Highly active ethylene/hydroxyl comonomers copolymerization using metallocene catalysts

Ethylene was copolymerized with 10‐undecen‐1‐ol and 5‐hexen‐1‐ol using stereorigid [rac‐ethylene(Ind)₂ZrCl₂], [rac‐ethylene(H₄Ind)₂ZrCl₂], and the new catalyst systems [rac‐norbornane(Ind)₂TiCl₂] and [mesonorbornane(Ind)₂TiCl₂], activated with methylaluminoxane. The characterization of the copolymers by ¹³C NMR spectroscopy revealed that the polymerization products were copolymers and that the conversion of the polar comonomer was strongly favored in the case of the zirconocene precursors. Very high catalytic activity values, nearly independent on the amount of comonomer in the feed, and comonomer incorporations up to 25.4%‐weight have been found for 10‐undencen‐1‐ol comonomer. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Comparative study of copolymerization and terpolymerization of ethylene/propylene/diene monomers using metallocene catalyst

(Ind)₂ZrCl₂ catalyst was synthesized and used for copolymerization of ethylene and propylene (EPR) and terpolymerization of ethylene propylene and 5‐ethyldiene‐2‐norbornene (ENB). Methylaluminoxane (MAO) was used as cocatalyst. The activity of the catalyst was higher in copolymerization of ethylene and propylene (EPR) rather than in terpolymerization of ethylene, propylene and diene monomers. The effects of [Al] : [Zr] molar ratio, polymerization temperature, pressure ratio of ethylene/propylene and the ENB concentration on the terpolymerization behavior were studied. The highest productivity of the catalyst was obtained at 60°C, [Al] : [Zr] molar ratios of 750 : 1 and 500 : 1 for copolymerization and terpolymerization, respectively. Increasing the molar ratio of [Al] : [Zr] up to 500 : 1 increased the ethylene and ENB contents of the terpolymers, while beyond this ratio the productivity of the catalyst dropped, leading to lower ethylene and ENB contents. Terpolymerization was carried out batchwise at temperatures from 40 to 70°C. Rate time profiles of the polymerization were a decay type for both copolymerization and terpolymerization. Glass transition temperatures (T_g) of the obtained terpolymers were between ?64 and ?52°C. Glass transition temperatures of both copolymers and terpolymers were decreased with increased ethylene content of the polymers. Dynamic mechanical and rheological properties of the obtained polymers were studied. A compounded EPDM showed good thermal stability with time. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of cocatalyst on the chemical composition distribution and microstructure of ethylene-hexene copolymer produced by a metallocene/Ziegler-Natta hybrid catalyst

A silica-magnesium bisupport (SMB) was prepared by a sol-gel method for use as a support for metallocene/Ziegler-Natta hybrid catalyst. The SMB was treated with methylaluminoxane (MAO) prior to the immobilization of TiCl₄ and rac-Et(Ind)₂ZrCl₂. The prepared rac-Et(Ind)₂ZrCl₂/TiCl₄/MAO/SMB catalyst was applied to the ethylenehexene copolymerization with a variation of cocatalyst species (polymerization run 1: triisobutylaluminum (TIBAL) and methylaluminoxane (MAO), polymerization run 2: triethylaluminum (TEA) and methylaluminoxane (MAO)). The effect of cocatalysts on the chemical composition distributions (CCDs) and microstructures of ethylene-hexene copolymers was examined. It was found that the catalytic activity in polymerization run 1 was a little higher than that in polymerization run 2, because of the enhanced catalytic activity at the initial stage in polymerization run 1. The chemical composition distributions (CCDs) in the two copolymers showed six peaks and exhibited a similar trend. However, the lamellas in the ethylene-hexene copolymer produced in polymerization run 1 were distributed over smaller sizes than those in the copolymer produced in polymerization run 2. It was also revealed that the rac-Et(Ind)₂ZrCl₂/TiCl₄/MAO/SMB catalyst preferably produced the ethylene-hexene copolymer with non-blocky sequence when TEA and MAO were used as cocatalysts.     

