Patent Application
20120283402
The present invention relates to porous magnesium dichloride/water adducts possibly containing specific amounts of organic hydroxy compounds. The adducts of the present invention are particularly useful as precursors of catalyst components to catalyst components suitable for the preparation of homopolymers and copolymers of ethylene having a broad molecular weight distribution (MWD) and to the catalysts obtained therefrom.
In particular the porous magnesium dichloride/water adducts possibly containing specific amounts of organic hydroxy compounds allow to prepare solid catalyst components, comprising titanium, magnesium and halogen characterized by a specific chemical composition which are suitable to prepare ethylene polymers having a set of properties making them particularly suitable for blow molding applications.
This specific application field is very demanding for ethylene polymers which, in order to be suitable for this use, need to show properties such as broad molecular weight distribution (MWD), proper melt strength/swell balance and ESCR.
The breath of molecular weight distribution (MWD) of the ethylene polymers can be expressed by a high melt flow ratio (F/E) value, which is the ratio between the melt index measured with a 21.6 Kg load (melt index F) and the melt index measured with a 2.16 Kg load (melt index E), determined at 190° C. according to ASTM D-1238. The MWD affects the rheological behavior, the processability of the melt and also the final ESCR properties. Polyolefin having a broad MWD, particularly coupled with relatively high average molecular weight, are preferred in high speed extrusion processing where polymers having a not proper MWD could cause melt fracture and higher shrinkage/warpage of the final items. However, it has been proven to be a very difficult task to obtain polymers combining broad MWD with a proper melt strength/swell balance. This is because MWD also affects melt strength and swell in a different way.
It would also be advisable that the catalyst is capable to work successfully under gas-phase polymerization conditions, as this kind of technique is nowadays the most effective, advantageous and reliable technology. This means that the catalyst needs to have a good morphological stability preventing its improper fragmentation and consequent formation of fines particle responsible of plant operation problems such as, hot spots, reactor sheeting, plugging etc.
MgCl2.alcohol adducts and their use in the preparation of catalyst components for the polymerization of olefins is well known in the art.
Catalyst components for the polymerization of olefins, obtained by reacting MgCl2.nEtOH adducts with halogenated transition metal compounds, are described for example in U.S. Pat. No. 4,399,054. The adducts are prepared by emulsifying the molten adduct in an immiscible dispersing medium and quenching the emulsion in a cooling fluid to collect the adduct in the form of spherical particles. In order to produce a catalytic components a transition metal compound must be fixed on the support. This is obtained by contacting the supports with large amounts of titanium compounds, in particular TiCl4, that causes removal of the alcohol and supportation of Ti atoms. The so obtained catalysts show very high activities but their morphological stability is not always satisfactory because, under polymerization conditions, it often gives rise to a non negligible amount of broken polymer particle that contribute to generate the fine polymer particles which negatively affect the operation of the polymerization plant.
U.S. Pat. No. 3,953,414 describes catalyst components having good morphological stability obtained by (i) spraying a hydrated Mg dihalide in the molten state or dissolved in water, and more particularly molten MgCl2.6H2O having sizes comprised in general between 1 and 300 micron, preferably 30 to 180 micron; (ii) subsequently subjecting said particles to a controlled partial dehydration to bring the crystallization water content to a value below 4 moles of H2O per mole of the Mg dihalide while avoiding hydrolysis of the Mg dihalide; thereafter (iii) reacting the partially dehydrated Mg dihalide particles in a liquid medium comprising a halogenated Ti compound, more particularly TiCl4, heated to a temperature generally higher than 100° C., and (iv) finally removing the unreacted Ti compound from the Mg dihalide particles, by further reaction with hot TiCl4. The document does not indicate whether the catalyst is suitable to produce broad MWD polymers or whether such polymers are suitable for blow molding. However, it is apparent that the polymerization activity is not sufficient.
