CATALYST COMPONENTS FOR THE POLYMERIZATION OF OLEFINS

FIELD OF THE INVENTION

[0001] The present disclosure relates to catalyst components for the (co)polymerization of olefins having improved flowability, including catalysts obtained from the catalyst components and their use in processes for the (co)polymerization of olefins.

BACKGROUND OF THE INVENTION

[0002] Ziegler-Natta catalyst components may be used for the stereospecific polymerization of olefins, such as propylene. The first catalyst of this type that was widely used in the industry comprised solid TiC obtained by the reduction of TiCU with aluminum alkyl compounds. However, the activity and stereospecificity of the catalysts were often not commercially viable and the resulting polymers had to be subjected to a de-ashing treatment to remove the catalyst residues, and to a washing step for removing any resulting atactic polymer. The catalysts presently used often comprise a solid catalyst component further comprising a magnesium dihalide and one or more of a supported titanium compound, an internal electron donor compound, and an Al-alkyl compound as a cocatalyst.

[0003] Depending on the type of polymerization technologies one may employ, the particle size of the catalyst may range from about 5 to about 200 μιη. However, this size range may be subject to cohesiveness problems that worsen flowability and decrease the homogeneous distribution of the catalyst particles in the reactor.

[0004] In order to address these issues, slip agents such as stearates or erucamide have been employed. However, these additives have generally not improved the flowability features. U.S. Pat. App. Pub. No. 2015/0344667 suggests coating the catalyst or carrier particles with a layer of nanoparticles made of conductive material, such as carbon black. However, this process is burdensome because an additional, separate step for the preparation of a gel comprising the nanoparticles must be performed. Moreover, the presence of an additional layer may prevent the necessary interaction between the catalytically active metal(s) and the carriers. Additionally, the procedure, which comprises the use of a water-based nanoparticles gel, can inactivate the Ti based catalyst.

[0005] A simple way of improving catalyst flowability without compromising its catalytic performance is therefore desirable.

[0006] Accordingly, the applicants have surprisingly found that enhanced catalyst flowability may be obtained by mechanically mixing the catalyst component particles with low amounts of separated inorganic particles having specific compositions.

SUMMARY OF THE INVENTION

[0007] An object of the present disclosure relates to a catalyst mixture comprising a mechanical mixture of (a) particles of solid catalyst component comprising titanium (Ti), magnesium (Mg), and chloride (CI), and (b) from 0.2 to 5.0% by weight of particles of a solid compound having a particle size ranging from 0.1 μιη to 1 mm and containing more than 50% by weight of S1O2 units.

DETAILED DESCRIPTION OF THE INVENTION

[0008] The term mechanical mixture indicates that the particles of solid catalyst component (a) are distinct and separated from those of solid compound (b). Said particles of catalyst component (a) and particles of compound (b) being brought in close proximity to each other by means of mechanic mixing.

[0009] Preferably, in the catalyst mixture of the present disclosure the inorganic solid compound has particle size ranging from 2 to 800 μιη, more preferably from 1 to 100 μιη and especially ranging from 1 to 30 μιη.

[0010] Preferably, the solid compound b) containing more than 50% by weight of Si0 ₂ units is selected from silica, silicates and diatomaceous earth. Among silicates, particularly preferred are phyllosilicates like talc. Preferred type of silica is the hydrophilic silica, i.e, silica that has not been modified to be made it hydrophobic. Among them, the use of crystalline silica in particular having size from 0.1 to 5 μιη is preferred. By the term crystalline silica is meant a silica based material showing an X- ray spectra with sharp reflections similar to those of quartz or cristobalite.

[0011] Also, the use of diatomaceous earth is preferred. Among them particularly preferred is the use of diatomaceous earth commercialized under the name Celite®. [0012] The particle size of the solid catalyst component preferably ranges from 4 to

120 μιη more preferably from 8 to 100 μιη and especially from 10 to 90 μιη.