Dynamic mechanical and rheological properties of metallocene-catalyzed long-chain-branched ethylene/propylene copolymers

The dynamic mechanical and rheological properties of five long-chain branched (LCB) and three linear ethylene/propylene (EP) copolymers were investigated and compared using a dynamic mechanical analyzer (DMA) and an oscillatory rheometer. The novel series of LCB EP copolymers were synthesized with a constrained geometry catalyst (CGC), [C₅Me₄(SiMe₂N^tBu)]TiMe₂, and had various propylene molar fractions of 0.01-0.11 and long-chain branch frequencies (LCBF) of 0.05-0.22. The linear EP copolymers were synthesized with an ansa-zirconocene catalyst, rac-Et(Ind)₂ZrCl₂ (EBI), and contained similar levels of propylene incorporation as the CGC copolymers, but no LCB. In dynamic mechanical analysis, the dynamic storage moduli (G′) and loss moduli (G″) of the copolymers decreased with an increase of propylene molar fraction. The α- and β-transitions of the CGC copolymers were overlaid with each other. High damping (tan δ) values were found with the CGC copolymers at temperatures below 0 °C. In oscillatory rheological analysis, compared to the linear EBI counterparts, the LCB CGC copolymer melts showed higher zero shear activation energies, broader plateaus of δ and larger elastic contributions, which are essential characteristics of LCB polymers. It was found that the long chain branching was the determining factor in controlling rheological properties of the polymer melts while the short chain branching from propylene incorporation played a decisive role in affecting dynamic mechanical properties. This work represents the first rheological evidence of LCB in EP copolymers synthesized with CGC.     

Synthesis of ethylene and norbornene copolymer with metallocene catalysts and characteristic analysis

To synthesis ethylene (E) and norbornene (NB) copolymer with high glass transition temperature and transparency, three metallocene catalysts with different symmetric structure were evaluated, respectively. The catalyst activity, NB fraction in copolymer and the transparency of copolymers produced under various conditions were investigated. It has been found that C₂ symmetric catalyst such as rac‐[En(Ind)₂]ZrCl₂ was the best choice to produce copolymer with high NB fraction while keeping high catalyst activity. Furthermore, the effects of reaction conditions on activity of rac‐[En(Ind)₂]ZrCl₂ and the resultant copolymer structure have also been thoroughly studied. The results indicate that increasing the NB/E ratio is the effective way to increase NB content of copolymer when NB/E ratio is less than 20. However, when NB/E ratio is over 20, further increase in NB/E ratio will lead to significant lower catalyst activity and very limited increase in NB content of copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation of styrene/1‐hexene copolymerization by homogeneous and heterogeneous bisindenyl ethane zirconium dichloride catalyst system

Homogeneous copolymerization of styrene and 1‐hexene was carried out in toluene at room temperature using bisindenyl ethane zirconium dichloride/methylaluminoxane (MAO). The supported catalyst was prepared with immobilization of Et(Ind)₂ZrCl₂/MAO on silica (calcinated at 500°C) with premixed method. Heterogeneous copolymerization of styrene/1‐hexene with different mole ratios was carried out in the presence of supported catalyst system. The copolymers obtained from homogeneous and heterogeneous catalyst system were characterized by ¹H NMR and ¹³C NMR. Composition of the resulting copolymers was determined by ¹H NMR data. Analysis of ¹³C NMR spectra of obtained copolymers by homogeneous and heterogeneous catalyst systems present isotactic olefin‐enriched copolymers. Molecular weight and thermal behavior of resulting copolymers was investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4008–4014, 2007     

