The investigation of novel non‐metallocene catalysts with phenoxy‐imine ligands for ethylene (co‐)polymerization

Phthaldialdehyde and phthaldiketone were treated with substituted phenols of 2‐amino‐4‐methylphenol, 2‐amino‐5‐methylphenol and 2‐amino‐4‐t‐butylphenol, respectively, and then treated with transition metal halides of TiCl₄, ZrCl₄ and YCl₃. A series of novel non‐metallocene catalysts (1–12) with phenoxy‐imine ligands was obtained. The structures and properties of the catalysts were characterized by ¹H NMR and elemental analysis. The catalysts (1–12) were used to promote ethylene (co‐)polymerization after activation by methylaluminoxane. The effects of the structures and center atoms (Ti, Zr and Y) of these catalysts, polymerization temperature, Al/M (M = Ti, Zr and Y) molar ratio, concentration of the catalysts and solvents on the polymerization performance were investigated. The results showed that the catalysts were favorable for ethylene homopolymerization and copolymerization of ethylene with 1‐hexene. Catalyst 10 is most favorable for catalyzing ethylene homopolymerization and copolymerization of ethylene with 1‐hexene, with catalytic activity up to 2.93 × 10⁶ gPE (mol Y)^?1 h^?1 for polyethylene (PE) and 2.96 × 10⁶ gPE (mol Y)^?1 h^?1 for copolymerization of ethylene with 1‐hexene under the following conditions: polymerization temperature 50 °C, Al/Y molar ratio 300, concentration of catalyst 1.0 × 10^?4 L^?1 and toluene as solvent. The structures and properties of the polymers obtained were characterized by Fourier transform infrared spectroscopy, ¹³C NMR, wide‐angle X‐ray diffraction, gel permeation chromatography and DSC. The results indicated that the obtained PE catalyzed by 4 had the highest melting point of 134.8 °C and the highest weight‐average molecular weight of 7.48 × 10⁵ g mol^?1. The copolymer catalyzed by 4 had the highest incorporation of 1‐hexene, up to 5.26 mol%, into the copolymer chain. © 2012 Society of Chemical Industry     

Preparation of ethylene/1‐octene copolymers from ethylene stock with tandem catalytic system

Tandem catalysis offers a novel synthetic route to the production of linear low‐density polyethylene. This article reports the use of homogeneous tandem catalytic systems for the synthesis of ethylene/1‐octene copolymers from ethylene stock as the sole monomer. The reported catalytic systems involving a highly selective, bis(diphenylphosphino)cyclohexylamine/Cr(acac)₃/methylaluminoxane (MAO) catalytic systems for the synthesis of 1‐hexene and 1‐octene, and a copolymerization metallocene catalyst, rac‐Et(Ind)₂ZrCl₂/MAO for the synthesis of ethylene/1‐octene copolymer. Analysis by means of DSC, GPC, and ¹³C‐NMR suggests that copolymers of 1‐hexene and ethylene and copolymers of 1‐octene and ethylene are produced with significant selectivity towards 1‐hexene and 1‐octene as comonomers incorporated into the polymer backbone respectively. We have demonstrated that, by the simple manipulation of the catalyst molar ratio and polymerization conditions, a series of branched polyethylenes with melting temperatures of 101.1–134.1°C and density of 0.922–0.950 g cm^?3 can be efficiently produced. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Behavior of poly(ethylene‐co‐olefin) polymers as elastomeric materials

The properties of two new ethylene‐α‐olefin copolymers, namely, ethylene–1‐hexene copolymer (EHC) and ethylene–1‐octadecene copolymers (EOC), synthesized via metallocene catalysts were evaluated. The copolymerization was carried out in an autoclave reactor with Et(Indenyl)₂ZrCl₂/methylaluminoxane as a catalyst system. These single‐site catalysts (metallocene type) allow one to obtain very homogeneous copolymers with excellent control of the molecular weight distribution and proportion of comonomer incorporation. So, copolymers with 18 mol % comonomer in the case of EHC and 12 mol % for EOC were shaped, and activities around 100,000 kg of polymer mol^?1 of Zr bar^?1 h^?1 were reached. The properties of these copolymers were compared with other commercial elastomers, such as ethylene–propylene copolymers synthesized by Ziegler–Natta catalysts and an ethylene–octene copolymer obtained via metallocene catalysts. The results show that these new copolymers, in particular, EOC, had excellent elastomeric properties. Furthermore, they had a relatively low viscosity, which implied a good response during processing. Moreover, the effectiveness of these copolymers as impact modifiers for polyolefins was also studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3008–3015, 2004     

