Patent Publication Number: US-2009233005-A1

Title: Microwave-promoted creation of catalytic species

Description:
This invention relates to the field of creating active catalytic species using microwave energy. 
     Heating and driving chemical reactions by the use of microwave energy has attracted considerable attention in recent years. Until then, safety and reliability issues associated with the flammability of organic solvents in a microwave field and the control of temperature and pressure were major drawbacks, but these have since mostly been overcome. A multitude of organic reactions have thus been performed using microwave energy as illustrated in Angew. Chem. Int. Ed. 2004, 43, 6250-6284: higher uniformity of temperature, leading to less overheating, allowing to limit degradation effects or to produce temperature-sensitive products more efficiently, higher reactions rates, higher productivity and/or better selectivity have often been claimed. These reactions were mainly performed in polar solvents and/or involving polar reagents. 
     The microwave region of the electromagnetic spectrum lies between the region of infrared radiation and radio frequency radiation and roughly corresponds to wavelengths between 1 cm and 1 m or frequencies between 300 MHz and 30 GHz. 
     The energy transfer to chemical entities, instead of occurring by convection or by conduction as in conventional heating, occurs by dielectric loss. Exposure to microwave radiation results in the molecules with polar or ionic moieties attempting to align their charges with the external oscillating electromagnetic field. The high oscillation frequency prevents largely that the molecules follow the imposed perturbation and thus part of the energy is absorbed through dielectric loss. 
     It is generally assumed today that, in the majority of cases, the reason for the observed reaction rate enhancement is a purely thermal/kinetic effect directly related to the high energy levels of the molecules that lead to a high reaction temperature that can rapidly and directly be attained when irradiating polar material in a microwave field. This high reaction rate may result both, from the rapid and uniform heating of a (polar) solvent that strongly absorbs the microwave energy or from high thermal energy levels of the reaction sites: the presence of hot spots at the site of the reactive species having a noticeably higher local temperature than the bulk temperature is probably responsible for most rate enhancements above the rates expected on the basis of the measured bulk temperature. 
     Increasing reaction rates and high conversion efficiencies are thus especially observed when the reagent structure preferentially and directly absorbs microwave energy that is thus not transferred by the heated solvent. Microwave heating excites the vibrational-rotational modes of the molecules and this energy is partially transferred to translational modes, thus resulting in dielectric loss and energy dissipation resulting in thermal effect whereby the absorbing molecules can reach a “local” temperature well above the bulk temperature; this may even allow to work at conditions beyond the usual boiling limits of a given solvent. In some cases, the molecule may absorb the microwave energy in a mode that is directly related to the chemical reaction, thus resulting in an even more efficient mode of energy absorption, which would represent a form of “specific” effect. The existence of specific microwave effects remains however an issue of much debate. 
     In the field of modifying the activity of catalyst systems, several methods were developed in the past. 
     For example U.S. Pat. No. 3,485,771 to Phillips referred to the use of a plasma to activate a catalyst at a lower activation temperature; the activation disclosed in that patent does not refer to the use of microwave energy and involves only the step of dehydration of the catalyst thereby forming the silylchromate. It does not involve the chromium reduction or an acid-base exchange step. 
     Microwave energy was used in relation to producing catalyst systems in UK-A-1530445. The patent refers to a process involving the use of microwave energy for the production of a supported Ziegler catalyst component comprising an inorganic oxide or elementary carbon and a magnesium compound. In this patent, microwave energy is used for producing the support and does not play any role in the activation step. 
     U.S. Pat. No. 5,719,095 and EP-A-0615981 disclosed the use of microwave energy for producing a supported catalyst system containing a metallocene catalyst, whereby the catalyst is fixed in a more efficient way to the support including the co-catalyst in order to limit the presence of free catalyst in the reactive medium. 
     WO04/089998 described a single step process for preparing a Ziegler type procatalyst system comprising magnesium chloride, supported titanium chloride with an internal electron donor, and a cocatalyst based on an organoaluminum compound, under microwave irradiation. Said catalyst system was used for the preparation of lower alfa-alkene polymers, notably polypropylene. 
     There is thus a need to develop a technology to use microwave energy in the field of production of active catalytic species. 
     It is an aim of the present invention to use microwave energy to produce active catalytic species. 
     It is another aim of the present invention to create more active sites in catalyst systems. 
     It is also an aim of the present invention to create catalytic species having a very high activity. 
     It is a further aim of the present invention to produce the catalytic species rapidly and efficiently. 
     It is yet a further aim of the present invention to produce reduced overheating at the reactor walls and thus lesser formation of secondary or degradation products than conventional methods. 
     Accordingly, the present invention discloses the use of microwave energy for producing active catalytic species involving structures having a dipolar or ionic nature. 
     Such structures are particularly suitable for interacting with a source of microwave energy and produce either more active species or a more active structure of active species than conventional methods. 
     In a preferred embodiment according to the present invention, microwave energy is used either to deposit the activating agent on the support and/or to deposit the catalyst component onto the impregnated support either simultaneously in a one-step method or consecutively in a two-step method. 
     The most preferred embodiment is the two-step method wherein the support is first impregnated with an activating agent and then a metallocene catalyst component is added to the impregnated support, any one step or both being carried out in a microwave oven. 
     The catalytic species that can be produced using microwave energy are not particularly limited and include for example metallocene and other coordination-complex, Ziegler-Natta and chromium-based catalyst systems. All these catalyst systems have in common that, when microwave energy is used either to deposit the activating agent on the support and/or to deposit the catalyst component onto the impregnated support or both, they all have a larger percentage of active species and/or the active species are more active. In addition, the creation of these active species takes a shorter time and they are created at much lower temperature than when conventional methods are used. 
     These catalyst systems are very sensitive to the presence of the most common microwave absorbing species such as polar solvents or ionic liquids that would inactivate or block the active catalytic species. Dielectric or microwave heating is therefore not considered as an efficient way for heating chemical mixtures containing the catalyst system up to the temperatures conventionally used for activating these systems. 
    