Kinetics of propylene polymerization by hafnocene diamide catalyst

The kinetics of propylene polymerization initiated by ansa‐metallocene diamide compound rac‐(EBI)Hf(NMe₂)₂ (EBI = C₂H₄‐(indenyl)₂, rac‐1) were investigated. The rac‐1 compound could be directly utilized for catalyst formations without converting to a dihalide or dialkyl complex in the presence or absence of methylaluminoxane (MAO). The MAO‐free system rac‐1/AlR₃/[Ph₃C][B(C₆F₅)₄] (2) is much more effective than the rac‐1/MAO catalyst. The activity of the rac‐1/Al(iBu)₃/2 system is much higher than that of the rac‐(EBI)HfCl₂/MAO or rac‐(EBI)ZrCl₂/MAO catalyst, and almost same as that of the rac‐(EBI)Zr(NMe₂)₂/Al(iBu)₃/2 catalyst under similar conditions. The alkylation of rac‐1 to rac‐(EBI)HfR₂ by using AlR₃ needs more time than the corresponding zirconocene analogue. The activity increases by a factor of 7 by increasing the aging time from 1 min to more than 4 h. The activity of the rac‐1/AlR₃/2 catalyst is very sensitive to the type and concentration of AlR₃, and decreases in the order: Al(iBu)₂H > Al(iBu)₃ > AlEt₃ > AlMe₃. The catalyst keeps high activity in a narrow range of the [Al]/[Hf] ratio. In addition, the activity is influenced by the concentration of 2, and as a result, the maximum activity is observed when 2/rac‐1 = 0.7. The activity of the rac‐1/AlR₃/2 catalyst is also sensitive to the polymerization temperature. The activation energies for the initiation and overall reactions are calculated as 7.61 and 7.14 kcal/mol, respectively. The properties of polymer such as isotacticity (as [mmmm]), molecular weight (MW), molecular weight distribution (MWD), melting temperature (T_m), and crystallinity are similar level with those obtained with the rac‐(EBI)HfCl₂/MAO system. The MW and isotacticity of the polymer produced by MAO‐free system decreases monotonically as T_p increases, and MWD becomes narrow from 2.90 to 2.10 when T_p increases from 30 to 90°C because of the compositional homogeneity of the polymer produced at high T_p, which is demonstrated by fractionation of the polymer. Both MW and [mmmm] values of polymers decrease as aging time and anion concentration increase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 843–855, 2000     

Copolymerization of Propylene with 1-Hexene and 4-Methyl-1-Pentene in Liquid Propylene Medium. Synthesis and Characterization of Random Metallocene Copolymers with Isotactic Propylene Sequences

Summary Propylene copolymerization with 1-hexene and 4-methyl-1-pentene in liquid propylene medium in presence of MAO-activated C₂-symmetry ansa-zirconocene rac-Me₂Si(4-Ph-2-MeInd)₂ZrCl₂ was studied. Random copolymers of propylene with 1-hexene and 4-methyl-1-pentene content up to 7 mol % were obtained at 60 °C. General kinetic characteristics of propylene/higher α-olefin copolymerization were evaluated. The distinct feature of propylene copolymerization with 1-hexene and 4-methyl-1-pentene in liquid propylene medium – the proximity of comonomer relative reactivity ratios (r₁∼r₂∼1) that indicates azeotropic nature of copolymerization processes in studied conditions. Synthesized copolymers were characterized with the use of IR, ¹³C NMR, GPC, WAXD, DSC techniques, and uniaxial tensile testing.     

The effect of TIBA on metallocene/MAO catalyzed synthesis of propylene oxazoline copolymers and their use in reactive blending

Oxazoline‐functionalized polypropylenes were synthesized by using the rac‐Et[1‐Ind]₂ZrCl₂/MAO catalyst system. The used comonomers were 2‐(9‐decene‐1‐yl)‐1,3‐oxazoline (R‐Ox1), 2‐(9‐decene‐1‐yl)‐4,4‐dimethyl‐1,3‐oxazoline (R‐Ox2), and 2‐(4‐(10‐undecene‐1‐oxy)phenyl)‐1,3‐oxazoline (R‐Ox3). The oxazolines reduce the catalyst activity in the order R‐Ox3 > R‐Ox1 > R‐Ox2. By the addition of triisobutylaluminum (TIBA), the catalyst poisoning is reduced and is most pronounced in the R‐Ox1‐ and R‐Ox2‐containing systems. The oxazoline‐containing copolymers were melt blended with carboxylic acid end‐functionalized polystyrene (PS‐COOH) at 200°C. Strong changes in the morphology of the reactive blends compared to the nonreactive blends, especially the cocontinuous morphology in a poly(propylene‐co‐R‐Ox3)/PS‐COOH blend, indicate the usefulness of the modified copolymers in the reactive blending processes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2174–2181, 2002     