The applicant has now found that certain porous magnesium chloride/water based adducts possibly containing additional amounts of organic hydroxy compounds, are able to generate catalyst components with high polymerization activity and enhanced morphological stability suitable to prepare ethylene polymers having a set of properties making them particularly suitable for blow molding applications.
The present invention therefore relates to solid adducts comprising MgCl2 and water and optionally an organic hydroxy compound (A) selected from hydrocarbon structures containing at least one hydroxy group, said compounds being present in molar ratio defined by the following formula MgCl2.(H20)n(A)p in which n is from 0.6 to 6, p ranges from 0 to 3, said adduct having a porosity (PF), measured by the mercury method and due to pores with radius equal to or lower than 1 μm, of at least 0.15 cm3/g with the proviso that when p is 0, (PF) is equal to or higher than 0.3 cm3/g.
When p is 0, n preferably ranges from 0.7 to 5.5, more preferably from 0.7 to 4 and especially from 1 to 3.5 with the range from 1 to 3 being the most preferred. The porosity preferably ranges from 0.35 to 1.5 and more preferably from 0.4 to 1 cm3/g.
When p is higher than 0, it preferably ranges from 0.1 to 2.5 and preferably from 0.3 to 2 cm3/g, while n ranges from 0.6 to 2 preferably from 0.8 to 1.5 and the porosity preferably ranges from 0.15 to 0.6 cm3/g.
The compound (A) may also contain two or more hydroxy groups. It can be selected either from unsaturated or saturated hydrocarbon structures. Example of such polyhydroxy compounds are glycols, polyhydroxybenzenes, polyhydroxy naphthalenes.
Preferably, the compound (A) is selected from alcohols of formula RIIOH where preferably selected from RII is an alkyl, cycloalkyl or aryl radical having 1-12 carbon atoms. Among them, Methyl, ethyl, isopropyl and cyclohexyl are preferred. Ethyl is especially preferred. Particularly when the compound (A) is selected from alcohols, the ratio n/p is preferably equal to or higher than 0.4. More preferably, such a ratio is in combination with the sum n+p being at least 1 and even more preferably higher than 1.5.
The adducts of the invention can be obtained by hydration of porous MgCl2 which is in turn obtained by thermally dealcoholating MgCl2nEtOH adducts in which n is from 1 to 6.
Adducts of this type can generally be obtained by mixing alcohol and magnesium chloride in the presence of an inert hydrocarbon immiscible with the adduct, operating under stirring conditions at the melting temperature of the adduct (100-130° C.). Then, the emulsion is quickly quenched, thereby causing the solidification of the adduct in form of spherical particles. Representative methods for the preparation of these spherical adducts are reported for example in U.S. Pat. No. 4,469,648, U.S. Pat. No. 4,399,054, and WO98/44009. Another useable method for the spherulization is the spray cooling described for example in U.S. Pat. Nos. 5,100,849 and 4,829,034. The so obtained adducts are then subject to a thermal and/or chemical dealcoholation process. The thermal dealcoholation process is carried out in nitrogen flow at temperatures comprised between 50 and 150° C. until the alcohol is totally removed or reduced to a sufficiently low value. A process of this type is described in EP 395083 and leads to the achievement of porous MgCl2 optionally containing residual amounts of alcohol. According to the preferred process of the present invention the porous MgCl2 is subject to a hydration process in which the desired amount of water is gradually added to the adducts. The hydration can be carried out in several ways. For example the porous MgCl2 can be suspended in an inert liquid hydrocarbon containing water and kept in motion until the desired water/Mg ratio is obtained. After that, the liquid phase can be removed and the solid adduct dried under moderate vacuum.
According to another method water can be sprayed in a chamber or a loop reactor within which the porous MgCl2 is kept in continuous motion, through mechanical stirring or inert gas fluidization. At the end of the water adduction the hydrated adduct is recovered via the usual means.