[0013] Preferably the amount of particles of solid compound (b) ranges from 0.5 to

5% more preferably from 0.75% to 4% and especially from 1 to 3%wt based on the total weight of catalyst mixture (a)+(b).

[0014] The solid catalyst component may be of granular, spheroidal irregular or spherical regular morphology.

[0015] Granular or otherwise irregular catalyst particle may be obtained by reacting

Ti-halides with precursors of general formula MgX _n (OR)2-n in which X is CI or a Ci-Cio hydrocarbon group, R is a Ci-Cs alkyl group and n ranges from 0 to 2. Such a reaction generates solid particles basically composed of MgCl ₂ on which Ti compound are fixed.

[0016] Catalyst components with a spherical morphology may be obtained by reacting

Ti-halides with precursors comprising adducts of formula where R is a Ci-C8 alkyl group, preferably ethyl, and n is from 2 to 6.

[0017] The preferred solid catalyst components according to the present disclosure are those having a prevailing spherical shape. In particular, prefererred are those characterized by a sphericity factor higher than 0.60 and preferably higher than 0.70. The sphericity factor being calculated using the image analysis technique described in the characterization section of the present application.

[0018] According to a specific embodiment, the solid catalyst component has a sphericity factor higher than 0.7 and a particle size ranging from 10 to 90 μιη.

[0019] Preferably, the amount of Mg in the solid catalyst component ranges from 8 to 30% more preferably from 10 to 25%wt.

[0020] Preferably, the amount of Ti ranges from 0.1 to 8%, more preferably from

0.5 to 5% and even more preferably from 0.7 to 3%wt.

[0021] The titanium atoms preferably belong to titanium compounds of formula

Ti(OR ² )nX4-n in which n is comprised between 0 and 4; X is halogen and R ² is an hydrocarbon radical, preferably alkyl, radical having 1-10 carbon atoms. 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 TiCl ₄ , and Ti(OEt)Cl ₃ . In a preferred aspect of the present disclosure the catalyst components further comprise an electron donor compound (internal donor). Preferably, it is selected from esters, ethers, amines, silanes, carbamates and ketones or mixtures thereof.

2] When an increased stereospecificity of the catalyst is desired, the internal donor is preferably selected from the group consisting of alkyl and aryl esters of optionally substituted aromatic mono or polycarboxylic acids such as for example esters of benzoic and phthalic acids, and esters of aliphatic acids selected from malonic, glutaric, maleic and succinic acids. Specific examples of such esters are n-butylphthalate, di-isobutylphthalate, di-n-octylphthalate, ethyl-benzoate and p-ethoxy ethyl-benzoate. Also, the diesters disclosed in WO2010/078494 and US patent 7,388,061 can be used. Among this class, particularly preferred are the 2,4-pentanediol dibenzoate derivatives and 3-methyl-5-t-butyl catechol dibenzoates. In addition, the internal donor can be selected among diol derivatives chosen among dicarbamates, monoesters monocarbamates and monoesters monocarbonates. Moreover, can be advantageously used also the 1,3 diethers of the formula:

wherein R, R ¹ , R ⁿ , R ^m , R ^w and R ^v equal or different to each other, are hydrogen or hydrocarbon radicals having from 1 to 18 carbon atoms, and R ^VI and R ^vn , equal or different from each other, have the same meaning of R-R ^v except that they cannot be hydrogen; one or more of the R-R ^vn groups can be linked to form a cycle. The 1,3- diethers in which R ^VI and R ^vn are selected from C1-C4 alkyl radicals are particularly preferred.

It is also possible to use mixtures of the above mentioned donors. Specific mixtures are those constituted by esters of succinic acids and 1,3 diethers as disclosed in WO2011/061134. [0023] When it is desired to increase the capability of the catalyst to distribute an olefin co-monomer within a polymer chain, such as in case of production of ethylene/a-olefin copolymers, it is preferred to choose the electron donor among monofunctional donors, in particular ethers and esters. Preferred ethers are the C2-C20 aliphatic ethers and in particulars cyclic ethers preferably having 3-5 carbon atoms cyclic ethers such as tetrahydrofurane, dioxane. Preferred esters are C1-C4 alkyl esters of aliphatic mono carboxylic acids such as ethylacetate and methyl formiate. Tetrahydrofurane and ethylacetate are the most preferred.