Synthesis and catalytic properties for olefin polymerization of new vanadium complexes containing silsesquioxane ligands with different denticity

A series of new vanadium‐silsesquioxanes ( 2a ? 2d ) was prepared by reacting VCl₄ with not fully condensed silsesquioxanes (having from one to four silanol groups) and evaluated as pre‐catalysts in olefin polymerization. The activation of 2a ? 2d with EtAlCl₂ generated highly active catalysts for ethylene polymerization, yielding high molar mass polymers with narrow dispersity. Ultra‐high molar mass polyethylenes, M _w up to 4 × 10⁶ g mol^?1, were obtained with methylaluminoxane and Al(i Bu)₃/[Ph₃C][B(C₆F₅)₄] as activators. Upon treatment with methylaluminoxane and boron compounds, all vanadium pre‐catalysts were active in 1‐octene polymerization as well, and produced isotactic‐rich poly(1‐octene)s with moderate monomer conversion (up to 23%). The polymerization parameters were optimized and the effect of the silsesquioxane structure on the catalytic activity and polymer properties was studied. © 2017 Society of Chemical Industry     

Synthesis and micellization behavior of amphiphilic graft copolymer with 1‐octene as hydrophobic moiety

Two new kinds of amphiphilic copolymers were synthesized in this work. Poly(1‐octene‐co‐acrylic acid) copolymers were prepared through the copolymerization of 1‐octene and tert‐butyl acrylate, and the hydrolysis of tert‐butyl acrylate units. Poly(1‐octene‐co‐acrylic acid)‐g‐poly (ethylene glycol) copolymers were obtained from the esterification reaction between poly(1‐octene‐co‐acrylic acid) and poly(ethylene glycol) monomethyl ether. They were characterized by means of ¹H‐NMR, ¹³C‐NMR, GPC, and FTIR. These amphiphilic copolymers can form stable micelles in aqueous solutions. The critical micelle concentration was determined by fluorescence spectroscopy. The micellar morphology and size distribution were investigated by transmission electron microscopy and dynamic light scattering. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Copolymerization of propylene with 1‐octene catalyzed by MgCl2/TiCl4/diether catalyst

MgCl₂/TiCl₄/diether is a fifth‐generation Ziegler–Natta catalyst for the commercial polymerization of propylene. The outstanding features of this catalyst are the high activity and high isotacticity for propylene polymerization without using an external electron donor. In this study, we explored the copolymerization of propylene and 1‐octene with MgCl₂/TiCl₄/diether catalyst. It was found that MgCl₂/TiCl₄/diether catalyst showed higher polymerization activity and led to greater 1‐octene content incorporation, compared with a fourth‐generation Ziegler–Natta catalyst (MgCl₂/TiCl₄/diester). With an increase in 1‐octene incorporation in polypropylene chains, the melting temperature, glass transition temperature and crystallinity of the copolymers decreased distinctly. The microstructures of the copolymers were characterized using ¹³C NMR spectroscopy, and the copolymer compositions and number‐average sequence lengths were calculated from the dyad concentration and distribution. This result is very important for the in‐reactor polyolefin alloying process, especially for the case of a single catalyst and two‐step (or two‐reactor) process. Copyright © 2011 Society of Chemical Industry     

Synthesis of ethylene/1‐octene copolymers with controlled block structures by semibatch living copolymerization

A kinetic model was developed for the living copolymerization of ethylene/1‐octene using the fluorinated FI‐Ti catalyst system, bis[N‐(3‐methylsalicylidene)‐2,3,4,5,6‐pentafluoroanilinato] TiCl₂/dried methylaluminoxane is presented. The model was first validated by batch polymerization experiments. Kinetic parameters were estimated from the model correlations with online ethylene consumption rates and end‐of‐batch copolymer molecular weight. The model was then used to calculate the microstructural properties of ethylene/1‐octene copolymers with controlled composition profiles (uniform, diblock, and step triblock), which were synthesized using sequential comonomer feeding policies in semibatch copolymerization. The synthesized block copolymers had the exact composition distributions and molecular weights as the model simulated. It was demonstrated that the polymer chain microstructure in the living copolymerization of olefins could be precisely regulated by using semibatch comonomer feeding policies. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4686–4695, 2013     

