ZIEGLER-NATTA CATALYSTS FOR OLEFIN POLYMERIZATION
20220363785 · 2022-11-17
Inventors
Cpc classification
C08F4/651
CHEMISTRY; METALLURGY
C08F210/16
CHEMISTRY; METALLURGY
C08F210/16
CHEMISTRY; METALLURGY
C08F2410/01
CHEMISTRY; METALLURGY
C08F4/643
CHEMISTRY; METALLURGY
International classification
Abstract
The present invention relates to substituted 2-iso-propyl-1, 3-dialkoxypropanes, and more particularly to their use as internal donors in Ziegler-Natta catalysts to obtain ethylene (co)polymers with desirable properties. The present disclosure further concerns use of Ziegler-Natta catalyst components comprising said substituted 2-iso-propyl-1, 3-dimethoxypropanes and use of Ziegler-Natta catalysts in ethylene (co)polymerization comprising said Ziegler-Natta catalyst components.
Claims
1-3. (canceled)
4. A Ziegler-Natta catalyst component comprising an internal donor selected from compounds of formula (I) ##STR00015## wherein R.sub.1 is C.sub.4-10-alkyl; and R.sub.2 and R.sub.3 are each independently C.sub.1-3-alkyl.
5. The Ziegler-Natta catalyst component according to claim 4 further comprising: (ii) a compound of a transition metal Group 4 to 6 of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005); (iii) a compound of metal Group 1 to 3 of the Periodic Table (IUPAC, 2005); and (iv) optionally, a compound of a element of Group 13 of the Periodic Table (IUPAC, 2005).
6. The Ziegler-Natta catalyst component according to claim 4 wherein the Ziegler-Natta catalyst component comprises: (ii) a Group 4 to 6 metal content (determined by ICP Analysis) in the range of 1.0 wt % to 15.0 wt % of the total weight of the Ziegler-Natta catalyst component; (iii) a Group 1 to 3 content (determined by ICP Analysis) in the range of 5.0 wt % to 30.0 wt % of the total weight of the Ziegler-Natta catalyst component; (iv) a Group 13 element content (determined by ICP Analysis) in the range of 0 wt % to 3.0 wt % of the total weight of the Ziegler-Natta catalyst component.
7. A Ziegler-Natta catalyst component according to claim 4, wherein the Ziegler-Natta catalyst component is prepared by a method comprising: (M-a) providing a solid support; (M-b) pre-treating the solid support of step (M-a) with a compound of Group 13 element; (M-c) treating the pre-treated solid support of step (M-b) with a transition metal compound of Group 4 to 6; (M-d) recovering the Ziegler-Natta catalyst component; wherein the solid support is contacted with an internal organic compound of formula (I) or mixtures therefrom before treating the solid support in step (M-c).
8. A method for producing a Ziegler-Natta catalyst component according to claim 4, comprising adding an internal donor selected from compounds of formula (I) ##STR00016## wherein R.sub.1 is C.sub.4-10-alkyl; and R.sub.2 and R.sub.3 are each independently C.sub.1-3-alkyl, to a process of preparing the Ziegler-Natta catalyst component.
9. A Ziegler-Natta catalyst for ethylene (co)polymerization, wherein the Ziegler-Natta catalyst comprises: (A) the Ziegler-Natta catalyst component as defined in claim 4; (B) a cocatalyst selected from element compounds of Group 13 of the Periodic Table (IUPAC, 2005); and (C) optionally, an external donor.
10. (canceled)
11. A method of ethylene (co)polymerization optionally with C.sub.3-20 comonomers, comprising: a) introducing into a polymerization reactor a Ziegler-Natta catalyst component comprising an internal donor of formula (I) ##STR00017## wherein R.sub.1 is C.sub.4-10-alkyl; and R.sub.2 and R.sub.3 are each independently linear or branched C.sub.1-3-alkyl.
12. The method as claimed in claim 11, wherein the internal donor of formula (I) is selected from compounds of formula (I-a) or (I-b) ##STR00018## wherein R.sub.1 is C.sub.4-10-alkyl.
13. The method according to claim 11, wherein the internal donor is comprised in a Ziegler-Natta catalyst component further comprising (ii) a transition metal compound of Group 4 to 6 of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005); (iii) a metal compound of Group 1 to 3 of the Periodic Table (IUPAC, 2005); and (iv) optionally, a compound of group 13 of the Periodic Table (IUPAC, 2005).