    
     
       LIST OF FIGURES 
         FIG. 1  represents the mechanism for activating chromium-based catalyst systems. 
         FIG. 2  represents the mechanism for activating Ziegler-Natta catalyst systems. 
         FIG. 3  represents the mechanism for activating silica-supported metallocene catalyst systems. 
     
    
    
     The mechanism for creating active species in chromium-based catalyst systems used for the polymerisation of alkenes is schematically illustrated in  FIG. 1 . It comprises a pre-activation step that is carried out in the absence of alkene and is represented in  FIG. 1(   a ) and ( b ) and the activation step that necessitates the presence of alkene and is represented in  FIG. 1(   c ) and ( d ). In conventional methods, chromium oxide is impregnated on the surface of the support (a). This impregnated support is dried and then dehydrated at high temperature and under a flow of dry air to fix the chrome VI as silyl chromate (b). The chromium VI is then reduced to chromium II by reaction with monomer or co-monomer (c). The active species is formed by acid-base exchange with a neighbouring silanol present on the support structure (d). This method allows the production of a low fraction of active catalytic species, typically involving some 10% of the chromium atoms. Typically, the chromium based catalyst systems comprise about 1 wt % of chromium and the fraction of active sites thus represents about 0.1 wt % as Cr. In the present invention, sequences (c) and (d) for producing the pre-active species can advantageously be carried out using microwave energy. This new method results in producing highly active catalyst systems: the improvement is measured by an increase in productivity of at least 20%. 
     The mechanism for creating active sites in Ziegler-Natta catalyst systems is schematically illustrated in  FIG. 2 . In conventional methods, a titanium chloride compound is supported. The support is either magnesium chloride that includes electron-donor compounds or the titanium chloride compound is precipitated together with the compounds forming the support and the electron-donor compounds; this supported structure is then modified by addition of an aluminium alkyl or aluminium alkyl chloride compound to produce the active catalytic species. In the present invention, that addition reaction is carried out using microwave energy. 
     In metallocene catalyst systems, the activation is carried out by addition of an activating agent having an ionising action. In a preferred embodiment of the invention, represented in  FIG. 3 , the activating agent is first added to a support and the metallocene component dissolved in a solvent is then added to the impregnated support. Alternatively, the metallocene and activating agent can first be mixed and then deposited on the support. 
     Metallocene catalyst components may be represented by formula I 
       R″s(CpR n )(C′pR′ m )MQ2 
     wherein
 
Cp and C′p are unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl;
 
each R is independently selected from hydrogen or hydrocarbyl having from 1 to 20 carbon atoms;
 
each R′ is independently selected from hydrogen or hydrocarbyl having from 1 to 20 carbon atoms;
 
R″ is an optional structural bridge imparting stereorigidity between the two cyclopentadienyl rings and s is 1 if the bridge is present and 0 if there is no bridge;
 
M is a metal Group 4 of the periodic Table;
 
Q is hydrogen or alkyl having from 1 to 6 carbon atoms or halogen.
 
