Supported hybrid early and late transition metal catalysts for the synthesis of polyethylene with tailored molecular weight and chemical composition distributions

Supported hybrid catalysts using metallocenes and a nickel diimine catalyst were synthesized and used for ethylene slurry polymerization and ethylene/1-hexene copolymerization. Two types of metallocenes, together with a nickel diimine catalyst were supported onto SiO₂ through chemical bonding, and a borate compound was physisorbed for the activation of the catalysts. These supported hybrid catalysts had high catalyst activities and made free-flowing polymer particles. The chemical composition distribution, molecular weight averages and distributions of resultant polymers were controlled by catalyst structure and polymerization conditions such as reaction temperature and the use of α-olefin. According to GPC-IR, ¹³C NMR and CEF characterization results of some polymers, more 1-hexene was incorporated in the high molecular weight region, short chain branches were generated by the chain walking mechanism in low molecular weight region. The morphologies of the resulting particles were investigated by SEM.     

Confinement effects on the kinetics of formation of sequential semi-interpenetrating polymer networks

Summary Peculiarities of formation kinetics of sequential semi-interpenetrating polymer networks based on crosslinked polyurethane with different cross-linking density and linear polystyrene and polybutylmethacrylate have been studied. Polyurethane networks were synthesized differing in molecular mass M_c of the chains between cross-links. Monomeric styrene and butyl methacrylate were introduced into these networks by swelling them in monomers up to equilibrium. The kinetics of polymerization of monomers in swollen networks was investigated. The experimental data show the dependence of the kinetic parameters of polymerization on M_c, this dependence being different for various monomers. Sharp discrepancy in molecular mass distribution of polymers formed in various matrices has been observed. The differences in dependencies of reaction kinetics and molecular mass distribution are supposed to be connected to various dependence of the chain growth and termination of various monomers on the density of network, i.e. on the confinements imposed by the intranetwork space.     

铬钒双金属催化剂乙烯聚合反应动力学模型化

双金属催化剂可催化乙烯聚合在单个反应器内制备双峰聚乙烯。考察了新型Cr-iV双金属催化剂及相应的单金属S-2和iV催化剂在不同实验条件下的乙烯均聚反应动力学。通过对Cr-iV催化剂聚合产物分子量分布曲线的解析发现铬钒活性中心之间存在相互作用,铬中心活性受到抑制,钒中心活性得到增强;聚合温度基本不改变铬钒活性中心生成的聚合物的质量分数。采用简化的单中心乙烯均聚动力学模型分别描述铬钒双活性中心的动力学行为,结合双金属催化剂的聚合实验结果确定了各个活性中心的动力学参数。相比单金属催化剂,Cr-iV催化剂中铬活性中心链增长速率常数降低,说明其聚合活性降低;而钒活性中心链失活速率常数减小,稳定性增强,活性提高。     

Semibatch styrene suspension polymerization processes

Emulsion and suspension polymerization processes have widely been studied for more than 40 years. Although both polymerization processes are performed in heterogeneous media, each one presents its own typical characteristics, such as the particle size distribution, molecular weight distribution, polymer particle nucleation rate, and polymerization rate. In this study, semibatch styrene suspension polymerizations were carried out with feed compositions typical of emulsion processes. The initial reactor charge resembled the recipe of standard styrene suspension polymerizations, and the emulsion polymerization constituents were added during the batch. The influence of the moment at which the emulsion feed was started on the course of the polymerization and the effects of the feed on the polymer properties were analyzed. The polymer particle morphology and the average molecular weights changed very significantly with the emulsion feed time, and the changes could lead to the production of broad molecular weight distributions. Core–shell polymer particles could also be obtained, with the core being formed of polymer particles originating from the suspension polymerization process and the shell being formed of polymer particles originating from the emulsion polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3021–3038, 2003     

Monodisperse polymer beads as packing material for high-performance liquid chromatography

A novel approach to monodispersed porous polymer beads allowing accurate control over a broad range of pore size distribution has been developed. It involves the use of monodispersed template particles which are used as polymeric porogens in the suspension polymerization of monomers such as styrene and divinylbenzene. The size uniformity of the template particles is retained by the final porous beads. The porous properties of the final beads are determined in large part by the characteristics of the porogenic mixture such as its composition, the molecular weight of the polymeric porogen, as well as the relative amount of monomers, polymeric and low molecular weight porogens used.     