By way of these methods, it is possible to obtain final hydrated adducts particles in spherical or spheroidal form. Such spherical particles have a ratio between maximum and minimum diameter lower than 1.5 and preferably lower than 1.3.
The adduct of the invention can be obtained in a broad range of particle size, namely ranging from 5 to 150 microns preferably from 10 to 100 microns and more preferably from 15 to 80 microns. Surprisingly, it has been found that said adducts have a porosity higher than that of the adducts in which the water is replaced by a corresponding amount of another donor, in particular an alcohol.
The adducts of the invention are converted into catalyst components for the polymerization of olefins by reacting them with a transition metal compound of one of the groups IV to VI of the Periodic Table of Elements.
Among transition metal compounds particularly preferred are titanium compounds of formula Ti(OR)nXy-n in which n is comprised between 0 and y; y is the valence of titanium; X is halogen and R is an alkyl radical having 1-8 carbon atoms or a COR group. Among them, particularly preferred are titanium compounds having at least one Ti-halogen bond such as titanium tetrahalides or halogenalcoholates. Preferred specific titanium compounds are TiCl3, TiCl4, Ti(OBu)4, Ti(OBu)Cl3, Ti(OBu)2Cl2, Ti(OBu)3Cl. Preferably the reaction is carried out by suspending the adduct in cold TiCl4 (generally 0° C.); then the so obtained mixture is heated up to 80-130° C. and kept at this temperature for 0.5-2 hours. After that the excess of TiCl4 is removed and the solid component is recovered. The treatment with TiCl4 can be carried out one or more times. As a result of the reaction, part of the Ti atoms can remained fixed on the catalyst as TiOCl2.
The reaction between transition metal compound and the adduct can also be carried out in the presence of an electron donor compound (internal donor) in particular when the preparation of a stereospecific catalyst for the polymerization of olefins is to be prepared. Said electron donor compound can be selected from esters, ethers, amines, silanes and ketones. In particular, the alkyl and aryl esters of mono or polycarboxylic acids such as for example esters of benzoic, phthalic, malonic and succinic acid are preferred.
The electron donor compound is generally present in molar ratio with respect to the magnesium comprised between 1:4 and 1:20.
Preferably, the particles of the solid catalyst components have substantially the same size and morphology as the adducts of the invention generally comprised between 5 and 150 μm. The solid catalyst components according to the present invention show a surface area (by B.E.T. method) generally between 10 and 500 m2/g and preferably between 20 and 350 m2/g, and a total porosity (by B.E.T. method) higher than 0.15 cm3/g preferably between 0.2 and 0.6 cm3/g.
The amount of titanium atoms is preferably higher than 4.5% more preferably higher than 5.5% and especially higher than 7% wt. According to a preferred embodiment more than 80% of the titanium atoms are in a +4 valence state and, more preferably, substantially all the titanium atoms are in such a valence state. Throughout the present application the wording “substantially all the titanium atoms are in valence state of 4” means that at least 95% of the Ti atoms have a valence state of 4.
The catalyst of the present invention may show also another additional interesting feature. The amount of total anions that are detected, according to the below reported methods, on the solid catalyst component are usually not enough to satisfy the total of positive valences deriving from the cations including, but not limited to, Mg, Ti even taking into account the possible presence of OR groups. In other words, it has been noticed that in the catalyst of the invention a certain amount of anions is often lacking in order to have all the valences of the cations satisfied. According to the present invention, this lacking amount is defined as “LA” factor where “LA” factor is the molar equivalent of anionic species lacking in order to satisfy all the molar equivalents of the cations present in the solid catalyst component which have not been satisfied by the total molar equivalent of the anions present in the solid catalyst component, all of the molar equivalents of anions and cations being referred to the Ti molar amount.