Study of the influence of the reaction parameters on the composition of the metallocene‐catalyzed ethylene copolymers using temperature rising elution fractionation and 13C nuclear magnetic resonance

Polyethylene copolymers prepared using the metallocene catalyst rac‐Et[Ind]₂ZrCl₂ were fractionated by preparative Temperature Rising Elution Fractionation (p‐TREF) and characterized by ¹³C nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), and gel permeation chromatography (GPC) to study the heterogeneity caused by experimental conditions. Two ethylene–1‐hexene copolymers with different 1‐hexene content and an ethylene–1‐octene copolymer all obtained using low (1.6 bar) ethylene pressure were compared with two ethylene–1‐hexene copolymers with different 1‐hexene content obtained at high ethylene pressure (7.0 bar). Samples obtained at low ethylene pressure and with low 1‐hexene concentration in the reactor presented narrow distributions in composition. Samples prepared with high comonomer concentration in the reactor or with high ethylene pressure showed an heterogeneous composition. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 155–163, 2002; DOI 10.1002/app.10284     

Thermal and dynamic mechanical behavior of ethylene/norbornene copolymers with medium norbornene contents

A range of ethylene/norbornene copolymers were synthesized using the commercially available rac‐Et(Ind)₂ZrCl₂ metallocene catalyst. A large window of norbornene contents, between 30 and 55 mol % was used to facilitate the interpretation of the results. The polymers were characterized by means of wide‐angle X‐ray scattering, differential scanning calorimetry, and dynamic mechanical thermal analysis. The X‐ray diffractograms showed two amorphous halos, the low‐angle one increasing in the intensity with norbornene content. Calorimetric and dynamic mechanical results led to a linear relation between the glass transition temperature and the norbornene content. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2159–2165, 2001     

Polymerization and characterization of ethylene/propylene and ethylene/1-octene copolymers produced with bridged Zr- and Hf-based metallocenes

Ethylene/propylene (E/P) and ethylene/1-octene (E/O) copolymers were polymerized with two bridged metallocene catalyst systems, Et(Ind)₂ZrCl₂/MAO and Et(Ind)₂HfCl₂/MAO, respectively. The copolymers produced and some commercial reference copolymers were characterized by DSC, SEC, DMA and ¹³C NMR. The Hf-catalysed E/P polymerizations showed much lower activities than the corresponding Zr-catalysed polymerizations but gave polymers with high molar mass. The Hf-based copolymers also showed two melting peaks which may be indicative of several active sites of the catalyst. A comparison of E/P copolymers, containing about 20 mol-% propylene and produced with Zr, Hf and homogeneous V-catalysts, respectively, indicated that the Hf and V-catalysts gave material more similar to each other. The E/O copolymers produced with Zr-catalysts gave very low molar masses and the reactivity ratios, calculated from the NMR data, indicated that the Hf-catalyst has a slightly higher reactivity for 1-octene and the Zr-catalyst some better reactivity for ethylene. Segregation fractionation studies by DSC indicated that a lower 1-octene feed gives more heterogeneous copolymers and the DMA measurements reveal the existence of a linear correlation between the 1-octene content and the intensity of the tan δ_max peak.     

Preparation of polypropylene‐based nanocomposites using nanosized MCM‐41 as support and in situ polymerization

MCM‐41 nanoparticles were used for preparing nanocomposites through the in situ polymerization of propylene. The performance of the catalytic system and the final properties of the materials obtained are highly dependent on the methodology used for impregnation of the catalyst onto the support particles, and therefore an optimization study for the impregnation methodology of the catalyst (Me₂Si(Ind)₂ZrCl₂) was carried out. Two different methodologies were used; the results in terms of catalytic activity and polymer molecular masses indicated that the most promising one involved the pre‐activation of the catalyst with the cocatalyst, methylaluminoxane, followed by impregnation onto the MCM‐41 nanoparticles. Thus, an optimized route for the preparation of polypropylene nanocomposites achieving significant improvements in catalyst activity was developed. The nanocomposite materials were characterized by GPC, TGA and DSC. The dispersion state and the size of the nanoparticles incorporated in the polypropylene matrix were investigated by transmission electron microcopy. Additionally, this methodology allows simultaneous control of the desired amount of support and the concentration of catalyst to be used in the in situ polymerization. © 2015 Society of Chemical Industry     