14. A process for producing ethylene homo- or copolymers, comprising: (P-a) introducing a Ziegler-Natta catalyst component, comprising: (i) an internal donor selected from compounds of formula (I), or from formulas (I-a) and (I-b) ##STR00019## wherein R.sub.1 is C.sub.4-10-alkyl; and R.sub.2 and R.sub.3 are each independently linear or branched C.sub.1-3-alkyl; (ii) a transition metal compound of Group 4 to 6 of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005); (iii) a metal compound of Group 1 to 3 of the Periodic Table (IUPAC, 2005); and (iv) optionally, a compound of group 13 of the Periodic Table (IUPAC, 2005) into a polymerisation reactor, (P-b) introducing a cocatalyst capable of activating the said Ziegler-Natta catalyst component into the polymerisation reactor; (P-c) introducing ethylene, optionally C.sub.3-20α-olefin comonomers, and optionally hydrogen into the polymerisation reactor; and (P-d) maintaining said polymerisation reactor in such conditions as to produce an ethylene homo- or copolymer.
15. The process according to claim 14, wherein (co)polymerizing ethylene is accomplished in a multi-stage polymerization process comprising at least one gas phase reactor for producing ethylene (co)polymers.
16. The process according to claim 14, wherein (co)polymerizing ethylene is accomplished in a multi-stage polymerization process comprising at least one slurry reactor, preferably two slurry reactors, and one gas phase reactor.
17. The Ziegler-Natta catalyst component according to claim 4, wherein compound of formula (I) is selected from compounds of formula (I-a) and (I-b) ##STR00020## wherein R.sub.1 is C.sub.4-10-alkyl.
Description
[0184] The advantages of the present invention are shown in the experimental part and in the figures:
[0185]
[0186]
[0187]
[0188] EXPERIMENTAL PART
[0189] Analytical Methods
[0190] A1, Mq, Ti contents in a catalyst component by ICP-OES
[0191] The sample consisting of dry catalyst component powder is mixed so that a representative test portion can be taken. Approximately 20-50 mg of material is sampled in inert atmosphere into a 20 mL volume vial and the exact weight of powder recorded.
[0192] A test solution of known volume (V) is prepared in a volumetric flask as follows. Sample digestion is performed in the cooled vial by adding a small amount of deionized and distilled (DI) water (5% of V), followed by adding concentrated nitric acid (65% HNO3, 5% of V). The mixture is transferred into a volumetric flask. The solution diluted with DI water up to the final volume V, and left to stabilise for two hours.
[0193] The elemental analysis of the resulting aqueous samples is performed at room temperature using a Thermo Elemental iCAP 6300 Inductively Coupled Plasma—Optical Emission Spectrometer (ICP-OES). The instrument is calibrated for A1, Ti and Mg using a blank (a solution of 5% HNC.sub.3) and six standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300 ppm of A1, Ti and Mg in solutions of 5% HNO3 DI water. Curvelinear fitting and 1/concentration weighting is used for the calibration curve.
[0194] Immediately before analysis the calibration is verified and adjusted (instrument function named “re-slope”) using the blank and a 300 ppm A1, 100 ppm Ti, Mg standard. A quality control sample (QC; 20 ppm A1 and Ti, 50 ppm Mg in a solution of 5% HNC.sub.3 in DI water) is run to confirm the re-slope. The QC sample is also run after every 5.sup.th sample and at the end of a scheduled analysis set.
[0195] The content of magnesium is monitored using the 285.213 nm line and the content for titanium using 336.121 nm line. The content of aluminium is monitored via the 167.079 nm line, when A1 concentration in test portion is between 0-10 wt % and via the 396.152 nm line for A1 concentrations above 10 wt %.
[0196] The reported values are an average of results of three successive aliquots taken from the same sample and are related back to the original catalyst sample based on input into the software of the original weight of test portion and the dilution volume.
