50 Years of Chemistry in Opole

Coordination (co)polymerization of olefins Marzena BIAŁEK*, Wioletta OCHĘDZAN-SIODŁAK, Katarzyna DZIUBEK, Krystyna CZAJA, Kornelia BOSOWSKA – Department of Chemical Technology and Polymer Chemistry, Faculty of Chemistry, Opole University, Opole, Poland Please cite as: CHEMIK 2014, 68, 4, 268–279

Introduction Middle 1950s may be treated as the beginning of the age of plastics – their global production in last 60 years have increased from approx. 1.5 mln to almost 290 mln tons. The dominating position in production and consumption of these materials for many years has been occupied by polyolefins (in Europe 48% from 57 mln tons of plastics) [1]. Forecasters predict that in coming years this trend will not change, as produced olefin polymers have wide range of diverse properties while the access to resources is easy and requirements for labour intensity and energy consumption are low, what results in low price. Polyethylene can be produced in the high-pressure process known since 1930s, where pressure of up to 300 MPa and temperature of up to 300°C [2] are applied, and reaction progresses according to radical mechanism. It can be also obtained in medium pressure process with use of Philips chromium catalysts [3]. However, there is no doubt that such crucial role of polyolefins in modern world results mainly from the early 1950s discovery and subsequent commercialization of organometallic Ziegler-Natta catalysts for polymerization of ethylene, propylene and higher olefins. Since then, intensive studies have been carried out both by academic and industrial research centres on development of new organometallic systems of increasing activity and especially of greater controllability over properties of polyolefin products. In these studies researchers from the Department of Chemical Technology and Polymer Chemistry of the Institute of Chemistry and since 2008 of the Faculty of Chemistry of Opole University (till 1994 State Higher Pedagogical College) have been participating almost from the very beginning – first under the guidance of prof. Maria Nowakowska and currently of prof. Krystyna Czaja. At this moment this is the only Polish research centre working in this research field. Olefin polymerization and copolymerization using Ziegler-Natta and metallocene catalysts Ethylene polymerization Activity of catalyst discovered by Ziegler et al., which was produced in reaction of titanium tetrachloride with triethylaluminum or diethylaluminium chloride and later developed for industrial process, was low, below 5 kg of polyethylene from 1 gram of titanium [2]. This catalyst, together with Natta catalyst for propylene polymerization, has been evolving over the years. However, only anchoring of Ziegler-Natta catalysts on appropriately modified MgCl2, where they have proven to be especially active, have enabled effective ethylene polymerization and have allowed to simplify polymerization process at the industrial scale [4]. In our studies, TiCl4 was immobilized on magnesium support in a form of complex of magnesium chloride with tetrahydrofuran. This results in very stable and active catalyst [5]. The use of bimetallic support [MgCl2(THF)2/AlEt2Cl] led to obtaining even more active catalytic system and at the same time confirmed that titanium Corresponding author: Marzena BIAŁEK, Ph.D., D.Sc., e-mail: [email protected]

