Al–H₂O catalyst system was studied. Presented are the effects of the addition order, aging time, and composition of catalysts on rates, polymer microstructure, and molecular weights. The polymerization was found to be initiated by the Co(acac)₃-hydrolized aluminum alkyl complex. The chain propagation proceeds according to a first-order reaction with respect to monomer and active species and is a strong function of Al/H₂O with an optimum ratio of 1.0, but independent of Al/Co. The nature of polymerization seems to change as Al/H₂O increases from less than 1 to greater than 1. Transfer reaction is significant. From the kinetic data it was found that the termination reaction is most likely to be by combination.     

H2O2+Fe2+体系引发制备聚丙烯酰胺

实验采用水溶液聚合法,利用H2O2+Fe2+氧化还原引发体系引发聚合丙烯酰胺(AM),合成了非离子型絮凝剂聚丙烯酰胺(PAM)。利用正交实验确定最佳工艺条件为:AM质量分数20%,引发剂与单体(AM)物质的量比为0.0001,引发体系中氧化剂与还原剂物质的量比5:1,反应时间为8h,得到相对分子质量超过6.5×106的PAM。通过改变充入氮气方法、加入引发剂方法、改变还原剂物质的量比等工艺对实验进行了初步放大,得到了相对分子质量超过7.0×106的PAM,实验结果可重现。该聚合反应为一级反应,在20℃下聚合反应速率方程为ln[M]t=-0.0307t+0.3447。     

Comparative study of homogeneous and heterogeneous styrene polymerizations with Ni(acac)2/MAO catalytic system

Styrene polymerization was carried out with Ni(acac)₂/MAO and Ni(acac)₂/SiO₂/MAO. The influence of reaction parameters (Al/Ni mole ratio, catalyst concentration, temperature and time polymerization) on styrene polymerization was evaluated. It was observed that both catalytic systems were affected by reaction parameters and that the heterogeneous catalyst presented higher activity than the homogeneous one. Polystyrenes with different molecular weight, stereoregularity and polydispersity were obtained. These results suggest that different active catalyst species could have been present. In addition, two types of methylaluminoxane (MAO) with different molecular weights were also evaluated as cocatalyst. As a result, the catalyst activity and stereospecificity were strongly affected by the MAO type.     

Polymerization of 1,3‐butadiene with VO(P204)2 activated by methylaluminoxane,purified methylaluminoxane,and trimethylaluminum

The effect of different aluminum‐based cocatalysts (MAO, pMAO, and TMA) on butadiene (Bd) polymerization catalyzed by VO(P204)2 was investigated. The bimodal dependence of the polymer yield on the [MAO]/[V] molar ratio was revealed, and an highest polymer yield was achieved at a rather low [MAO]/[V] molar ratio ([MAO]/[V] = 13). The microstructures of the resulting poly(Bd)s were also significantly influenced by the ratio. In the TMA or pMAO system, the polymer yields were also very sensitive to the [Al]/[V] molar ratio. However, the microstructures of the resulting poly(Bd)s were almost independent of the ratio. In relation to the microstructures of poly(Bd)s obtained by the MAO and TMA systems at various temperatures, the 1,2‐unit contents were found to be the most abundant microstructure for both systems. In the pMAO system, the trans‐1,4‐units were the most abundant. The results of the additions of Lewis bases (THF and TPP) into Bd polyerization system comfirmed the existing of the two types of the reactions of VO(P₂₀₄)₂‐MAO catalyst and had the polymerization process controlled to some extent. The different thermal behaviors of these catalytic systems also show that multiple types of active centers were formed during the reaction between VO(P₂₀₄)₂ and MAO. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Indirect Synthesis of Bis(2‐PhInd)ZrCl2 Metallocene Catalyst,Kinetic Study and Modeling of Ethylene Polymerization

Bis(2‐phenylindenyl)zirconium dichloride (bis(2‐PhInd)ZrCl₂) catalyst was synthesized via the preparation of bis(2‐phenylindenyl)zirconium dimethyl (bis(2‐PhInd)ZrMe₂) followed by chlorination to obtain the catalyst. Performance of the catalyst for ethylene polymerization and its kinetic behavior were investigated. Activity of the catalyst increased as the [Al]:[Zr] molar ratio increased to 2333:1, followed by reduction at higher ratios. The maximum activity of the catalyst was obtained at a polymerization temperature of 60 °C. The rate‐time profile of the reaction was of a decay type under all conditions. A general kinetic scheme was modified by considering a reversible reaction of latent site formation, and used to predict dynamic polymerization rate and viscosity average molecular weight of the resulting polymer. Kinetic constants were estimated by the Nelder‐Mead numerical optimization algorithm. It was shown that any deviation from the general kinetic behavior can be captured by the addition of the reversible reaction of latent site formation. Simulation results were in satisfactory agreement with experimental data.     

Polymerization of styrene with diphenylzinc-cocatalyst systems

Summary The diphenylzinc-H₂O and diphenylzinc-H₂O-Bu^tCl systems were used as catalysts for styrene polymerization in solution at various temperatures and solvents. The systems are greatly influenced by the molar ratio H₂O/Ph₂Zn, and the maximum catalyst activity, in both cases, was found at a molar ratio of 0.75. GPC results strongly suggest the presence of more than one active species. For Ph₂Zn-H₂O-Bu^tCl system, in dichloromethane at-78°C with the molar ratio of H₂O/Ph₂Zn=0.75, the reaction is first order with respect to monomer with k_p=2.45×10^-3 Lmol^-1sec^-1.     

Stereospecific polymerization of styrene with novel half‐sandwich titanium complexes—RCpTi(o‐MeOPhCPh2O)Cl2/methylaluminoxane

Two new half‐sandwich titanocene catalysts for the stereospecific polymerization of styrene, RCpTi(o‐MeOPhCPh₂O)Cl₂ (R = H (1); R = Me (2)), were prepared by reaction of the corresponding RCpTiCl₃ complexes with o‐methoxyphenyldiphenylmethanol (o‐MeOPhCPh₂OH) in the presence of triethylamine. Upon activation with excess methylaluminoxane (MAO), they showed high activities and high thermal stabilities for the stereospecific polymerization of styrene. The influences of polymerization temperature, Al/Ti molar ratio, solvent (aliphatic or aromatic) and time on the activity and syndiotacticity of the styrene polymerization were investigated. Copyright © 2006 Society of Chemical Industry