Isobutylaluminum aryloxides as metallocene activators in Homo‐ and copolymerization of olefins

The article describes that sterically hindered isobutylaluminum aryloxides with bulky ^tBu substituents at 2,6‐ positions of aryl fragment, i.e. (2,6‐di‐^tBu,4‐R‐C₆H₂O)AlⁱBu₂ (R = H ( 1‐DTBP ), Me ( 1‐BHT ), ^tBu ( 1‐TTBP )) and (2,6‐di‐^tBu,4‐R‐C₆H₂O)₂AlⁱBu (R=H( 2‐DTBP ), Me( 2‐BHT )) can serve as cocatalysts for metallocene complexes. Isobutylaluminum aryloxides have been applied for activation of rac‐Et(2‐MeInd)₂ZrMe₂ in homopolymerization of ethylene, propylene, copolymerization of ethylene and propylene, and terpolymerization of ethylene, propylene, and 5‐ethylidene‐2‐norbornene at Al/Zr = 300 mol/mol. The type of R substituent at 4‐position has a significant effect on catalyst activity. The catalytic system with 1‐TTBP showed the highest activity in all homo‐ and copolymerization processes. Diisobutylaluminum aryloxides provide much higher activity to the systems in all polymerization processes and stronger ability for propylene incorporation in copolymer than diaryloxides. The activities of the systems with isobutylaluminum aryloxides are similar or exceed that of the system with MAO as activator as have shown for propylene polymerization. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43276.     

Copolymerization of styrene with an α‐olefin via atom transfer radical polymerization

This investigation reports the preparation of styrene–α‐olefinic random copolymers, using 1‐octene as an α‐olefin, via atom transfer radical polymerization. Atom transfer radical copolymerization of styrene with 1‐octene was successfully carried out using phenylethyl bromide as initiator and CuBr as catalyst in combination with N, N, N′, N″, N″‐pentamethyldiethylenetriamine as ligand. The copolymers had controlled molecular weight, narrow dispersity and well‐defined end groups with significant 1‐octene incorporation in the polymer. Incorporation of 1‐octene in the copolymers was confirmed using ¹H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectroscopy. An increase in 1‐octene content in the monomer feed led to an increase in the level of incorporation of the α‐olefin in the copolymer. An increase in the concentration of 1‐octene led to a decrease in the rate of polymerization and an increase in dispersity. The glass transition temperature of the copolymer gradually decreased as the incorporation of 1‐octene increased. Copyright © 2011 Society of Chemical Industry     

Preparation of polymer‐supported zirconocene catalysts and olefin polymerization

A novel polymer‐supported metallocene catalyst with crosslinked poly(styrene‐co‐acrylamide) (PSAm) as the support has been prepared and characterized. The probability of long sequences of acrylamide (Am) in PSAm is still low even at an Am amount of 32.8 mol %, implying the relatively homogeneous distribution of Am. The infrared spectra of PSAm and the supported catalyst substantiate that an amide group in PSAm coordinates with methylaluminoxane through both oxygen and nitrogen atoms. Ethylene/α‐octene copolymerization showed that the catalytic activity is not markedly affected by adding α‐octene. ¹³C NMR analysis of the ethylene/α‐octene copolymer indicated that the composition distribution of the copolymer is uniform. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2253–2258, 1999     

Polyethylene‐block‐poly(ε‐caprolactone) diblock copolymers: synthesis and compatibility