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compound in developed systems is not incorporated into crystal structure of magnesium chloride [6, 7]. Application of this support for immobilization of vanadium compounds VCl4 and VOCl3 limited disadvantageous reduction of transition metal by organoaluminium compound and have resulted in highly stable catalytic systems of activity significantly higher than activity of respective titanium catalyst [8, 9]. Furthermore, polyethylene produced using vanadium system might be considered as a product of type UHMW-PE (ultrahigh-molecular-weight polyethylene), as its molecular weight reaches value of several millions g/mole (Tab. 1) [8, 10]. Polymers of such high molecular weight have number of advantageous physicochemical and mechanical properties compared to typical HD-PE. Particularly, very high abrasion and cracking resistance, good impact strength and resistance to frost, low friction coefficient and they maintain these properties in wide range of temperatures [10, 11]. Possibility of producing polyethylene of particularly high molecular weight using supported vanadium system results probably from the presence of oxygen atom in the direct vicinity of active site. Such cause is also indicated by the formation of UHMW-PE in process carried out with titanium catalysts with alkoxy ligands [12, 13] and titanium catalyst supported on Al2O3 [14, 15]. The latter system allows to obtain PE of molecular weight up to 6×106 g/mole. The 1980s discovery of homogeneous catalysts based on metallocene compounds, activated by methylaluminoxane or by boron compounds, allowed to synthesise PE with extremely high activities, e.g polyethylene was obtained using Cp2ZrCl2/MAO with yield equal to 25·106 gPE/(gZr·h·atm) [16]. Moreover, in contrast to multi-site Ziegler-Natta catalysts, metallocene catalyst have uniform active sites (being so called single-site catalysts) what as a result leads to the formation of uniform products of homo- and copolymerization in terms of both molecular weight chemical composition distribution. At the same time, other properties change, e.g. their transparency and strength improve [17]. Low molecular weight of metallocene polymers (which is connected to the phenomenon of contaminating reactor with low molecular weight fraction, so called reactor fouling), necessity to use large excess of expensive activator (MAO), low stability in the course of polymerization, as well as impossibility to use homogeneous systems in existing industrial installations, in which process usually occurs in suspension or gas phase, have resulted in the start of extensive research in the field of heterogenization of metallocene systems by immobilizing them on support. Various research groups have used for that mainly silica of different characteristics [18,  19], while our group for heterogenization of metallocene complex used magnesium supports [20÷25] commonly used in Ziegler-Natta systems and in metallocene systems considered only marginally due to i.a. problem of desorption of complex from the support surface. Other papers have shown that magnesium compounds may not only be successfully used for immobilization of metallocene, but at the same time play role of an activator [26]. Research carried out at FCh OU involved using as support magnesium compounds in the form of complex of magnesium

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chlorodiethylaluminium [24], that did not undergo disactivation for at least 90 minutes of reaction and moreover gave product of advantageous properties (higher molecular weight and bulk density) in comparison to product obtained with homogeneous system (Tab. 1) [24]. Table 1

Effect of support on activity of successive generations of catalysts used for ethylene polymerization and on properties of obtained polyethylene Ziegler-Natta catalysts Type of system

Non-supported system

Type of transition metal compound

Support Activator Activity kgPE·(molMt)-1

Polyethylene properties

References *)

Supported system

catalysts

Supported

Non-supported system

VOCl3

system

Supported

Non-supported system

system

Supported

Non-supported system

system

Cp2ZrCl2

MgCl2(THF)2

-

Post-metallocene

Metallocene catalysts

MgCl2(THF)2/ Et2AlCl

-

Et2AlCl

-

MAO

MgCl2(THF)0,32(Et2AlCl)0,36

-

MAO

MgCl2(THF)2/ Et2AlCl Et2AlCl

76

944

6225

101*)

21

168*)

63

2617

Tt=138.6oC

Tt=141.3oC

Tt=133.5oC

-

Tt=134.2oC

Tt=138.4oC

Tt=138.3oC

Tt=136.4oC

-

-

χ=63.9%

-

χ=72.8%

χ=57.3%

χ=66.5%

χ=52.8%

Mv=1400·103

Mv=2340·103

Mw=94.1·103

Mw=135.6·103

Mw=360·103

Mw=1152·103

-

Mw=1318.8·103

-

-

Mw/Mn=1.4

-

Mw/Mn=6.9

Mw/Mn=9.1

-

Mw/Mn=8.2

[8]

[8]

[20]

[23]

[43]

[43]

[38]

[38]

unpublished data

Ethylene copolymerization Properties of PE, mainly its density and crystallinity might be modified by copolymerization of ethylene with higher 1-olefin, obtaining in this way linear low density polyethylene (LLD-PE). However, the controllability of polymer properties in processes catalysed by Ziegler-Natta systems is limited, as comonomer incorporation into polyethylene chain is small. Vanadium catalysts proved to be definitely more effective than titanium catalysts in this regard (Tab. 2) [27, 28]. While metallocene catalysts have shown not only higher yield of copolymerization, but at the same time allowed to obtain products of much higher degree of comonomer incorporation and of high composition uniformity. Furthermore, catalytic properties in this process might be controlled by modification of catalyst structure. For copolymerization, zirconium was found to be most favourable metallic site in metallocene, presence of titanium not only has negative impact on comonomer incorporation efficiency, but also leads to production of copolymers of broad composition distribution (Tab. 2) [20]. Due to that zirconocene systems (of various cyclic ligand structure and linking bridges) are mainly studied and applied in copolymerization processes. Among complexes containing in their structure ligands Cp, Me5Cp, t-BuCp, n-BuCp, i-PrCp, the highest amount of comonomer 10 %mol, for comonomer concentration in reaction environment equal to 0.82 mole/dm3, is incorporated when using catalyst t-BuCp2ZrCl2/MAO.