POLYMERIZATION KINETICS AND MODELING OF SLURRY ETHYLENE POLYMERIZATION PROCESS WITH METALLOCENE/MAO CATALYSTS

Polymerization methods of ethylene include the slurry, solution, and gas-phase processes. This study investigates polymerization conditions and kinetics under slurry process. Typical metallocene catalyst/cocatalyst Cp₂ZrCl₂/MAO system was used for ethylene polymerization. Two kinds of polymerization kinetics were compared in this study, multiple active-site model and transfer-effect model. The kinetic studies used metallocene-type polymerization kinetics, including catalyst activation, initiation, chain propagation, chain transfer, and termination steps. In addition, kinetic constants of polymerization reaction model were calculated. Calculation results of catalyst activity and molecular weight were compared with experimental results, indicating their good correlation. Moreover, the conventional polymerization was modified to accurately predict the molecular weight behaviors under various reaction conditions with the proposed transfer-effect model. Exactly, how reaction time, pressure, catalyst concentration, and cocatalyst ratio affect catalyst activity and molecular weight of the polymer were also discussed.     

Homo- and copolymerizations of ethylene and α-olefins in <Emphasis Type="Italic">n</Emphasis>-hexane catalyzed by Ni(ii)-α-diimine catalyst

Ni(II)-α-diimine catalyst [(2,6-i-Pr)₂C₆H₃-DAB(An)]NiBr₂ plus methylaluminoxane was successfully used in the homopolymerization of ethylene, 1-hexene, and 1-octene and the copolymerization of ethylene with 1-hexene and 1-octene in n-hexane. The polymerization of 1-octene was conducted in a controlled manner with a narrow molecular weight distribution (M _w/M _n = 1.2–1.5) and with the weight-average molecular weight increasing linearly with the monomer conversion. The molecular weights, T _g, T _m, branching degree, and density of the obtained (co)polymers were greatly controlled by ethylene pressure and polymerization temperature. Compared with that of ethylene homopolymer, the branching degree of the copolymers prepared by the copolymerization of ethylene with 1-hexene or 1-octene increased, whereas the molecular weight, density, T _m, and catalyst activity decreased. However, compared with those of the homopolymer of 1-hexene or 1-octene, the copolymer density, T _m, and catalyst activity increased, whereas the branching degree declined.     

Study of the morphology and kinetics of novel Ziegler–Natta catalysts for propylene polymerization

The morphological and kinetic characteristics of novel Ziegler–Natta catalysts were studied. Catalysts were prepared by Borealis Polymers Oy using a new synthesis technique (emulsion technology). Video microscopy was used to study the growth of single catalyst particles during polymerization in the gas and liquid phases. The distribution of single particle activity was very narrow in the catalyst without external support and was rather broad in the the silica‐supported catalyst. Video microscopy of molten polymer particles allowed observation of the process and degree of fragmentation of the catalyst particles. A correlation between the activation period during the initial stage of polymerization and catalyst fragmentation was found. Fragmentation was faster and more uniform with the catalyst without external support than with the silica‐supported catalyst. Scanning electron microscopy provided information on morphology evolution and shape replication of the catalyst particles. With the catalyst without external support, good shape replication was observed, and compact and spherical particles were formed. With the silica‐supported catalyst, shape replication was poor, and nonspherical porous polymer particle were formed. Modeling of the kinetics of propylene polymerization was done using a simple three‐step reaction scheme neglecting mass and heat transport effects. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2191–2200, 2005     

Modeling of molecular weight distribution of gas‐phase polymerization of butadiene