[0024] In general, the final amount of electron donor compound in the solid catalyst component may range from 0.5 to 40% by weight preferably in the range from 1 to 35% by weight.

[0025] The preparation of the solid catalyst component can be carried out according to several methods. One method comprises the reaction between magnesium alcoholates or chloroalcoholates (in particular chloroalcoholates prepared according to U.S.Pat. 4,220,554) and an excess of TiCU in the presence of the electron donor compounds at a temperature of about 80 to 120°C.

According to a preferred method, the solid catalyst component can be prepared by reacting a titanium compound of formula Ti(OR ² )m-yXy, where m is the valence of titanium and y is a number between 1 and m and R ² has the same meaming as previously specified, preferably TiCU, with a magnesium chloride deriving from an adduct of formula MgCl2*pR ³ OH, where p is a number between 0.1 and 6, preferably from 2 to 3.5, and R ³ is a hydrocarbon radical having 1-18 carbon atoms. The adduct can be suitably prepared in spherical form 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. Examples of spherical adducts prepared according to this procedure are described in USP 4,399,054 and USP 4,469,648. The so obtained adduct can be directly reacted with Ti compound or it can be previously subjected to thermal controlled dealcoholation (at a temperature in a range of about 80-130°C) so as to obtain an adduct in which the number of moles of alcohol is lower than 3, preferably between 0.1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholated or as such) in cold TiCU (about 0°C); the mixture is heated up to 80-130°C and kept at this temperature for 0.5-2 hours. The treatment with TiCl ₄ can be carried out one or more times. The electron donor compound is preferably added during the treatment with TiCl ₄ . The preparation of catalyst components in spherical form are described for example in European Patent Applications EP-A-395083, EP-A-553805, EP-A-553806, EPA601525 and WIPO Pat. App. Pub. No. WO98/44009.

[0026] The catalyst mixture comprising the particles made of solid catalyst component (a) and the particles (b) made of the S1O2 unit based compound, can be prepared with several blending methods the preferred of which comprises dry blending the two solids in a suitable apparatus. Preferably the dry blending is carried out at room temperature for a time ranging from 0.2 to 20 hours, preferably from 0.5 to 15 hours and more preferably from 0.5 to 5 hours in a nitrogen environment.

[0027] It is also possible preparing the mixture by stirring a liquid hydrocarbon slurry of the particles (a) and (b) and afterwards removing the liquid phase followed by drying the particles.

[0028] As it can be seen from the examples, the so obtained catalyst mixtures show a reduced break energy with respect to the catalyst particles (a) as such. The improvement is particularly pronounced in combination with the use of catalyst having a sphericity factor higher than 0.60 and preferably higher than 0.70. These catalysts show flowability improvement also in the avalanche energy and in the funnel test thereby proving that the improvement can be seen in various stages of the catalyst handling. Also, the polymerization test carried out on the catalyst mixture confirms that the performances are at the same level as those of the solid catalyst component not containing the Si0 ₂ unit based compound.

[0029] The solid catalyst components according to the present disclosure are converted into catalysts for the polymerization of olefins by reacting them with organoaluminum compounds. In particular, an object of the present disclosure is a catalyst for the polymerization of olefins CH ₂ =CHR, in which R is a hydrocarbyl radical with 1-12 carbon atoms, optionally in mixture with ethylene, comprising the product obtained by contacting:

(i) the solid catalyst component as disclosed above and

(ii) an alkylaluminum compound and,

(iii) an external electron donor compound.

[0030] The alkyl-Al compound (ii) is preferably chosen among the trialkyl aluminum compounds such as for example triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides or alkylaluminum sesquichlorides, such as AlEt ₂ Cl and Al ₂ Et ₃ Cl ₃ , possibly in mixture with the above cited trialkylaluminums.