     Preferred metallocene components may be selected from bridged bisindenyl, bridged bis tetrahydroindenyls, bridged cyclopentadienyl-fluorenyl such as bridged (3-t-butyl,5-methyl-cyclopentadienyl)(3,6-tert-butyl-fluorenyl) or unbridged bis(n-butyl-cyvlopentadienyl) components. 
     Any activating agent having an ionising action known in the art may be used for activating the metallocene component. For example, it can be selected from aluminium-containing or boron-containing compounds. The aluminium-containing compounds comprise aluminoxane, alkyl aluminium and/or Lewis acid. 
     The aluminoxanes are preferred and may comprise oligomeric linear and/or cyclic alkyl aluminoxanes represented by the formula: 
     
       
         
         
             
             
         
       
     
     for oligomeric, linear aluminoxanes and 
     
       
         
         
             
             
         
       
     
     for oligomeric, cyclic aluminoxane,
 
wherein n is 1-40, preferably 10-20, m is 3-40, preferably 3-20 and R is a C 1 -C 8  alkyl group and preferably methyl.
 
     Suitable boron-containing activating agents that can be used comprise a triphenylcarbenium boronate such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium as described in EP-A-0427696, or those of the general formula [L′-H]+[B Ar 1  Ar 2  X 3  X 4 ]— as described in EP-A-0277004 (page 6, line 30 to page 7, line 7). 
     The support, if present, can be a porous mineral oxide. It is advantageously selected from silica, alumina and mixtures thereof. Preferably it is silica. 
     In the preferred embodiment according to the present invention a silica support is impregnated with an aluminoxane, preferably with methylaluminoxane (MAO) and the impregnation may take place under microwave energy. The impregnation time in conventional methods is of about 2 hours at a temperature of about 110° C. It is reduced to less than one hour, preferably to less than 30 minutes, more preferably to less than 10 minute and most preferably less than 5 minutes when microwave energy is used because the solvent does not need to be heated through. A metallocene catalyst component is then deposited on the impregnated support either in a microwave oven or not, depending upon the method of impregnation of the support. If the metallocene is deposited in a microwave oven, the time necessary for the deposition is also reduced to less than one hour, preferably to less than 30 minutes, more preferably to less than 10 minute and most preferably less than 5 minutes instead of the about two hours necessary when the classical method is used. At least one of the two steps must take place in a microwave oven. A reduction of time of more than 50%, preferably more than 75% is then obtained for each step carried under microwave energy. 
     Without wishing to be bound by a theory, it is believed that because of the polar structure of MAO and of the silica support, they are easily excited by microwave energy and thereby leading to a fast and efficient supporting reaction. 
     The microwave frequencies that can be used in the present invention range between 300 MHz and 30 GHz. Preferably all work is carried out in the range between 1 and 5 GHz. 
     The productivity of the catalyst systems prepared according to the present invention is increased by at lest 20%, preferably by at least 40%, with respect to the equivalent catalyst systems prepared by conventional methods 
     The active catalytic species of the present invention are suitable for polymerising ethylene and alpha-olefins using any known polymerisation method. 
     It is observed that less undesirable secondary products are formed during the preparation of the active catalytic species than in prior art method, thus leading to cleaner products. 
     EXAMPLES 
     Metallocene catalyst component ethylene-bis(tetrahydroindenyl) zirconium dichloride (THI) was deposited on a silica support impregnated with methyl aluminoxane (MAO) as follows. 
     Example 1 
     Synthesis of Silica/MAO 