A mathematical model of the molecular weight distribution (MWD) based on a multilayer model and an improved intrinsic kinetics model was proposed to simulate the MWD of the gas‐phase polymerization of butadiene with a heterogeneous catalyst. Intrinsic kinetics and heat and mass‐transfer resistances based on the multilayer model of a polymeric particle were considered in the modeling of the MWD. The effects of the reaction conditions, catalyst particle size, mass‐transfer resistance, deactivation of active sites, and transfer of the polymer chain on the molecular weight and MWD were simulated. The results show that the effects of the deactivation of active sites and transfer of the polymer chain on the average molecular weight are significant and that the effect of the catalyst particle size on the MWD is not significant. The simulation results of the molecular weight and MWD are compared with the experimental results. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 88–103, 2003     

Zum Einfluß des Polymermolekulargewichts auf das Phasenverhalten von Gas-Polymer-Systemen unter Hochdruck

The phase behaviour of gas-polymer-systems, which is important in the polymerization of gaseous monomers and in the separation of the polymers formed, was studied at a constnat temperature of 130°C and at pressures of 100–2000 bar. Dissolving polyethylenes of different average molecular weights in compressed ethylene, it was found, that the solubility of the polymer is decreased with increasing molecular weight of the polymer. The maximum in pressure of the phase-boundary curves increases and is shifted towards lower polymer concentrations. The analysis of the samples from the gas and the liquid phase showed that the average molecular weight as well as the molecular weight distribution of the polymer is different in the two phase and differs also from the polymer in the homogeneous mixture. The results were compared with the data of other authors. Furthermore it was tried to show with other systems.     

Copolymerization of ethylene/α‐olefins using bis(2‐phenylindenyl)zirconium dichloride metallocene catalyst: structural study of comonomer distribution

Catalysts have a major role in the polymerization of olefins and exert their influence in three ways: (1) polymerization behaviour, including polymerization activity and kinetics; (2) polymer particle morphology, including bulk density, particle size, particle size distribution and particle shape; and (3) polymer microstructure, including molecular weight regulation, chemical composition distribution and short‐ and long‐chain branching. By tailoring the catalyst structure, such as the creation of a bridge or introducing a substituent on the ligand, metallocene catalysts can play a major role in the achievement of desirable properties. Kinetic profiles of the metallocene catalyst used in this study showed decay‐type behaviour for copolymerization of ethylene/α‐olefins. It was observed that increasing the comonomer ratio in the feedstock affected physical properties such as reducing the melting temperature, crystallinity, density and molecular weight of the copolymers. It was also observed that the heterogeneity of the chemical composition distribution and the physical properties were enhanced as the comonomer molecular weight was increased. In particular, 2‐phenyl substitution on the indenyl ring reduced somewhat the melting point of the copolymers. In addition, the copolymer produced using bis(2‐phenylindenyl)zirconium dichloride (bis(2‐PhInd)ZrCl₂) catalyst exhibited a narrower distribution of lamellae (0.3–0.9 nm) than the polymer produced using bisindenylzirconium dichloride catalyst (0.5–3.6 nm). The results obtained indicate that the bis(2‐PhInd)ZrCl₂ catalyst showed a good comonomer incorporation ability. The heterogeneity of the chemical composition distribution and the physical properties were influenced by the type of comonomer and type of substituent in the catalyst. Copyright © 2010 Society of Chemical Industry     

Mechanistic study of boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol

Boron trifluoride catalyzed ε‐caprolactone polymerization in the presence of glycerol can produce poly(ε‐caprolactone) with a high weight‐average molecular weight and a broad molecular weight distribution. This article reports an investigation of the polymerization mechanism to determine the formation of these molecular weight features through a study of the polymerization kinetics and the molecular structure with NMR. The polymerization proceeds via an activated monomer mechanism, resulting in polymer molecules with hydroxyl chain ends. The broad molecular weight distribution can be attributed to the etherification reactions between hydroxyl chain ends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3900–3906, 2006     