Preparation and properties of ethylene/POSS copolymer with rac‐Et(Ind)2ZrCl2 catalyst

The various monovinyl‐functional polyhedral oligomeric silsesquioxane (POSS) monomers had been copolymerized with ethylene (E) using rac‐Et(Ind)₂ZrCl₂ and a modified methylaluminoxane (MMAO) cocatalyst. The unreacted POSS monomer could be removed completely by washing the copolymerization product with n‐hexane. And the copolymers were characterized with ¹H NMR, TEM, DSC, TGA, and GPC to know the composition, thermal properties, molecular weight and its distribution, respectively. According to ¹H NMR data, the monomer reactivity ratios of various POSS monomers were calculated by the Fineman‐Ross and Kelen‐Tudos methods. Thermogravimetric analysis of E/POSS copolymers exhibited an improved thermal stability with a higher degradation temperature and char yields, demonstrating that the inclusion of inorganic POSS nanoparticles made the organic polymer matrix more thermally robust. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Modification of a Ziegler-Natta catalyst with a metallocene catalyst and its olefin polymerization behavior

A Ziegler-Natta catalyst was modified with a metallocene catalyst and its polymerization behavior was examined. In the modification of the TiCl₄ catalyst supported on MgCl₂ (MgCl₂-Ti) with a rac-ethylenebis(indenyl)zirconium dichloride (rac-Et(Ind)₂ZrCl₂, EIZ) catalyst, the obtained catalyst showed relatively low activity but produced high isotactic polypropylene. These results suggest that the EIZ catalyst might block a non-isospecific site and modify a Ti-active site to form highly isospecific sites. To combine two catalysts in olefin polymerization by catalyst transitioning methods, the sequential addition of catalysts and a co-catalyst was tried. It was found that an alkylaluminum like triethylaluminum (TEA) can act as a deactivation agent for a metallocene catalyst. In ethylene polymerization, catalyst transitioning was accomplished with the sequential addition of bis(cyclopentadienyl)zirconium dichloride (Cp₂ZrCl₂)/methylaluminoxane (MAO), TEA, and a titanium tetrachloride/vanadium oxytrichloride (TiCl₄/VOCl₃, Ti-V) catalyst. Using this method, it was possible to control the molecular weight distribution (MWD) of polyethylene in a bimodal pattern. In the presence of hydrogen, polyethylene with a very broad MWD was obtained due to a different hydrogen effect on the Cp₂ZrCl₂ and Ti-V catalyst. The obtained polyethylene with a broader MWD exhibited more apparent shear thinning.     

Long Chain Branched Polypropene Prepared by Means of Propene Copolymerization with 1,7‐Octadiene Using MAO‐Activated rac‐Me2Si(2‐Me‐4‐Phenyl‐Ind)2ZrCl2

Small amounts of 1,7‐octadiene (OD) comonomer, ranging from 0.5–5.0 mol‐%, were added during propene polymerization, catalyzed with methylalumoxane (MAO) activated rac‐Me₂Si(2‐Me‐4‐phenyl‐Ind)₂ZrCl₂ (MPI), in order to incorporate long chain branches and small amounts of high molecular mass polypropene (PP), thus improving melt processability of isotactic metallocene‐polypropene. As a function of the OD content the PP melting temperatures varied from 120 to 160°C. The presence of long chain branches was reflected by increased zero shear viscosities combined with pronounced shear thinning behavior in the case of propene/OD copolymers with molecular mass distribution of M̄_w/M̄_n < 4. Rheological measurements clearly revealed crosslinking occurring at high OD content. OD addition impaired catalyst activities. However, in the presence of trace amounts of ethene, catalyst activities increased significantly even in the presence of high OD content.     