The Al/Ti ratio is higher than 1 and is preferably comprised between 50 and 2000. Suitable external electron-donor compounds include silicon compounds, ethers, esters, amines, heterocyclic compounds and particularly 2,2,6,6-tetramethylpiperidine and ketones.

[0031] Another class of preferred external donor compounds is that of silicon compounds of formula (R6) _a (R7)bSi(OR8) _c , where a and b are integers from 0 to 2, c is an integer from 1 to 4 and the sum (a+b+c) is 4; R ₆ , R ₇ , and Rs, are alkyl, cycloalkyl or aryl radicals with 1-18 carbon atoms optionally containing heteroatoms. Particularly preferred are the silicon compounds in which a is 1, b is 1, c is 2, at least one of R ₆ and R ₇ is selected from branched alkyl, cycloalkyl or aryl groups with 3-10 carbon atoms optionally containing heteroatoms and Rs is a Ci-Cio alkyl group, in particular methyl. Examples of such preferred silicon compounds are methylcyclohexyldimethoxysilane (C donor), diphenyldimethoxysilane, methyl- t-butyldimethoxysilane, dicyclopentyldimethoxysilane (D donor), diisopropyldimethoxysilane, (2- ethylpiperidinyl)t-butyldimethoxysilane, (2-ethylpiperidinyl)thexyldimethoxysilane, (3,3,3-trifluoro-n-propyl)(2-ethylpiperidinyl)dimethoxysilan e, methyl(3,3,3-trifluoro-n- propyl)dimethoxysilane. Moreover, the silicon compounds in which a is 0, c is 3, R ₇ is a branched alkyl or cycloalkyl group, optionally containing heteroatoms, and Rs is methyl are also preferred. Examples of such preferred silicon compounds are cyclohexyltrimethoxysilane, t-butyltrimethoxysilane and thexyltrimethoxysilane.

[0032] The electron donor compound (iii) is used in such an amount to give a molar ratio between the organoaluminum compound and said electron donor compound (iii) of from 0.1 to 500, preferably from 1 to 300 and more preferably from 3 to 100. Therefore, it constitutes a further object of the present disclosure a process for the (co)polymerization of olefins CH ₂ =CHR, in which R is hydrogen or a hydrocarbyl radical with 1-12 carbon atoms, carried out in the presence of a catalyst comprising the product of the reaction between:

(i) the solid catalyst component of the present disclosure;

(ii) an alkylaluminum compound and,

(iii) optionally an electron-donor compound (external donor).

[0033] The polymerization process can be carried out according to various techniques, for example slurry polymerization using as diluent an inert hydrocarbon solvent, or bulk polymerization using the liquid monomer (for example propylene) as a reaction medium. Moreover, it is possible to carry out the polymerization process in gas-phase operating in one or more fluidized or mechanically agitated bed reactors.

[0034] The polymerization is may be carried out at temperature of from 20 to

120°C, preferably of from 40 to 80°C. When the polymerization is carried out in gas- phase the operating pressure is ranges from 0.5 and 5 MPa, preferably from 1 to 4 MPa. In the bulk polymerization the operating pressure is may range from 1 to 8 MPa, preferably from 1.5 to 5 MPa.

[0035] The following examples are given in order to better illustrate the invention without limiting it.

EXAMPLES

[0036] Determination of X.I.

2.5 g of polymer and 250 ml of o-xylene were placed in a round-bottomed flask provided with a cooler and a reflux condenser and kept under nitrogen. The obtained mixture was heated to 135°C and kept under stirring for about 60 minutes. The final solution was allowed to cool to 25°C under continuous stirring, and the insoluble polymer was then filtered. The filtrate was then evaporated in a nitrogen flow at 140°C to reach a constant weight. The content of said xylene- soluble fraction is expressed as a percentage of the original 2.5 grams and then, by difference, the X.I. %.