A strategy is introduced for the synthesis of polyethylene‐block‐poly(ε‐caprolactone) block copolymers by a combination of coordination polymerization and ring‐opening polymerization. First, end‐hydroxylated polyethylene (PE‐OH) was prepared with a one‐step process through ethylene/3‐buten‐1‐ol copolymerization catalyzed by a vanadium(III) complex bearing a bidentate [N,O] ligand ([PhN?C(CH₃)CHC(Ph)O]VCl₂(THF)₂). The PE‐OH was then used as macroinitiator for ring‐opening polymerization of ε‐caprolactone, leading to the desired nonpolar/polar diblock copolymers. The block structure was confirmed by spectral analysis using ¹H NMR, gel permeation chromatography and differential scanning calorimetry. The unusual topologies of the model copolymers will establish a fundamental understanding for structure–property correlations, e.g. compatibilization, of polymer blends and surface and interface modification of other polymers. © 2014 Society of Chemical Industry     

Gas‐phase ethylene polymerization using zirconocene supported on mesoporous molecular sieves

Mesoporous molecular sieves, with pore diameters of 2.6–25 nm, were impregnated with methylaluminoxane and bis(butylcyclopentadienyl)zirconium dichloride and tested as catalysts for the gas‐phase homopolymerization of ethylene at ethylene pressures of 200 psi and temperatures of 50–100°C and for 1‐hexene/ethylene copolymerization at 70°C. The activities and activity profiles, at constant Zr and Al contents, depended on the pore size of the supports and the polymerization temperature. Maximum activities for both the homopolymerizations and copolymerizations were observed for catalysts made with supports having pore diameters of 2.6 and 5.8 nm. Homopolymerization activities were highest at temperatures of 70–80°C; average homopolymerization and copolymerization activities up to 9000 kg of polyethylene/(mol of Zr h) were obtained. The weight‐average molecular weights (M_w's) were not a function of the support pore size but decreased with increasing reaction temperatures, from about 260,000 at 50°C to about 165,000 at 100°C. The polydispersities were essentially constant at 2.5 ± 0.2 for the homopolymers. M_w's for the 1‐hexene/ethylene copolymers had an average value of 117,000 with an average polydispersity of 2.8. The amount of triisobutyl aluminum added to the reactor significantly affected the activity and activity profiles. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1161–1177, 2003     

Preparation and properties of fluorine‐containing polysiloxanes obtained via ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane catalyzed by rare earth solid superacid SO$_{4}^{2-}$/TiO2/Ln3+

Traditional catalysts such as (CH₃)₄NOH, NaOH, KOH, n‐BuLi and CF₃SO₃H can catalyze the copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane to afford fluorine‐containing polysiloxanes. However, use of these catalysts poses significant difficulties in handling and separation. In this work, fluorine‐containing polysiloxanes were synthesized through a novel and environmentally friendly method: ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane catalyzed by rare earth solid superacid SO /TiO₂/Ln³⁺. The effects of reaction conditions were examined in detail. The yield sequence of various rare earth catalysts is Nd ～ La ～ Y ～ Sm > Gd, while the number‐average molecular weight sequence is Nd > La > Y > Sm > Gd. The optimum conditions for the ring‐opening copolymerization of trifluoropropyltrimethylcyclotrisiloxane with cyclotetrasiloxane are as follows: [Nd³⁺] = 0.05 mol L^?1 and mol L^?1 in the immersing solution, SO /TiO₂/Nd³⁺ calcined at 500 °C and the copolymerization conducted at 80 °C for 40 min. Structures of resulting copolymers were characterized using size exclusion chromatography, ¹H NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis and contact angle measurements. According to the copolymerization features, a cationic equilibrium reaction mechanism is proposed. Copyright © 2012 Society of Chemical Industry     

Ethylene/α‐olefin copolymerization by nonbridged (cyclopentadienyl)(aryloxy)titanium(IV) dichloride/AliBu3/Ph3CB(C6F5)4 catalyst systems