Propylene polymerization using combined syndio‐ and isospecific metallocene catalysts supported on silica/MAO

Syndiotactic and isotactic polypropylene were produced using the metallocene compounds Ph₂C(Flu)(Cp)ZrCl₂ and SiMe₂(2‐Me,4‐Ph‐Ind)₂ZrCl₂ in homogeneous system and supported on silica/MAO. These catalysts were evaluated either isolated or as a binary system. In the latter case, the iso‐ and syndiospecific metallocene complexes were immobilized together during the preparation of the supported catalyst. In a further experimental set, the syndio‐ and isospecific isolated heterogeneous catalysts were mixed at the moment of propylene polymerization. The polypropylenes obtained were evaluated using differential scanning calorimetry. The catalytic activities were also investigated. At all the studied polymerization temperatures, the results showed that the binary catalyst produced polypropylenes with lower melting temperatures in comparison with those obtained when the mixture of isolated supported syndio‐ and isospecific catalysts was employed. Moreover, the activation energies for the polymerization of all catalysts systems were calculated, resulting in a lower value for the binary system when compared to that employing the catalyst mixture and to both the isolated supported metallocene catalysts. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 628–637, 2006     

Comparative study of propylene polymerization using Me2Si(RInd)2ZrCl2/SiO2-SMAO/AlR3 and Me2Si(RInd)2ZrCl2/MAO (R = Me, H)

A mechanistic analysis of propylene polymerization was performed, in which the catalyst system was Me₂Si(R¹Ind)₂ZrCl₂/SMAO/AlR₃² (in situ supported catalyst onto MAO-modified silica) or Me₂Si(R¹Ind)₂ZrCl₂/MAO (homogeneous), where R¹ = H or CH₃, cocatalyzed by AlR₃² = TEA (triethylaluminum), IPRA (isoprenylaluminum), or TIBA (triisobutylaluminum). The catalyst activity of the homogeneous system Me₂Si(2-Me-Ind)₂ZrCl₂/MAO was almost 8 times higher than that observed for Me₂Si(Ind)₂ZrCl₂/MAO (38 vs 4.6 kg PP/g cat h), while the polypropylene molar mass was 3 times higher (M_w: 93 vs 34 kg/mol). Conversely, the in situ supported systems Me₂Si(Ind)₂ZrCl₂/SMAO/AlR₃ and Me₂Si(2-Me-Ind)₂ZrCl₂/SMAO/AlR₃ showed similar activities, ranging from 0.2 to 1.5 kg PP/g cat h. The molar mass of the resulting polymers prepared using the in situ procedure was dependent on the AlR₃ nature and on the Al/Zr ratio. Generally, the heterogeneous catalysts produced PP with higher molecular weights than that obtained with homogeneous ones. The influence of the alkylaluminum, used as the cocatalyst, on the chain-transfer termination reaction to the alkyl compound was evident from the activity and the molecular weight of the produced polymers.     

Synthesis of 1-hexene/1,7-octadiene copolymers using coordination polymerization and postfunctionalization with triethoxysilane

Homo- and copolymerization of 1-hexene (H) and 1,7-octadiene (O) were done using two different catalysts 1,4-bis(2,6-diisopropylphenyl)acenaphthenediiminedibromo nickel (II) and rac-ethylenebis(indenyl)zirconium dichloride [rac-Et(Ind)₂ZrCl₂]. The metallocene catalyst showed higher activity than the nickel α-diimine catalyst in homo- and copolymerization. The ¹H NMR studies confirmed the formation of copolymers containing 8–47% of 1,7-octadiene. In the copolymerization of hexene and diene, as the amount of incorporated diene in the copolymers increased, their T _g increased. TGA results showed that thermal stability of the polymer increases with the increase of 1-hexene incorporation in the polymer chain. Finally 1-hexene/1,7-octadiene copolymers were functionalized by triethoxysilane in the presence of hexachloroplatinic acid. The ¹H NMR spectrum of the functionalized samples showed that the double bonds in the copolymer structure were completely eliminated. The DSC analysis showed higher T _gs for the functionalized copolymer. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48934.