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This is due to the fact that this metallocene contains more rigid cyclic ligands of different bending angles and as a consequence it is easier for comonomer to reach active site [20]. At the same time copolymerization leads to significant change in product properties, e.g. decrease of molecular weight (from 61 kg/mole to 3.8 kg/mole) and melting point (from 132 to 101°C) [20]. Immobilized metallocene catalysts usually have lower ability to incorporate higher olefin into polyethylene chain. Steric hindrance caused by support hinders larger comonomer molecule insertion into active site, which decreases incorporability regardless of the type of used support (magnesium or silica) [20, 21, 24]. On the other hand, when using heterogeneous catalysts it is possible to obtain copolymers with higher molecular weights than for their homogeneous analogues for the same comonomer content [20]. Zirconocene catalysts containing bridge linking cyclic ligands proved to be effective in copolymerization of ethylene with large comonomers, e.g. silsesquioxanes containing vinyl groups. Preliminary studies on copolymerization with such comonomers indicate decrease of polymer melting points and degree of crystallinity, in comparison to respective polyethylene, change of product morphology, and – what is even more important – improvement of polymer thermal properties [29]. Such promising results have caused that current research on copolymerization of ethylene with silsesquioxane monomers (POSS) is continued on larger scale.

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chloride with tetrahydrofuran or methyl alcohol, additionally modified with simple organoaluminium compound, as well as silica-based support produced in sol-gel synthesis [22, 24]. One system proved to be most effective and fully heterogeneous – system immobilized on MgCl2(THF)2 modified with

50 Years of Chemistry in Opole

Table 2 Ethylene copolymerization with a-olefin in the presence of supported and non-supported organometallic catalysts Ziegler-Natta catalysts

Catalytic system

MgCl2(THF)2/ VCl4/Et2AlCl

Metallocene catalysts

MgCl2(THF)2/ TiCl4/Et2AlCl

(t-BuCp)2 ZrCl2/MAO

Post-metallocene catalysts

MgCl2(THF)2-TIBA/ Cp2TiCl2/MAO MgCl2(THF)0,32(Et2AlCl)0,36/ Me3Al

Comonomer Activity kgPE·(molMt)-1 Comonomer content in copolymer

1-hexene, 0.06 mol·dm-3

1-hexene, 0.11 mol·dm-3

1-hexene, 0.43 mol·dm-3

1-hexene, 0.43 mol·dm-3

7743

1382

5000

0.47

0.57

-

MgCl2(THF)2Et2AlCl/ MAO

1-octene,

1-octene,

1-octene,

0.75 mol·dm-3

0.43 mol·dm-3

0.21 mol·dm-3

1700

18

173

4312

8.85

1.42

4.70

0.87

0.71

Tt=137.6oC

Tt=111.6oC

Tt=137.7oC

Tt=122.1oC

Tt=133.4oC

Tt=139.9oC

-

-

χ=46.3%

χ=30.4%

χ=31.1%

χ=56.2%

χ=46.7%

-

-

Mw=5.3·103

Mw=450.3·103

Mw=1136·103

Mw=806·103

-

-

-

Mw/Mn=1.6

Mw/Mn=6.4

Mw/Mn=144.5

Mw/Mn=10.5

-

[27]

[37]

[20]

[20]

[40]

[43]

[38]

mol%

Co-polymer properties

References

Characterization of ethylene/1-olefin copolymers Copolymers obtained using organometallic catalysts of the same qualitative and quantitative composition might differ in terms of chemical composition distribution (CCD). For its characterization preparative methods such as TREF (Temperature Rising Elution Fractionation) [30] can be used, as well as analytical ones, including methods based on DSC [31]. Characterization of composition distribution of ethylene/1-hexene copolymers obtained with supported vanadium Ziegler-Natta and metallocene catalysts by means of one DSC technique, i.e. successive self-nucleation/annealing method (SSA) allowed to conclude that least uniform in terms of chemical composition are copolymers obtained with Ziegler-Natta catalysts, while products obtained using supported metallocene catalysts are more uniform, but still are inferior in this respect to copolymers produced using homogenous metallocene systems [32]. The latter catalysts, despite that they are called single-site, do not give completely uniform copolymerization products, wherein their non-uniformity depends on metallocene structure [33]. Post-metallocene catalysts in copolymerization of olefins Non-supported catalysts New generation of catalysts containing spatially extended ligands other than metallocene, usually multidonor due to the chronology are commonly called post-metallocene catalysts. Such catalysts containing ligands of type [ONNO] and [ON]: salen [34÷36], salan [37], phenoxyimine [34, 38] and diamino-bis(phenolate) [37], their synthesis and characterization of their catalytic properties in olefin homo- and copolymerization are also subject of our research. The properties of these complexes in ethylene polymerization depend to great extent on type of complexed transition metal (vanadium, titanium, zirconium) and type of used activator. 276 •