     2 g of silica sold by Grace under the trade name Sylopol® 952X1836 thoroughly dried were introduced into a 20 ml glass reactor equipped with a magnetic stirrer. 11 mL of toluene were then added to the reactor followed by the addition of 4 mL of methyl aluminoxane (30 wt %). The reactor (tube) was sealed and placed immediately in the microwave oven and the reaction was allowed to take place: the microwave power was of 300 watt. After reaction, the suspension was filtered on a porosity 3 fritt. The filtrate was then washed 3 times with 10 mL of toluene, 3 times with 10 mL of pentane and dried under reduced atmosphere until a constant weight was obtained. It was observed that the silica/MAO support was very efficiently produced in a shorter time than by the conventionalmethod and without affecting the integrity of the SiO 2  structure. 
     Ethylene-bis-(tetrahydro-indenyl) zirconium dichloride (THI) was then deposited on silica impregnated with MAO. 
     Example 2 
     One-Pot Method 
     11 mL of toluene were placed in a 20 mL glass reactor. 4 mL of MAO (30 wt %) were added and the mixture was stirred for 1 minute with a magnetic stirrer. 0.04 g of THI were then added to the reactor and the mixture was stirred for 3 minutes. 2 g of the same silica Sylopol® 952X1836 were added to the reactor under stirring in order to homogenise the reaction medium. The reactor (tube) was sealed and placed immediately in the microwave oven and the reaction was allowed to take place: the microwave power was of 300 watt. After reaction, the suspension was filtered, washed and dried as described in example I . The number of active sites showed a substantial increase as compared to that obtained with the same ingredients mixed using the conventional technique. That increase was measured by an increase in productivity. 
     Example 3 
     Deposition of Ligand on Silica/MAO 
     Silica/MAO was prepared by the conventional method: 2 g of silica sold by Grace under the trade name Sylopol® 952X1836 thoroughly dried were introduced into a 20 ml glass reactor equipped with a magnetic stirrer. 11 mL of toluene were then added to the reactor followed by the addition of 4 mL of methyl aluminoxane (30 wt %). The mixture was kept under stirring at a temperature of 110° C. for a period of time of 2 hours. 2 g of that silica/MAO were placed in a 20 mL glass reactor equipped with a magnetic stirrer. 11 mL of toluene were added to the reactor followed by the addition of 0.04 g of THI under stirring. The reactor (tube) was sealed and placed immediately in the microwave oven wherein magnetic stirring occurred and the reaction was allowed to take place for a period of time of 2 minutes and with a microwave power of 300 watt. After reaction, the suspension was filtered, washed and dried as described in example I . As in the previous example, an increased number of active sites was observed, as measured by an increase in productivity. 
     Comparative Example 
     Synthesis of Silica/MAO and Deposition of Catalyst Component 
     The reference silica/MAO and the deposition of the catalyst component were carried out using the classical method, without microwave irradiation. 
     2 g of silica sold by Grace under the trade name Sylopol® 952X1836 thoroughly dried were introduced into a 20 ml glass reactor equipped with a magnetic stirrer. 11 mL of toluene were then added to the reactor followed by the addition of 4 mL of methyl aluminoxane (30 wt %) and the reaction was allowed to take place for a period of 2 hours at a temperature of 110° C. In a closed Biotage reactor of the type used for microwave reactions, 3.3 mg of ethylene-bis-(tetrahydro-indenyl) zirconium dichloride (THI) were then added to 150 mg of impregnated silica in 500 μL of toluene, under light stirring, at room temperature (about 25° C.) and during a period of time of 2 hours. The pale yellow solution was filtered and the solid was rinsed twice with 500 μL of toluene and 4 times with 1200 μL of pentane. 111 mg of pale yellow powder were obtained. It is the reference catalyst system Cref. 
     Example 4 
     Synthesis of Silica/MAO Under Microwave Irradiation and Deposition of Catalyst Component by Classical Method 
     In a glove box, 200 mg of dry silica were added to 225 μL of MAO in 1200 μL of toluene in a microwave vial. The reaction was carried out in a microwave oven up to a temperature of 60° C., with the times and powers displayed in Table I. The solution was then filtered and the solid was rinsed twice with 500 μL of toluene and 4 times with 1200 μL of pentane. The white solid was dried. The catalyst component was then added following the classical method of example 4. Catalyst systems C1 to C4 were obtained. 
     