The role of diffusion in the Ziegler polymerization of ethylene

A theoretical and experimental study has been made of the polymerization of ethylene in a slurry reactor using a highly active Ziegler catalyst in the presence of hydrogen. A model of the polymerization system has been set up in which polymerization is assumed to proceed with encapsulation of catalyst subparticles. Allowance is made for an experimentally observed first-order decay in intrinsic catalyst activity. The theoretical prediction of the model for the monomer absorption rate behavior and the molecular weight characteristics of the polymers formed are in agreement with experimental findings. Experimental evidence is presented that in the earliest moments of a polymerization significant amounts of polymer are formed with molecular weights 100 times those in the balance of the polymerization. It is concluded that in this system the polymerization is diffusion controlled throughout the major part of the catalyst lifetime. This diffusion phenomenon, together with the gradual loss of active sites, is of vital importance in determining the molecular weight and molecular weight distribution of the polyethylene product.     

Kinetics of short‐duration ethylene polymerization with MgCl2‐supported Ziegler–Natta catalyst: Two‐stage initiation evidenced by changes in active center concentration

The kinetics of ethylene polymerization with a TiCl₄/MgCl₂‐type Ziegler–Natta catalyst was studied. Changes in polymerization activity and concentration of active centers ([C*]) in the first 5 min were determined. Initiation of the active centers was found to proceed in two stages. In the first stage, [C*]/[Ti] quickly rose to about 1% in less than 30 s and then remained stable in the subsequent 60 s. Then the [C*]/[Ti] value started to increase again, forming the second buildup stage. The polymerization activity was found to change roughly in parallel with the change in [C*]/[Ti]. Changes in the polymer/catalyst particle morphology and polymer molecular weight distribution with polymerization time were studied. A mechanistic model was proposed to explain the two‐stage kinetics: initiation of active sites on the outer surface of catalyst particles takes place in the first stage, and initiation of active sites buried inside the particles takes place in the second stage. These buried sites are released when the catalyst particles are fragmented by the expanding polymer phase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45187.     

HDPE/LLDPE reactor blends with bimodal microstructures—Part II: rheological properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and vice versa HMW homopolymer to LMW copolymer. The shear flow characteristics of these polymers in the typical processing range mostly depend on the molecular weight and MWD of the polymer and are independent of the short chain branch content. From oscillatory shear measurements, it was observed that the viscosity of HMW polymers was reduced with the addition of LMW material. For the polymers produced with this two-step polymerization process, the LMW homopolymer and HMW copolymer blends and HMW homopolymer and LMW copolymer blends were melt miscible, despite the large viscosity differences of the pure components.     

Synthesis of amino acid‐based polymers having metronidazole moiety and study of their controlled release in vitro

A new polymeric drug carrier system using amino acid‐based polymers was developed. Amino acid‐based polymers with controlled molar mass and narrow molecular weight distribution have been synthesized by reversible addition‐fragmentation chain transfer polymerization of four amino acid‐carrying monomers having different chirality and hydrophilicity. Metronidazole (MTZ) was immobilized onto the amino acid‐based polymers, and the release profiles of the polymer‐MTZ adducts were investigated in phosphate buffer solutions (pH = 2.0, 7.4, and 8.5). The model drug was released by the hydrolysis of the ester group, and the release rate and behavior of the polymeric prodrugs strongly depended on the configuration of the amino acid‐based polymers‐MTZ adducts and the pH of the release media. The release kinetics was determined using the Higuchi and Korsmeyer equations, which revealed the release mechanism of the polymeric prodrugs. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel functionalized bis(imino)pyridine cobalt(II) catalysts for ethylene polymerization

This report describes synthesis and ethylene polymerization in the various conditions by two novel 2,6-bis(imino)pyridine (BIMP) catalysts B and C based on cobalt activated by methylaluminoxane (MAO) in a slurry semi-batch reactor. The catalyst activities as well as polymer properties were affected dramatically by electronic effects of the attached substitutions on the para-position of the pyridine ring. Theoretical study exhibited more positive charge on the central metal of the catalyst B resulted in higher activity at the expense of lower thermal stability and lifetime. The polymer obtained using the catalysts exhibited high molecular weight and almost narrow molecular weight distribution (MWD) ranging from 2.35 to 4.10 at the employed polymerization conditions. The highest and lowest molecular weight of the obtained polymers were produced by the catalyst A and C respectively. Hydrogen could slightly increase the catalyst activities with the exception of the catalyst B. The catalyst C bearing electron-donor OMe substitution at the para-position of the pyridine ring, produced PE with narrower PDI relative to the polymer resulted by catalysts A and B.     