Vanadium complexes proved to be most active after application of EtAlCl2 as activator, while the same was true for titanium complexes in combination with Et2AlCl, wherein latter were also quite active after activation with MAO. Whereas polymer was generated in the presence of zirconium complexes only when activated by MAO. The properties of ethylene polymerization products depend also on the transition metal type and type of activator. Linear high molecular weight polyethylenes are produced in the presence of vanadium catalysts, regardless of activator and ligand type, while for titanium systems – if organoaluminium activator is halogen-free (Tab. 1). In the presence of titanium complexes having salen or phenoxy-imine ligands activated by Et2AlCl PE of low molecular weight is produced and oligomer mixture is formed as a by-product. We found that differences in properties of products obtained using various activators result from different reactions leading to termination of polymer chain. In the processes with presence of vanadium complexes, β-hydrogen elimination and/ or chain transfer to monomer reactions occur, leading to formation of vinyl terminal groups in macromolecules, while for titanium complexes activated with Et2AlCl additional termination reaction occurs involving organoaluminium cocatalyst [39]. When salan complexes activated with Et2AlCl are used, bimodal polyethylene is formed consisting of two fractions of very narrow molecular weight distribution and very high difference of molecular weights – Mw is of order million and several thousands. Average fraction molecular weights and their percentage can be modified by changing the structure of salan ligand. Discussed complexes are also active in copolymerization [37, 40], wherein titanium catalysts regardless of comonomer concentration give copolymers, while vanadium catalysts for high comonomer concentrations give product mixture, including polyethylene. Higher olefin homopolymers synthesized using salen complexes also exhibit interesting properties. Such process leads

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Supported catalysts Potential application of post-metallocene catalysts, similarly to metallocene ones, in industrial processes occurring in gas or suspended phase usually used in low-pressure olefin polymerization would be impossible. This results mostly from the fact that these catalysts give polymers of wrong morphology and low bulk density. Therefore, they must be immobilized on support. Studies carried out in this field with the use of titanium salen complex [42] have shown that silica supports regardless their surface properties and modification methods are not suitable support for such precursors, mainly due to their low activity. Supported catalysts of very high activity are produced only after immobilization of salen and bis(phenoxy-imine) complexes on magnesium support (Tab.  1) [38, 43÷45]. Additional advantage of systems immobilized on MgCl2(THF)2 and MgCl2(EtOH)3,4 modified with organoaluminium compounds, mainly titanium systems, is their long-term stability as well as thermal stability. Supported catalysts might be activated both by simple organoaluminium compounds of type R3Al, where R=CH3 or C2H5, as well as MAO, in both cases showing equally high efficiency. Moreover, anchoring these complexes on supports reduces probability of chain transfer reaction, what results in great increase of obtained polymers molecular weight. As a result polymer of type UHMWPE is obtained of molecular weight of order several millions g/mole. Immobilization also significantly improves morphological properties of polymers, mainly there is significant increase of bulk density. Supported titanium and vanadium catalysts are also active in co-polymerization of ethylene with higher 1-olefin, but their comonomer incorporability is low [40]. Application of ionic liquids in ethylene polymerization The alternative solution to anchoring organometallic catalysts on solid support is their immobilization in ionic liquid being one of the phases of the two-phase systems for ethylene polymerization. In our studies, conducted in the Department of Chemical Technology and Polymer Technology UO, various imidazolium and pyridinium chloroaluminate ionic liquids were used as one of the phases in two-phase (ionic liquid/hexane) ethylene polymerization conducted in presence of metallocene catalyst (Cp2TiCl2) [46÷52]. Certain advantages of such ethylene polymerization are following: easy separation of the pure product by means of simple decantation, elimination of the necessity to use aromatic solvents and expensive MAO as tytanocene activator and replacing it with cheaper, traditional organoaluminium compound (AlEtCl2 or AlEt2Cl). Furthermore,