The LA factor is determined by first determining the molar contents of all the anions and cations detected by the analysis. Then, the molar content relative to all of the anions (including but not limited to Cl− and —OR) and cations (including but not limited to Mg, and Ti) is referred to Ti by dividing it for the Ti molar amount which is therefore considered as the molar unity. Afterwards, the total number of molar equivalents of cations to be satisfied is calculated for example by multiplying the molar amount of Mg++ (referred to Ti) by two and the molar amount of Ti+4 (molar unity) by four. The so obtained total value is then compared with the sum of the molar equivalents deriving from anions, for example Cl and OR groups, always referred to titanium. The difference resulting from this comparison, and in particular the negative balance obtained in terms of anion molar equivalents, indicates the LA factor.
The “LA” factor is usually higher than 0.5, preferably higher than 1 and more preferably in the range from 1.5-6.
The catalyst components of the invention form catalysts for the polymerization of alpha-olefins CH2═CHR, wherein R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms, by reaction with organo-Al compounds. Among them preferred are hydrocarbyl compound of the formula AlR3-zXz above, in which R is a C1-C15 hydrocarbon alkyl or alkenyl radical, X is halogen preferably chlorine and z is a number 0≦z<3. The organo-Al compound is preferably chosen among the trialkyl aluminum and trialkenyl compounds such as for example trimethylaluminum triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, triisoprenylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides such as AlEt2Cl and Al2Et3Cl3 optionally in mixture with said trialkyl aluminum compounds.
The Al/Ti ratio is higher than 1 and is generally comprised between 20 and 2000, preferably from 20 to 800.
It is possible to use in the polymerization system an electron donor compound (external donor) which can be the same or different from the compound that can be used as internal donor disclosed above. The external donor is preferably selected from those of the following formula
wherein:
R2, equal to or different from each other, are hydrogen atoms or C1-C20 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the periodic table of the elements or alkoxy groups of formula —OR1, two or more of the R2 groups can be connected together to form a cycle; R1 are C1-C20 hydrocarbon radicals optionally containing heteroatoms belonging to groups 13-17 of the periodic table of the elements.
Preferably, at least one of R2 is −OR1.
In general, it is preferred that the two —OR1 groups are in ortho position to each other.
Accordingly, 1,2-dialkoxybenenes, 2,3-alkyldialkoxybenzenes or 3,4-alkyldialkoxybenzenes are preferred. The other R2 groups are preferably selected from hydrogen, C1-05 alkyl groups and OR1 groups. When two R2 are alkoxygroup OR1, a trialkoxybenzene derivative is obtained and in this case the third alkoxy may be vicinal (ortho) to the other two alkoxy or in meta position with respect to the closest alkoxygroup. Preferably, R1 is selected from C1-C10 alkyl groups and more preferably from C1-05 linear or branched alkyl groups. Linear alkyls are preferred. Preferred alkyls are methyl, ethyl, n-propyl, n-butyl and n-pentyl.
When one or more of the R2 is a C1-05 linear or branched alkyl groups, alkyl-alkoxybenzenes are obtained. Preferably, R2 is selected from methyl or ethyl. According to a preferred embodiment one of the R2 is methyl.
One of the preferred subclasses is that of the dialkoxytoluenes, among this class preferred members are 2,3-dimethoxytoluene, 3,4-dimethoxytoluene, 3,4-diethoxytoluene, 3,4,5 trimethoxytoluene.
It has to be noted that, with respect to the hydrated adducts of the prior art the adducts of the invention are capable to give catalyst components showing higher polymerization activity at the same level of morphological stability.
As previously indicated the components of the invention and catalysts obtained therefrom find applications in the processes for the (co)polymerization of olefins of formula CH2═CHR in which R is hydrogen or a hydrocarbon radical having 1-12 carbon atoms.
The spherical components of the invention and catalysts obtained therefrom find applications in the processes for the preparation of several types of olefin polymers.