[0037] Average Particle Size

Determined by a method based on the principle of the optical diffraction of monochromatic laser light with the "Malvern Instruments 2000" apparatus. The average size is given as P50. P10 and P90 are also determined with this method.

P90 - P10

The particle size distribution (SPAN) is calculated with the formula ^"50 wherein P90 is the value of the diameter such that 90% of the total volume of particles have a diameter lower than that value; P10 is the value of the diameter such that 10% of the total volume of particles have a diameter lower than that value and P50 is the value of the diameter such that 50% of the total volume of particles have a diameter lower than that value.

[0038] The Malvern Mastersizer 2000 particle size analyzer is divided into three units :

[0039] 1) an optical unit; Optical core unit for measurements of solids of sizes ranging from 0,02 to 2000μ, equipped with two laser beam sources: red He/Ne laser, power 5mw, wave length 633 nm., blue (diode) laser, wave length 450nm.

[0040] 2) a sampling Unit; Hidro 2000S automatic Sampling Unit for volumes between 50 and 120 ml, operating with internal capacity, centrifuge pump, stirrer and ultrasound probe with 40W power output.

[0041] 3) a PC console; Portable LG Pentium series, using Malvern Professional software for Windows 2000 or NT. Method of data elaboration using Mie optics theory

(Refractive Index for sample =1.596; Refractive Index for n-heptane =1.39).

[0042] Method description

[0043] For the measurements described herein n-heptane (plus 2 g/1 antistatic Span

80) is used as dispersing agent.

[0044] The Measuring cell is loaded with dispersing agent, while pump/agitator speed is set up to 2205 RPM. Background measurement is then taken. Then sample is loaded, by using a dedicated loading mean for solids or slurries. A that point, before being subject to PS Determination, the sample undergoes 30 seconds of ultrasound treatment. After that, the measurement is taken.

[0045] Determination of Break Energy and Avalanche Energy

[0046] Measurements were carried out with a Revolution Powder Analyzer

(Mercury Scientific Inc., Newtown, CT, USA). Specific measurement conditions are provided in the user manual revised on August 30, 2014.

[0047] Determination of Sphericity Factor

[0048] The determination was carried out with the image analyzer commercial software Analysis Pro 3.2 which describes the sphericity of a particle using an algorithm applied to a source of image constituted by a SEM picture the dimension of which are selected based on the average size of the catalyst particle so as to include a statistically representative number of particles. For the catalyst sample having average particle size of 70μιη the size of the picture was 2.5x2.5mm. For instance, for the catalyst sample having particle size of about 9 μιη the size of the picture was 150 μιη xl50 μιη.

EXAMPLES

[0049] Procedure for the preparation of the spherical adduct

An initial amount of micro spheroidal MgCi2-2.8C2H50H was prepared according to the method described in Example 2 of USP 4,399,054 but operating at 3,000 rpm instead of 10,000. The so resulting adduct had an average particle size of 70μιη was then subject to thermal dealcoholation at increasing temperatures from 30 to 130°C in nitrogen current until the alcohol content is about 42%wt.

[0050] Procedure for the preparation of the spherical solid catalyst component

Three lots of solid catalyst component were prepared according to the following procedure. Into a 500 ml round bottom flask, equipped with mechanical stirrer, cooler and thermometer 300 ml of TiCU were introduced at room temperature under nitrogen atmosphere. After cooling to 0°C, while stirring, diisobutylphthalate and 9.0 g of the spherical adduct (prepared as described above) were sequentially added into the flask. The amount of charged internal donor was such to meet a Mg/donor molar ratio of 8. The temperature was raised to 100°C and maintained for 2 hours. Thereafter, stirring was stopped, the solid product was allowed to settle and the supernatant liquid was siphoned off at 100°C. After the supernatant was removed, additional fresh TiCU was added to reach the initial liquid volume again. The mixture was then heated at 120°C and kept at this temperature for 1 hour. Stirring was stopped again, the solid was allowed to settle and the supernatant liquid was siphoned off. The solid was washed with anhydrous hexane six times in temperature gradient down to 60°C and one time at room temperature. The resulting solid was then dried under vacuum and characterized. Its sphericity factor resulted to be 0.77 for the lot A, 0.79 for Lot B, and 0.75 for Lot C.