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possibility of multiple use of catalytic system in successive polymerization cycles confirmed high stability and immobilization durability of metallocene catalyst in ionic liquid phase [47÷52]. Among used ionic liquids, the best results were obtained when following ionic liquids were used: 1-n-alkylpyridinium chloroaluminate [Cn-py][AlCl4] [52] and mixture of ionic liquids [C4-mim][AlCl4]/ [Ph-C2mim][AlCl4] – their application provided both high activity of catalysts (reaching approx. 200 and 350 kgPE·(molTi·h)-1, respectively) [50], as well as important for two-phase catalysis, easy transfer of produced polyethylene between phases and separation of phases after reaction completion. The unique feature of polyethylene obtained in two-phase polymerization using some of ionic liquids is its very high degree of crystallinity (reaching 98%) and important, from technological perspective, advantageous morphological properties including large bulk density (~500 g/dm3) and very regular shape of granules [49, 50] typical for polyethylene obtained in process involving supported metallocene system [19, 53]. Pyridinium and imidazolium chloroaluminate ionic liquids were also found to be useful media for immobilization of titanium and vanadium catalysts containing phenoxy-imine and salen ligands. The course of polyreaction carried out in such systems depended mostly on the type of metallic active site of used post-metallocene catalyst – in the presence of titanium complex mixture of oligomers was obtained, while for vanadium – polyethylene of average molecular weight equal to approx. 500·103 g/mole [37]. The promising method allowing to improve efficiency of polymerization process and wider use of metallocenes, postmetallocenes and ionic liquids might be use of the concept of Supported Ionic Liquids Phase (SILP) [54, 55]. The Opole group developed procedure of heterogenization of metallocene and postmetallocene catalysts involving immobilization of transition metal compounds in ionic liquid deposited on silica support. The activity of systems SILP with Cp2TiCl2 exceeded 1000 kgPE·(molTi·0,5h)-1 [56] – this was greatly superior to two-phase systems and was comparable to the activity achieved for supported titanocene catalysts [57, 58]. Thereby, application of SILP systems in ethylene polymerization allowed to combine benefits related to application of ionic liquid, solid support and organometallic catalysts. Summary Huge demand for environmentally friendly polyolefins with favourable advantageous properties contributes to continuous growth of research on development of new efficient organometallic catalysts for olefin polymerization. Low-pressure polymerization of olefins with use of organometallic catalysts and characterization of resulting product properties are a subject of constant research works in many laboratories worldwide, including Opole group. This search for more and more active catalytic systems for olefin polymerization and copolymerization that allow control in wide range of polyreaction course and obtaining polymers of planned structural and functional properties to great extent determines development of existing polyolefin technologies and promotes constant expansion of their applications fields. References 1. Plastics – Facts 2013. An analysis of European latest plastics production, demand and waste data, study of Association of Plastics Manufacturers, Plastics Europe, Polish version http://www.plasticseurope.pl/Document/ tworzywa-sztuczne---fakty-2013.aspx?FolID=2 2. Böhm L.L.: The ethylene polymerization with Ziegler catalysts: fifty years after the discovery. Angew. Chem. Int. Ed. 2003, 42, 41, 5010–5030. 3. Weckhuysen B.M., Schoonheydt R.A.: Olefin polymerization over supported chromium oxide catalysts. Catal. Today 1999, 51, 2, 215–221. 4. Barbé P.C., Cecchin G., Noristi L.: The catalytic system Ti-complex/MgCl2. Adv. Polym. Sci. 1986, 81, 1–81.