For example the following can be prepared: high density ethylene polymers (HDPE, having a density higher than 0.940 g/cm3), comprising ethylene homopolymers and copolymers of ethylene with alpha-olefins having 3-12 carbon atoms; linear low density polyethylene's (LLDPE, having a density lower than 0.940 g/cm3) and very low density and ultra low density (VLDPE and ULDPE, having a density lower than 0.920 g/cm3, to 0.880 g/cm3 cc) consisting of copolymers of ethylene with one or more alpha-olefins having from 3 to 12 carbon atoms, having a mole content of units derived from the ethylene higher than 80%; elastomeric copolymers of ethylene and propylene and elastomeric terpolymers of ethylene and propylene with smaller proportions of a diene having a content by weight of units derived from the ethylene comprised between about 30 and 70%, isotactic polypropylenes and crystalline copolymers of propylene and ethylene and/or other alpha-olefins having a content of units derived from propylene higher than 85% by weight; shock resistant polymers of propylene obtained by sequential polymerization of propylene and mixtures of propylene with ethylene, containing up to 30% by weight of ethylene; copolymers of propylene and 1-butene having a number of units derived from 1-butene comprised between 10 and 40% by weight.
However, as previously indicated they are particularly suited for the preparation of broad MWD polymers and in particular of broad MWD ethylene homopolymers and copolymers containing up to 20% by moles of higher α-olefins such as propylene, 1-butene, 1-hexene, 1-octene.
In particular the catalysts of the invention are able to give ethylene polymers, in a single polymerization step, with a broad molecular weight distribution as evidenced by the high ratio of the F/E ratio, defined as mentioned above, and also endowed with a suitable set of properties for the blow molding application.
The catalysts of the invention can be used in any kind of polymerization process both in liquid and gas-phase processes. Catalysts in which the solid catalyst component has small average particle size, such as less than 30 μm, preferably ranging from 5 to 20 μm, are particularly suited for slurry polymerization in an inert medium, which can be carried out continuously stirred tank reactor or in loop reactors. In a preferred embodiment the solid catalyst components having small average particle size as described are particularly suited for the use in two or more cascade loop or stirred tank reactors producing polymers with different molecular weight and/or different composition in each reactor. Catalysts in which the solid catalyst component has medium/large average particle size such as at least 30 μm and preferably ranging from 50 to 100 μm are particularly suited for gas-phase polymerization processes which can be carried out in agitated or fluidized bed gas-phase reactors.
The following examples are given to further illustrate without limiting in any way the invention itself.
The properties reported below have been determined according to the following methods:
A sample of spherical magnesium chloride bi-hydrate complex was prepared according the following method. For the test a starting microspheroidal MgCl2.2.8C2H5OH was used, prepared according to the method described in ex.2 of WO98/44009 but operating on larger scale and under stirring conditions so as to have an average size of 69.5 μm. The said adduct was then subject to thermal dealcoholation at increasing temperatures from 30 to 130° C. and operating in nitrogen current until a chemical composition of 45.1% wt. ethanol, 1.7% wt. water, 53.2% magnesium chloride was reached. Once obtained, 5949 g of this material were loaded into a 150 mm diameter glass jacketed fluidized bed reactor equipped with dedicated heating systems for both fluidization nitrogen and for the reactor main body, processed with nitrogen flow rate kept at 1200 l/h providing a good fluidization, and then warmed up from 60° C. to 110° C. in 3 hrs, and kept at 110° C. for an extra hour. After that time (at a new composition of about 40% ethanol by weight) a calibrated amount of water (1198 g) was added to the reactor by a volumetric peristaltic pump, operating at a feed rate of about 100 ml/h. The water was fed directly into the fluidizing (jacketed) nitrogen line, warmed up to 104-106° C. and then introduced to the fluidized reactor. The moist nitrogen stream temperature was measured just below the fluidizing grid, operating between 85° C. and 94° C., and recorded. After about 11.5 hrs of continuous water feeding into the reactor the total desired amount of water was fed, while ethanol was removed out of the reactor by the fluidizing nitrogen. Part of the condensed ethanol (520 ml) was collected and recovered in the cyclones section of the nitrogen line after the reactor (no fines or solid is found in the cyclones at the chosen fluidization conditions). After completion of water adduction, the support is cooled down to room temperature and discharged (4212 grams, corresponding to a yield/recovery in magnesium of 96.9% compared to the theoretical expected weight). Chemical analyses showed a residual 0.3% ethanol content by weight, 27.3% wt. of water, 18% of elemental magnesium. The final adduct showed a porosity of 0.83 cm3/g
A micro sample of spherical mixed MgCl20.48*EtOH.1.15H2O. complex was prepared according to the following method. For the test a starting microspheroidal MgCl2.2.8C2H5OH was used, prepared as described in example 1 with the only difference that the stirring conditions were adjusted so as to obtain a solid adduct having an average size of 45.6 μm. The said adduct was then subject to thermal dealcoholation at increasing temperatures from 30 to 130° C. and operating in nitrogen current until a chemical composition of EtOH=24.2% wt, H2O=3.2% wt. magnesium chloride=72.6 wt. was reached. The support obtained (500 g) was loaded into a 65 mm diameter glass jacketed fluidized bed reactor equipped with dedicated heating systems for both fluidization nitrogen and for the reactor main body, fluidized with nitrogen at 1300 l/h providing a good fluidization and warmed up from room temperature to 40° C. in few minutes, and then kept at 40° C. for a total reaction time of 9 hours. After warming-up time, a calibrated amount of water (75 g) was slowly added to the reactor by a precise volumetric peristaltic pump, operating at a feed rate of about 0.14 ml/min. The water was fed directly into the fluidizing (jacketed) nitrogen line, warmed up to 46-48° C. and then introduced to the fluidized reactor as water vapor. The moist nitrogen stream temperature was measured just below the fluidizing grid, operating between 40-41° C., and recorded. After about 9 hrs of continuous water feeding into the reactor the total desired amount of water was fed. Nitrogen flow was progressively reduced from 1300 down to 700 l/h to prevent mass loss. After completion of water adduction, the support is cooled down to room temperature and discharged (490 g). Chemical analyses showed 17.4% Mg, 14.8% water, 15.7% EtOH and corresponding to a complex of the following composition: 0.48 EtOH.1.15H2O.MgCl2. The final adduct showed a porosity of 0.52 cm3/g
A sample of spherical mixed 1.17*EtOH.1.02*H2O.MgCl2 complex was prepared according to the following method. For the test a starting microspheroidal MgCl2.2.8C2H5OH was used, prepared as described in example 1 with the only difference that the stirring conditions were adjusted so as to obtain a solid adduct having an average size of 73.4 μm. The so obtained adduct, was then subject to thermal dealcoholation at increasing temperatures from 30 to 130° C. and operating in nitrogen current until a chemical composition of EtOH=45.6% wt, H2O=1.3% wt. magnesium chloride=53% wt. was reached. Once obtained, 500 g of this material were loaded into a 65 mm diameter glass jacketed fluidized bed reactor equipped with dedicated heating systems for both fluidization nitrogen and for the reactor main body, fluidized at 1080 l/h providing a good fluidization, and warmed up from room temperature to 45° C. in few minutes. After warming-up time, a calibrated amount of water (58 g) was slowly added to the reactor by a precise volumetric peristaltic pump, operating at a feed rate of about 0.14 ml/min (8.5 ml/h) and kept at 45° C. for a total reaction time of about 7 hours. The water was fed directly into the fluidizing (jacketed) nitrogen line, warmed up to 52-53° C. and then introduced to the fluidized reactor as water vapor. The moist nitrogen stream temperature was measured just below the fluidizing grid, operating at 45° C., and recorded. After about 7 hrs of continuous water feeding into the reactor the total desired amount of water was fed. Nitrogen flow was kept at 1080 l/h for the whole duration of the trial. After completion of water adduction, the support is cooled down to room temperature and discharged (440 g). Chemical analyses showed 14.3% Mg, 10.8% water, 31.7% ethanol, corresponding to a complex of the formula 1.17EtOH.1.02H2O.MgCl2 complex. The final adduct showed a porosity of 0.32 cm3/g