       
         
           
               
               
               
             
               
                 TABLE I 
               
               
                   
               
               
                 Catalyst 
                 Time (min) 
                 Power (W) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 C1 
                 4 
                 100 
               
               
                 C2 
                 2 
                 300 
               
               
                 C3 
                 34 
                 100 
               
               
                 C4 
                 32 
                 300 
               
               
                   
               
            
           
         
       
     
     Example 5 
     Synthesis of Silica/MAO by Classical Method and Deposition of Catalyst Component Under Microwave Irradiation 
     Silica was impregnated with MAO following the classical method of example 4. In a glove box, 3.3 mg of ethylene-bis-(tetrahydro-indenyl) zirconium dichloride (THI) were added to 150 mg of impregnated silica in 900 μL of toluene in a microwave vial. The reaction was carried out in a microwave oven up to a temperature of 60° C., with the times and powers displayed in Table II. The pale yellow solution was then filtered and the solid was rinsed twice with 500 μL of toluene and 4 times with 1200 μL of pentane. The pale yellow solid was dried. Catalyst systems C5 to C8 were obtained. 
     
       
         
           
               
               
               
             
               
                 TABLE II 
               
               
                   
               
               
                 Catalyst 
                 Time (min) 
                 Power (W) 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                 C5 
                 10 
                 100 
               
               
                 C6 
                 2 
                 300 
               
               
                 C7 
                 40 
                 100 
               
               
                 C8 
                 32 
                 300 
               
               
                   
               
            
           
         
       
     
     Example 6 
     Polymerization of Ethylene with the Catalyst Systems of Examples 4 and 5 
     The active catalyst system was introduced into the reactor using the amounts displayed in Table III and the following general conditions. 
     Ethylene pressure=10 bars.
 
TIBAL as cocatalyst with [Al]:[Zr]=500.
 
10 μL of TIBAL were also used as scavenger with the solvent.
 
Polymerisation temperature=50° C.
 
The solvents were dry heptane, (distilled under sodium benzophenone, distilled in “trap to trap”, degassed and stocked under Ar) and dry Vestan oil.
 
Useful reactor volume=5 mL.
 
     The procedure was as follows: 
     The reactor was dried under Ar at a temperature of 100° C. for a period of time of 30 minutes. 
     The reactor was purged 5 times with Ar and then 5 times with ethylene. It was then heated to the desired temperature and the solvent and scavenger were injected. The pressure was increased to the desired level and the catalyst solution was injected into the reactor. The polymerisation reaction was stopped after about one hour by hydrolysis with 1 mL of methanol/HCl (10%). The results are displayed in Table III. 
     
       
         
           
               
               
               
               
               
             
               
                 TABLE III 
               
               
                   
               
               
                   
                 Catalyst amount 
                 Time 
                 Mass PE 
                 Activity 
               
               
                 Catalyst 
                 mmol 
                 (min) 
                 (g) 
                 Kg/mol/h 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
            
               
                 Cref 
                 6.9 
                 59.8 
                 0.34 
                 3500 
               
               
                 C1 
                 10 
                 59.9 
                 0.58 
                 5700 
               
               
                 C2 
                 11 
                 59.7 
                 0.585 
                 6000 
               
               
                 C3 
                 8.3 
                 59.9 
                 0.47 
                 4700 
               
               
                 C4 
                 9.5 
                 59.8 
                 0.525 
                 5200 
               
               
                 C5 
                 11.9 
                 51.2 
                 0.635 
                 7500 
               
               
                 C6 
                 10.5 
                 59.8 
                 0.62 
                 6200 
               
               
                 C7 
                 9.6 
                 59.8 
                 0.545 
                 5400 
               
               
                 C8 
                 10.3 
                 59.8 
                 0.61 
                 6000 
               
               
                   
               
               
                 Note: 
               
               
                 all data appearing in this table are averages over 2 to 5 runs carried out under identical conditions. 
               
            
           
         
       
     
     As can be seen from this table, all the catalyst systems for which one of the two steps was carried out in a microwave oven show a better activity than the reference catalyst system prepared by the classical method. In addition, as showed in tables I and II, the times necessary to prepare each step were reduced to a few minutes instead of 2 hours. 
     Samples C5 to C8, prepared with the catalyst deposition in the microwave oven, gave slightly better activities than samples C1 to C4 for which the silica was impregnated with MAO in the microwave oven. 
     Example 7 
     Polymerization of Ethylene with the Catalyst Systems of Example 3 
     The reactor, conditioned under nitrogen at a temperature of 100° C., was further conditioned under nitrogen flow for a period of time of 15 min at a temperature of 100° C. It was then set to the reaction temperature and purged with the diluent. Half of the total quantity of diluent was then injected, followed by injection of hexene, of ethylene up to the set pressure, of hydrogen. The catalyst, scavenger and cocatalyst were then added with the remaining half of the diluent to start the polymerisation reaction. 
     Following compositions and conditions were used into the reactor for polymerisation of ethylene in the presence of the supported catalyst:
         3.2 up to 4.3 mg of supported catalyst   6.4 mg TiBAL as scavenger and 19.2 mg TiBAL as cocatalyst   90 ml of dried iso-butane as diluent in presence of 2.4% hexene and 0.01 NI of H2   polymerisation temperature=85° C.   ethylene pressure=28.3 bar   polymerisation time=60 minutes       

     The productivity, expressed in g polymer per g supported catalyst per hour obtained are as follows 
     The reference catalyst system of comparative example had a productivity of between 3800 and 4000 g/g/h whereas the catalyst system of example 3 had a productivity of between 5200 and 5800 g/g/h, thus clearly much larger than that of the reference catalyst system.