A series of nonbridged (cyclopentadienyl) (aryloxy)titanium(IV) complexes of the type, (η⁵‐Cp′)(OAr)TiCl₂ [OAr = O‐2,4,6‐^tBu₃C₆H₂ and Cp′ = Me₅C₅ ( 1 ), Me₄PhC₅ ( 2 ), and 1,2‐Ph₂‐4‐MeC₅H₂ ( 3 )], were prepared and used for the copolymerization of ethylene with α‐olefins (e.g., 1‐hexene, 1‐octene, and 1‐octadecene) in presence of AlⁱBu₃ and Ph₃CB(C₆F₅)₄ (TIBA/B). The effect of the catalyst structure, comonomer, and reaction conditions on the catalytic activity, comonomer incorporation, and molecular weight of the produced copolymers was examined. The substituents on the cyclopentadienyl group of the ligand in 1 – 3 play an important role in the catalytic activity and comonomer incorporation. The 1 /TIBA/B catalyst system exhibits the highest catalytic activity, while the 3 /TIBA/B catalyst system yields copolymers with the highest comonomer incorporation under the same conditions. The reactivity ratio product values are smaller than those by ordinary metallocene type, which indicates that the copolymerization of ethylene with 1‐hexene, 1‐octene, and 1‐octadecene by the 1–3/ TIBA/B catalyst systems does not proceed in a random manner. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Chain transfer reaction in metallocene catalyzed ethylene copolymerization with allyltrimethylsilane

Summary In order to investigate the polymerization behavior of allytrimethylsilane as a comonomer, ethylene was copolymerized with allyltrimethylsilane at 80°C in toluene using methylaluminoxane (MAO) activated metallocene catalysts. The catalytic activity of the polymerization strongly depended on both the type of the catalysts and the concentration of allyltrimethylsilane. End group analysis of the copolymers by means of ¹H and ¹³C NMR spectroscopy revealed that allyltrimethylsilane rather act as a chain transfer agent in the copolymerization, even though considerable amount of allyltrimethylsilane was incorporated in the polymer chain with rac-Et(Ind)₂ZrCl₂ catalysts. The chain transfer reaction influence strongly the molecular weight and comonomer content of the copolymers. Received: 22 June 1999/Revised version: 9 September 1999/Accepted: 30 September 1999     

Poly(1‐octene) synthesis using high performance supported titanium catalysts

Poly(1‐octene) was synthesized by polymerization of 1‐octene using high performance MgCl₂‐supported TiCl₄ in combination with triethyl aluminum (TEAl) as cocatalyst in n‐hexane for 2 h. Two catalysts, C₁ (diester catalyst) having di‐isobutyl phthalate as internal donor and C₂ (monoester catalyst) having ethyl benzoate as internal donor were utilized for the atmospheric polymerizations to evaluate the influence of structurally different internal donors on the productivity, rate of polymerization and molecular weight profiles. The kinetic profile assessed in terms of variation of reaction parameters like temperature, cocatalyst to catalyst molar ratio and monomer concentration was found to be dependent on them. From these kinetic analyses, optimize conditions for polymerizations of 1‐octene using diester as well as monoester catalyst were elucidated. The difference in the performance of diester and monoester catalyst system can be explained in terms of stability of active titanium species and chain transfer process. NMR spectroscopy of synthesized poly(1‐octene) indicate predominantly isotactic nature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

FI Catalysts: A New Family of High Performance Catalysts for Olefin Polymerization

This paper reviews a new family of olefin polymerization catalysts. The catalysts, named FI catalysts, are based on non‐symmetrical phenoxyimine chelate ligands combined with group 4 transition metals and were developed using “ligand‐oriented catalyst design”. FI catalysts display very high ethylene polymerization activities under mild conditions. The highest activity exhibited by a zirconium FI catalyst reached an astonishing catalyst turnover frequency (TOF) of 64,900 s ^–1 atm ^–1, which is two orders of magnitude greater than that seen with Cp₂ZrCl₂ under the same conditions. In addition, titanium FI catalysts with fluorinated ligands promote exceptionally high‐speed, living ethylene polymerization and can produce monodisperse high molecular weight polyethylenes (M_w/M_n<1.2, max. M_n>400,000) at 50 °C. The maximum TOF, 24,500 min ^–1 atm ^–1, is three orders of magnitude greater than those for known living ethylene polymerization catalysts. Moreover, the fluorinated FI catalysts promote stereospecific room‐temperature living polymerization of propylene to provide highly syndiotactic monodisperse polypropylene (max. [rr] 98%). The versatility of the FI catalysts allows for the creation of new polymers which are difficult or impossible to prepare using group 4 metallocene catalysts. For example, it is possible to prepare low molecular weight (M_v∼10³) polyethylene or poly(ethylene‐co‐propylene) with olefinic end groups, ultra‐high molecular weight polyethylene or poly(ethylene‐co‐propylene), high molecular weight poly(1‐hexene) with atactic structures including frequent regioerrors, monodisperse poly(ethylene‐co‐propylene) with various propylene contents, and a number of polyolefin block copolymers [e.g., polyethylene‐b‐poly(ethylene‐co‐propylene), syndiotactic polypropylene‐b‐poly(ethylene‐co‐propylene), polyethylene‐b‐poly(ethylene‐co‐propylene)‐b‐syndiotactic polypropylene]. These unique polymers are anticipated to possess novel material properties and uses.     