A sample of spherical 1.07H2O.MgCl2 complex was prepared according to the following method. For the test a starting microspheroidal MgCl2.2.8C2H5OH was used, prepared as described in example 1 with the only difference that the stirring conditions were adjusted so as to obtain a solid adduct having an average size of 44 μm. The so obtained adduct was then subject to thermal dealcoholation at increasing temperatures from 30 to 130° C. and operating in nitrogen current until a chemical composition of EtOH=24.2% wt, H2O=1.6% wt., magnesium chloride 74.2% wt. was reached. Once obtained, 500 g of this material were loaded into a 65 mm glass jacketed fluidized bed reactor as described in Example 2, were first fluidized using nitrogen at a feed rate of 600 l/h and then gradually lowering to 360 l/h in the second part of the preparation, always providing a good fluidization; the spherical support was warmed up from room temperature to 120° C. in 30 minutes, and then kept at 120° C. for 2 hrs., then 130° C. for 2 hrs., and finally 135° C. for 4 hrs, while the nitrogen was warmed up by a heating system operated at the same temperature, achieving a warming up the gas to 72-78° C. under reactor grid. After warming-up time, a calibrated amount of water (68 g) was slowly added to the reactor by a precise volumetric peristaltic pump, operating at a feed rate of about 0.19 ml/min for 6 hrs. The water was fed directly into the fluidizing (jacketed) nitrogen line, warmed up to 72-78° C. and then introduced to the fluidized reactor as water vapor. After about 6 hrs of continuous water feeding into the reactor plus and extra equilibration processing time of 2 hrs (with no water supply), the total desired amount of water was fed. After completion of water adduction, the support is cooled down to room temperature and discharged (406 g). Chemical analyses showed 21.7% Mg, 17.2% water, corresponding to a complex of formula 1.07H2O.MgCl2 which also showed a porosity of 0.746 cm3/g.
A sample of spherical 5.91*H2O.MgCl2 complex was prepared in a rotavapor, which was employed as flowing/rolling-bed reactor. The flask was loaded with 100 g of bi-hydrate MgCl2 complex prepared as described in example 1. The flask was then attached to the rotavapor and the support was thus allowed to roll into the flask, while external moist air was continuously circulated into the flask of rolling support, carrying along small amounts of water vapor. The water was thus supplied in a continuous way, resulting in a progressive weight increase of the flask & support gross weight. After 120 hours of rolling, 156 g of spherical material were collected, having a composition of 5.91H2O.MgCl2 and a porosity of 0.369 cm3/g.
A sample of spherical 3.57H2O.MgCl2 complex was prepared in a rotavapor used as flowing/rolling bed reactor as above.
Hydration was followed by measuring weight increase as above. After 12 h of rolling, 100 g of bi-hydrate MgCl2 complex prepared as described in example 1 were transformed into 113.2 g of a spherical support, having a composition of 3.6H2O.MgCl2 having porosity of 0.533 cm3/g.
A sample of spherical 2*H2O.MgCl2 complex was prepared by dehydration in an oven of an adduct MgCl2.6H2O prepared according to Example 1 of U.S. Pat. No. 3,953,414. The porosity determination gave a result of 0.21 cm3/g.
A magnesium chloride and alcohol adduct was prepared following the method described in example 2 of U.S. Pat. No. 4,399,054, but working at 2000 RPM instead of 10000 RPM. The adduct containing about 3 mols of alcohol and 3.1% wt of H2O and had an average size of about 70 μm. The adduct were subject to a thermal treatment, under nitrogen stream, over a temperature range of 50-150° C. until an adduct having formula 0.8*EtOH.0.2*H2O.MgCl2 was reached.