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to formation of atactic product of high molecular weight of order several hundred thousands, but unfortunately with low yield [41]. Slightly different properties are exhibited by titanium and zirconium diamino-bis(phenolane) complexes [37], which despite that they do not show high activity in ethylene polymerization, are very active in polymerization of higher 1-olefins, whereas product molecular weights, that can be in range from hundreds to hundreds of thousands g/mole, as well as chain microstructures are determined by catalyst structure and activator type. Currently we are commencing research on catalytic properties of new, not used before for olefin (co)polymerization, organometallic catalysts based on complexes containing silsesquioxanes as ligands, and metals of earlier (Zr, Ti, V) and later (Ni, Fe) periodic table groups as metallic site. Used complexes will differ in, among others, POSS structure (i.e. structure of substituents in silicon-oxygen cage and method of bonding with metal). The impact of complex structure, as well as, process conditions including type and content of organoaluminium activator, monomer type and comonomer type and concentration on system activity and product properties will be evaluated.

50 Years of Chemistry in Opole

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29. Skotniczny K., Rozpoznawcze badania nad zastosowaniem silseskwioksanów w polimeryzacji olefin. Praca magisterska, Opole 2012. 30. Wild L., Ryle T.R., Knobeloch D.C., Preat I.R.: Determination of branching distributions in polyethylene and ethylene copolymers. J. Polym. Sci. Pol. Phys. 1982, 20, 3, 441–455. 31. Müller A.J., Hernández Z.H., Arnal M.L., Sánchez J.J.: Successive selfnucleation/annealing (SSA): A novel technique to study molecular segregation during crystallization. Polym. Bull. 1997, 39, 4, 465–472. 32. Czaja K., Sacher B., Białek M.: Studies of intermolecular heterogeneity distribution in ethylene/1-hexene copolymers using DSC method. J. Thermal. Anal. Cal. 2002, 67, 3, 547–554. 33. Białek M., Czaja K., Sacher-Majewska B.: Studies of structural composition distribution heterogeneity in ethylene/1-hexene copolymers using thermal fractionation technique (SSA). Effect of catalyst structure. Thermochim. Acta 2005, 429, 2, 149–154. 34. Białek M., Czaja K., Szydło E.: Transition metal complexes of tetradentate and bidentate Schiff bases as catalysts for ethylene polymerization: Effect of transition metal and cocatalyst. J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 2, 565–575. 35. Białek M., Czaja K.: Metal salen complexes as ethylene polymerization catalysts – effect of catalytic system composition on its activity and properties of polymerization products. Polimery 2008, 53, 5, 364–370. 36. Białek M., Czaja K.: Dichlorovanadium(IV) complexes with salen-type ligands for ethylene polymerization. J. Polym. Sci. Part A: Polym. Chem. 2008, 46, 20, 6940–6949. 37. Unpublished results 38. Krasuska A., Białek M., Czaja K.: Ethylene polymerization with FI complexes having novel phenoxy-imine ligands: effect of metal type and complex imobilization. J. Polym. Sci. Part A: Polym. Chem. 2011, 49, 7, 1644–1654. 39. Białek M.: Effect of catalyst composition on chain-end-group of polyethylene produced by salen-type complexes of titanium, zirconium and vanadium. J. Polym. Sci. Part A: Polym. Chem. 2010, 48, 14, 3209–3214. 40. Białek M., Czaja K., Pietruszka A.: Ethylene/1-olefin copolymerization behaviour of vanadium and titanium complexes bearing salen-type ligand. Polym. Bull. 2013, 70, 5, 1499–1517. 41. Białek M., Bisz E.: A comparative study on the polymerization of 1-octene promoted by vanadium and titanium complexes supported by phenoxyimine and salen type ligands. J. Polym. Res. 2013, 20, 164, DOI: 10.1007/ s10965–013–0164-y. 42. Białek M., Garłowska A., Liboska O.: Chlorotitanium(IV) tetradentate schiff-base complex immobilized on inorganic supports: support type and other factors having effect on ethylene polymerization activity. J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 18, 4811–4821. 43. Białek M., Pietruszka A.: Titanium(IV) chloride complexes with salen ligands supported on magnesium carrier: synthesis and use in ethylene polymerization. J. Polym. Sci. A Polym. Chem. 2009, 47, 23, 6693–6703. 44. Białek M., Liboska O.: Vanadium complex with tetradentate [O,N,N,O] ligand supported on magnesium type carrier for ethylene homopolymerization and copolymerization. J. Polym. Sci. Part A: Polym. Chem. 2010, 48, 2, 471–478. 45. Białek M., Pietruszka A.: Ethylenebis(5-chlorosalicylideneiminato)vanadium dichloride immobilized on MgCl2-based supports as a highly effective precursor for ethylene polymerization. J. Polym. Sci. Part A: Polym. Chem. 2009, 47, 14, 3480–3489. 46. Ochędzan-Siodłak W., Sacher-Majewska B.: Biphasic ethylene polymerisation using ionic liquid over a titanocene catalyst activated by an alkyl aluminium compound. Eur. Polym. J. 2007, 43, 8, 3688–3694. 47. Ochędzan-Siodłak W., Dziubek K., Siodłak D.: Biphasic ethylene polymerisation using 1-n-alkyl-3-methylimidazolium tetrachloroaluminate ionic liquid as a medium of the Cp2TiCl2 titanocene catalyst. Eur. Polym. J. 2008, 44, 11, 3608–3614. 48. Ochędzan-Siodłak W., Dziubek K., Czaja K.: Comparison of imidazolium and pirydinium ionic liquids as mediums of the titanocene catalyst for biphasic ethylene polymerization. Polimery 2009, 54, 7–8, 501–506. 49. Ochędzan-Siodłak W., Dziubek K., Czaja K.: Effect of immobilization of titanocene catalyst in aralkyl imidazolium chloroaluminate media on performance of biphasic ethylene polymerization and polyethylene properties. Polym. Bull. 2013, 70, 1, 1–21.