The propylene polymerization test for catalyst Lot A produced PP with a catalyst activity of 23 kg/gcat and 97.1% of Xylene insolubility.

[0051] Procedure for the polymerization of propylene

[0052] A 4 liter (L) steel autoclave equipped with a stirrer, pressure gauge, thermometer, catalyst feeding system, monomer feeding lines and thermostatic jacket, was used. The reactor was charged with 0.01 grams, of solid catalyst component 0,76 g of TEAL, 0.063 grams of cycloexylmethyldimethoxy silane, 3.2 1 of propylene, and 2.0 1 of hydrogen. The system was heated to 70°C over 10 min. under stirring, and maintained under these conditions for 120 min. At the end of the polymerization, the polymer was recovered by removing any unreacted monomers and was dried under vacuum.

[0053] The autoclave was closed and the desired amount of hydrogen was added

(in particular, 2 NL in D donor tests, 1.5 NL in C donor tests and 1.25 NL in tests without external donor were used). Then, under stirring, 1.2 kg of liquid propylene was fed into the reaction. The temperature was raised to 70°C in about 10 minutes and the polymerization was carried out at this temperature for 2 hours. At the end of the polymerization, the non-reacted propylene was removed; the polymer was recovered and dried at 70°C under vacuum for 3 hours. The resulting polymer was weighed and characterized. [0054] EXAMPLES

[0055] Examples 1-4 and Comparative Example 1

[0056] A series of four mixtures was prepared by dry mixing the lot A of the solid catalyst component prepared according to the general procedure with the specific amount reported in Table 1 of Celite® a diatomeaceous earth commercially available from Sigma-Aldrich having mean particle size of 22 μιη. The blending was carried out as follows. 100 grams of the solid catalyst component were introduced in a 1L glass bottle and then, the amount of Celite® reported in table lwas also added.

[0057] The solids were mixed by tumbling the bottle for lh at 60rpm.

[0058] The resulting mixtures were subject to energy break and avalanche energy determination and the results are reported in Table l._A polymerization test for the mixtures of examples 1 and 2 was carried out. The propylene polymerization test for catalyst Example 1 produced PP with a catalyst activity of 25 kg/gcat and 96.9% of xylene insolubility while the test for example 2 produced PP with a catalyst activity of 23 kg/gcat and 96.9% of xylene insolubility. This demonstrates that the use of the S1O2 based compound does not alter the catalyst performances.

[0059] Examples 5-18 and Comparative Examples 2-5

[0060] The mixture were prepared as described in Examples 1-4 with the difference that Lot B was used instead of Lot A and S1O2 based unit compounds reported in Table 1 were used instead of Celite®.

[0061] Silica S5631 having mean particle 0.9 μιη (commercially available from

Fluka).

[0062] Silica S342890 having mean particle 10 μιη (commercially available from

Sigma-Aldrich).

[0063] Silica S342831 having more than 90% of particles with size of greater than

800 μιη was commercially available from Sigma-Aldrich.

[0064] Gasil AB 200DF is commercialized by PQ corporation. It is an amorphous silica with P50 size of 5 μιη.

[0065] Gasil AB 735 is commercialized by PQ corporation. It is an amorphous silica with P50 size of 3 μιη. [0066] Comparative Examples 7-9

[0067] The mixture were prepared as described in Examples 1-4 with the difference that Lot C was used instead of Lot A and the slip agents reported in Table 1 were used instead of Celite®.

[0068] Examples 14-15 and Comparative example 10

[0069] The mixtures were prepared as described in Examples 1-4 with the difference that the solid catalyst component was of a granular type prepared as described in example 1 of U.S. Pat. No 7,759,445 (having a sphericity factor of 0.55) were tested for energy break and avalanche energy determination and the results are reported in Table 1.

Table 1

Table 1 Cont.