Kinetics of high conversion polymerization of vinyl acetate. Effects of mixing and reactor type on polymer properties

In the present article the kinetics of polymerization of vinyl acetate in suspension up to high conversion was studied. The molecular weight distribution and the side chain branching of polyvinyl acetate produced were examined with respect to micro and macro mixing as well as to reactor type. The following results were achieved: the time–activity curves of the polymerization can be described up to high conversions considering the exponential increase in viscosity of the polymerizing system and combining the viscosity with rate constants of the polymerization. The change of volume of the polymerizing system has no significant influence on kinetics. The narrowest molecular weight distribution of the poly(vinyl acetate) produced was achieved when polymerizing in the homogeneous continuous stirred tank reactor while the broadest molecular weight distribution was observed in the segregated continuous stirred tank reactor. The batch reactor and the flow tube reactor produce polymers with molecular weight distributions lying in between. Considering the side chain branching, another order was found. The batch reactor and the tube reactor show the lowest side chain branching, the homogeneous continuous stirred tank reactor shows a larger one and the segregated continuous stirred tank reactor shows the largest. Possible reasons for the different behavior of the different reactors are discussed. The degree of segregation was determined by experiments.     

Polymerization of olefins through heterogeneous catalysis. VI. Effect of particle heat and mass transfer on polymerization behavior and polymer properties

The multigrain model for polymerization of olefins over solid catalysts is used to predict kinetic behavior, molecular weights, and polydispersities. The effects of intraparticle and external boundary layer transport resistance on the kinetic behavior and polymer properties are explored. Means for the experimental detection of intraparticle diffusion resistance are suggested. The importance of catalyst physical properties, such as the porosity, and the catalyst loading is illustrated through simulation. Finally, the hypotheses of diffusion resistance and site heterogeneity as explanations for the broad molecular weight distributions of olefin polymers are critically evaluated, and molecular weight distribution control in industrial catalysts is discussed.     

Progress in the catalyst for ethylene/α-olefin copolymerization at high temperature

Ethylene/α-olefin copolymers are one of the most widely-used polyolefin materials. With the continuous improvement of polyolefin catalysts, high-performance polyolefin materials were synthesized by adjusting the chain microstructure, changing the comonomer type and comonomer insertion amount, among which the ethylene/α-olefin random copolymer elastomer (POE) and olefin block copolymer elastomer (OBC) are the most famous and well accepted by the market. The excellent properties of POE and OBC first depend on their polymer chain microstructure. The chain microstructure of polyolefins is fundamentally determined by the catalysts, polymerization conditions, comonomer feed policies, and reaction engineering. High-performance ethylene/α-olefin copolymer elastomers are currently prepared by high-temperature solution polymerization process, which needs to be carried out at a temperature above the melting point of the polymer and is beneficial to speed up the polymerization reaction rate and control the polyolefin chain microstructure. However, the high-temperature solution polymerization process launched more stringent requirements for the olefin coordination polymerization catalyst. Systematic reports on catalysts for high-temperature solution copolymerization of ethylene and α-olefins are lacking. In this review, we screened some catalysts suitable for the controllable copolymerization and high-temperature solution copolymerization of ethylene/α-olefin based on the catalyst's heat resistance, copolymerization activity, comonomer insertion ability, molecular weight, and distribution of the copolymer, including traditional Z–N catalysts, metallocene catalysts, and post-metallocene catalysts. And the future development of catalysts for high-temperature solution copolymerization of olefins, catalysts for precise control of polyolefin chain microstructures, and catalysts for olefin copolymerization with polar monomers at high temperature are envisaged.