Catalysts were prepared starting from the different MgCl2 based complexes as obtained in the examples 1-6 and comparative example 8 according to the following general procedure.
Into a 2 l glassware reactor provided with a stirrer, 1.0 L of TiCl4 at 0° C. and the amount of spherical support needed to get a total Lewis Base concentration of 0.8 mol/L were gently introduced. The whole was heated to 135° C. over 150 minutes and these conditions were maintained for a further 4.5 h. The stirring was interrupted and after 30 minutes the liquid phase was separated from the solid. Thereafter 6 washings with anhydrous hexane (1.01) were performed two of which were carried out at 60° C. and four at room temperature. After drying under vacuum at about 50° C., a free flowing solid was recovered and analyzed. Catalyst characteristics are reported in Table 1.
Catalysts were prepared starting from the different MgCl2 based complexes as obtained in the examples 1-6 and comparative example 8 according to the following general procedure.
Into a 2 l glassware reactor provided with a stirrer, 1.0 L of TiCl4 at 0° C. and the amount of spherical support needed to get a total Lewis Base concentration of 0.8 mol/L were gently introduced. The whole was heated to 135° C. over 150 minutes and these conditions were maintained for a further 4.5 h. The stirring was interrupted and after 30 minutes the liquid phase was separated from the solid.
Fresh TiCl4 (1.0 L) was loaded into the reactor and the resulting slurry was warmed to 130° C. for one hour. Then, the stirring was stopped and after 30 minutes, the liquid phase was drawn off. Thereafter 6 washings with anhydrous hexane (1.0 L) were performed two of which were carried out at 60° C. and four at room temperature. After drying under vacuum at about 50° C., a free flowing solid was recovered and analyzed. Catalyst characteristics are reported in Table 1.
The whole set of catalysts obtained as described in the previous examples were tested in ethylene polymerization experiments according to the following procedure.
Into a 4 liters stainless steel autoclave, degassed under N2 stream at 70° C., 1600 cc of anhydrous hexane, 0.08 g of spherical catalyst and 0.3 g of triisobutylaluminum (Tiba) were introduced. The whole was stirred, heated to 75° C. and thereafter 7 bar of H2 and 7 bar of C2H4 were fed. The polymerization lasted 2 hours feeding ethylene to keep the pressure constant. At the end, the reactor was depressurised and the temperature was dropped to 30° C. The collected polymer was dried at 70° C. under a nitrogen flow. The obtained resulted are showed in Table 2.
The whole set of catalysts obtained as described in the previous examples were tested in ethylene polymerization experiments according to the following procedure.
Into a 4 liters stainless steel autoclave, degassed under N2 stream at 70° C., 1600 cc of anhydrous hexane, 0.1 g of spherical catalyst and 0.5 g of triethylaluminum (Tea) were introduced. The whole was stirred, heated to 85° C. and thereafter 9 bar of H2 and 3 bar of C2H4 were fed. The polymerization lasted 2 hours feeding ethylene to keep the pressure constant. At the end, the reactor was depressurised and the temperature was dropped to 30° C. The collected polymer was dried at 70° C. under a nitrogen flow.
The obtained resulted are reported in Table 2.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10150409.0 | Jan 2010 | EP | regional |
This application is the U.S. national phase of International Application PCT/EP2010/070010, filed Dec. 17, 2010, claiming priority to European Application 10150409.0 filed Jan. 11, 2010 and the benefit under 35 U.S.C. 119(e) of U.S. Provisional Application No. 61/284,680, filed Dec. 23, 2009; the disclosures of International Application PCT/EP2010/070010, European Application 10150409.0 and U.S. Provisional Application No. 61/284,680, each as filed, are incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2010/070010 | 12/17/2010 | WO | 00 | 6/18/2012 |
| Number | Date | Country | |
|---|---|---|---|
| 61284680 | Dec 2009 | US |