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Prof. Krystyna CZAJA, Ph.D., D.Sc., Eng. has graduated in 1970 from the Faculty of Chemical Technology and Engineering of the Silesian University of Technology. She received academic titles from the Faculty of Chemistry of the Warsaw University of Technology: Ph.D. degree (1977) and the title of D.Sc. of chemical sciences (1992). She received full professorship in the field of chemical sciences in 2002. She has been working in Opole academy since 1973, currently as full professor in the Faculty of Chemistry of the Opole University. Specialization: polymer chemistry and technology, mainly polyolefins, including synthesis of organometallic catalysts and their application in low-pressure (co)polymerization of olefins, physical and chemical modification of polymers, polymer composites and nanocomposites, characterization of structural, molecular and functional properties of polymer materials, particularly studies of thermo-, photoand biodegradation processes. e-mail: [email protected], +48 77 452 7140

* Marzena BIAŁEK, Ph.D., D.Sc., Assoc. Prof. of OU is a graduate of the Faculty of Physics, Mathematics and Chemistry of the State Higher Pedagogical College in Opole (1994). She received her Ph.D. degree from the Faculty of Mathematics, Physics and Chemistry of the Opole University, while the title of D.Sc. from the Faculty of Chemistry of the Warsaw University of Technology. Currently she works in the Faculty of Chemistry of the Opole University (Department of Chemical Technology and Polymer Chemistry) as Associate Professor. Scientific interests: polymer chemistry, in particular synthesis and characterization of polyolefins and catalysts used in their synthesis. e-mail: [email protected], +48 77 452 7145

Wioletta OCHĘDZAN-SIODŁAK, Ph.D. is a graduate of the Faculty of Mathematics, Physics and Chemistry of the University of Opole (1996). She received her Ph.D. degree in 2004 from the Faculty of Mathematics, Physics and Chemistry of the Opole University. Currently she works in the Department of Chemical Technology and Polymer Chemistry of the Opole University as a lecturer. Scientific interests: heteregeneous catalysis, polymer chemistry. e-mail: [email protected], +48 77 452 7147

Katarzyna DZIUBEK Ph.D. is a graduate of the Faculty of Mathematics, Physics and Chemistry of the Opole University (2008). She received her Ph.D. degree in 2013 from the Faculty of Chemistry of the Opole University. Currently she works in the Department of Chemical Technology and Polymer Chemistry of the Opole University as a research assistant. Scientific interests: organometallic chemistry, polymer chemistry. e-mail: [email protected], +48 77 452 7147

Kornelia BOSOWSKA, Ph.D. is a graduate of the Faculty of Physics, Mathematics and Chemistry of the State Higher Pedagogical College in Opole (1988). She obtained her Ph.D. degree from the Faculty of Physics, Mathematics and Chemistry of the Opole University in 1996. Currently she works in the Department of Chemical Technology and Polymer Chemistry of the Opole University as lecturer. Scientific interests: coordination polymerization, living and controlled polymerization, stimuli responsive polymers. e-mail: [email protected], +48 77 452 7143