Comonomer effects in copolymerization of ethylene and 1‐hexene with MgCl2‐supported Ziegler‐Natta catalysts: New evidences from active center concentration and molecular weight distribution

In this article, comonomer effects in copolymerization of ethylene and 1‐hexene with four MgCl₂‐supported Ziegler‐Natta catalysts using either ethylene or 1‐hexene as the main monomer were investigated. It was found that no matter which monomer was used as the main monomer, the polymerization activity was significantly enhanced by introducing small amount of comonomer. In copolymerization with ethylene as the main monomer, the strength of comonomer effects was much stronger in active centers producing low‐molecular‐weight polymer than those producing high‐molecular‐weight polymer. In copolymerization with 1‐hexene as the main monomer, the number of active centers ([C*]/[Ti]) was determined, and the propagation rate constants (k_p) were calculated. Deconvolution of the polymer molecular weight distribution into Flory components were made to study the active center distribution. Introduction of small amount of ethylene caused marked increase in the number of active centers and decrease in average chain propagation rate constant. Introducing internal electron donor in the catalyst enhanced not only the number of active centers but also the chain propagation rate constant. In copolymerization of 1‐hexene with small amount of ethylene, the internal donor weakened the comonomer effects to some extent and changed the distribution of comonomer effects among different types of active centers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41264.     

Copolymerization of ethylene and propylene catalyzed by novel magnesium chloride supported,vanadium‐based catalysts

Two novel magnesium chloride supported, vanadium‐based Ziegler–Natta catalysts with 9,9‐bis(methoxymethyl)fluorene and di‐i‐butyl phthalate as internal donors were prepared and used in the copolymerization of ethylene and propylene. The catalytic behaviors of these catalysts were investigated and compared with those of traditional magnesium chloride supported, vanadium‐based catalysts without internal donors. Differential scanning calorimetry, gel permeation chromatography, and ¹³C‐NMR spectroscopy analysis were performed to characterize the melting temperatures, molecular weights, and molecular weight distributions as well as structures and compositions of the products. The copolymerization kinetic results indicated that the novel catalyst with 9,9‐bis(methoxymethyl)fluorene as an internal donor had the highest catalytic activity and optimal kinetic behavior in ethylene–propylene copolymerization with an ethylene/propylene molar ratio of 44/56. Low‐crystallinity and high‐molecular‐weight copolymers were obtained with these novel magnesium chloride supported, vanadium‐based catalysts. The reactivity ratio data indicated that the catalytic systems had a tendency to produce random ethylene–propylene copolymers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The architecture of hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE via one‐pot strategy combining living free radical polymerization with coordination polymerization

The copolymerization of styrene with ethylene was promoted by CpTiCl₃/BDGE/Zn/MAO catalyst system combining free radical polymerization with coordination polymerization via sequential monomer addition strategy in one‐pot. The effect of polymerization conditions such as temperature, time, ethylene pressure, and Al/Ti molar ratio on the polymerization performance was investigated. The hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE triblock copolymer was obtained by solvent extraction and determined by GPC, DSC, WAXD, and ¹³C‐NMR. The DSC result indicated that the aPS‐b‐random copolymer‐b‐PE had a T_g at 87°C and a T_m at 119°C which attributed to the T_g of aPS segment and the T_m of PE segment, respectively. The microstructure of the hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE was further confirmed by WAXD, ¹³C‐NMR, and ¹H‐NMR analysis; and these results demonstrated that the obtained block copolymer consisted of aPS segment, S‐E random copolymer segment, and crystalline PE segment. The connection polymerization of the hydroxy‐functionalized aPS with random copolymer‐b‐PE was revealed by GPC results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011