Aktualności z firm News from the Companies Dokończenie ze strony 273 NOWE INWESTYCJE Kluczowe inwestycje Grupy Azoty S.A. Grupa Azoty SA rozpoczyna realizację inwestycji w segmentach tworzywowym i nawozowym. Sztandarowe inwestycje – Wytwórnia Poliamidu 6 i Instalacja Granulacji Mechanicznej II – o łącznym budżecie około 460 mln PLN zostaną oddane do użytku w 2016 r. Nowe instalacje zapewnią zatrudnienie 110 pracownikom. Spółka posiada już wszystkie wymagane zgody korporacyjne do prowadzenia tych procesów. Wytwórnia Poliamidu 6 o zdolności produkcyjnej 80 tys. ton/rok i budżecie do 320 mln PLN będzie realizowana ze środków własnych oraz kredytu bankowego. Inwestycja sąsiadująca bezpośrednio z istniejącą wytwórnią PA6 ma być zlokalizowana w rozszerzanej obecnie podstrefie Specjalnej Strefy Ekonomicznej na powierzchni 3,5 ha. Decyzja o jej realizacji jest konsekwencją konsolidacji mocy produkcyjnych kaprolaktamu w Grupie Azoty i będzie stanowić odpowiedź na skokową zmianę jaka nastąpiła w ostatnim czasie

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na rynku tego produktu w świecie. Tymczasem w Polsce, ze względu na rosnącą rolę przemysłu samochodowego i innych branż opartych na włóknach konstrukcyjnych zauważyć można rosnące zapotrzebowanie na tworzywa. Na rynku zauważyć też można wzrastającą rolę małych i średnich prywatnych, często rodzinnych firm, które korzystają z lokalnej bazy poliamidów i kompozytów. Tarnowska Spółka ma szansę stać się regionalnym centrum zaopatrzenia w te półprodukty. Kolejnym rozpoczynanym zadaniem jest instalacja Granulacji Mechanicznej II, której celem  zgodnym ze strategią Spółki będzie optymalizacja asortymentu nawozów oraz dalsze podwyższenie wartości produkowanego siarczanu amonu. Zadanie to wycenione jest na kwotę 141 mln zł i podobnie jak wcześniejsza inwestycja realizowane będzie ze środków własnych i kredytu bankowego. Projekt jest kontynuacją działań związanych z obroną pozycji konkurencyjnej firmy na rynku saletrzaku rozpoczętych w latach 2006–2009 poprzez budowę pierwszej Instalacji Granulacji Mechanicznej. (em) (źródło: info. prasowa Grupa Azoty, 1.04.2014 r.)

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50 Years of Chemistry in Opole

50. Ochędzan-Siodłak W., Dziubek K.: Improvement of biphasic polymerization by application of binary ionic liquid mixture. Chem. Eng. Process. 2013, 72, 74–81. 51. Ochędzan-Siodłak W.: Ionic liquids in biphasic ethylene polymerization, in: A. Kokorin (ed.) Ionic liquids: applications and perspectives, Intech, Rijeka, 2011, pp 29–44. 52. Patent application no. P.395396, Poland 53. Heurtefeu B., Bouilhac C., Cloutet É., Taton D.A., Deffieux H., Cramail H.: Polymer support of “single-site” catalysts for heterogeneous olefin polymerization. Prog. Polym. Sci. 2011, 36, 1, 89–126. 54. Mehnert C.P.: Supported ionic liquid catalysis. Chem. Eur. J. 2005, 11, 1, 50–56. 55. Van Doorslaer C., Wahlen J., Mertens P., Binnemans K., De Vos D.: Immobilization of molecular catalysts in supported ionic liquid phases. Dalton Trans. 2010, 39, 36, 8377–8390. 56. Patent application no. P.395396, Poland 57. Sensarma S., Sivaram S.: Polymerization of ethylene using a SiO2–MgCl2 supported bis(cyclopentadienyl)zirconium(IV) or titanium(IV) dichloride catalyst. Polym. Int. 2002, 51, 5, 417–423. 58. Ihm S.-K., Chu K.-J., Yim J.-H.: Molecular weight distribution control with supported metallocene catalysis, in K. Soga, M. Terano (eds) Catalyst design for tailor-made polyolefins, Kodansha Ltd., Tokio, 1994, pp. 299–306.