[0197] CI Content in a Catalyst Component by Potentiometric Titration
[0198] Chloride content of catalyst components is determined by titration with silver nitrate. A test portion of 50-200 mg of a catalyst component is weighed under nitrogen in a septum-sealed vial. A solution of 1 part of concentrated HNC.sub.3 (68%, analytical grade) and 4 parts of deionized and distilled (DI) water are added to the sample in an aliquot of 2.5 mL using a syringe. After the reaction completion and dissolution of the catalyst component material, the solution is transferred into a titration cup using an excess of DI water. The solution is then immediately titrated with a commercially certified solution of 0.1M AgNO3 in a Mettler Toledo T70 automatic titrator. The titration end-point is determined using an Ag-electrode.
[0199] The total chloride amount is calculated from the titration and related to the original sample weight.
[0200] Volatiles in a Catalyst Component by GC-MS
[0201] A test solution using a 40-60 mg test portion of catalyst component powder is prepared by liquid-liquid extraction of the sample and internal standard in water and dichloromethane:first, 10 mL of dichloromethane are added to the test portion, followed by addition of 1 mL of the internal standard solution (dimethyl pimelate, 0.71 vol % in deionized water) using a precision micro-syringe. The suspension is sonicated for 30 min and left undisturbed for phase separation. A portion of the test solution is taken from the organic phase and filtered using a 0.45 μm syringe filter.
[0202] For the calibration, five standard stock solutions with different analyte concentrations are prepared by dosing five increasing portions of analyte standard materials accurately into volumetric flasks and filling up to mark with methanol. For the preparation of the calibration samples, aliquots of 200 μL from the stock solutions are extracted with the aqueous ISTD solution and dichloromethane in the same volume ratios as for the samples. The analyte amount in the final calibration samples ranges from 0.1 mg to 15 mg.
[0203] The measurement is performed using an Agilent 7890B Gas Chromatograph equipped with an Agilent 5977A Mass Spectrometer Detector. The separation is achieved using a ZB-XLB-HT Inferno 60 m×250 μm×0.25 μm column (Phenomenex) with midpoint backflush through a three channel auxiliary EPC and a pre-column restriction capillary of 3 m×250 μm×0 μm. The initial oven temperature is 50° C. and the hold time is 2 min. The oven ramp consists of a first stage of 5° C./min to 150° C. and a second stage of 30° C./min to 300° C. followed by a 1 min post-run backflush at 300° C.
[0204] The inlet operates in split mode. Injection volume is 1 μL, inlet temperature 280° C., septa purge 3 mL/min, total flow 67.875 mL/min and split ratio 50:1. Carrier gas is 99.9996% He with pre-column flow of 1.2721 mL/min and additional flow of 2 mL/min from the backflush EPC to the analytical column. The MS detector transfer line is kept at 300° C. The MSD is operated in Electron Impact mode at 70 eV and Scan mode ranging from 15-300 m/z.
[0205] The signal identities are determined by retention times (heptane 4.8, toluene 6.3, dimethyl-pimelate 23.2) and target ion m/z (heptane 71.1, toluene 91.1, dimethyl pimelate 157.1). Additionally, qualifier ions are used for confirmation of the identification (heptane, toluene). The target ion signals of each analyte and the internal standard are integrated and compared to calibration curve, established in the beginning of each run with the five calibration samples. The calibration curves for the response ratios are linear without sample concentration weighting. A quality control sample is used in each run to verify the standardization. All test solutions are run in two replicate runs. The mass of the test portion is used for calculating the analyte concentration in the sample for both replicates and the result reported as the average.
[0206] Polymer melting and crystallization properties by DSC Polymer Differential Scanning calorimetry analysis (DSC) is performed using a Mettler Toledo DSC2 on 5-10 mg samples. The polymer powder or pellet cut or MFR string cut sample is placed in a 40 μL aluminium pan, weighed to the nearest 0.01 mg and the pan is sealed with a lid. DSC is run according to ISO 11357-3 or ASTM D3418 in a heat/cool/heat run cycle with a scan rate of 10° C./min. The flow of nitrogen purge gas is set to 50-80 mL/min. The temperature range of the first heating run is 30° C. to 180° C. The temperature range of the cooling run and the second heating run is 180° C. to 0° C. (or lower). The isotherm times for the first heating run and the cooling run are 5 min. The first melting run is used to remove the thermal history of the sample. Crystallization temperature (TO is determined from the cooling run, while main melting temperature (T.sub.m), degree of crystallinity (Cryst. %) and heat of melting (H.sub.m) are determined from the second heating run.
[0207] Polymer Melt Flow Rate
[0208] The melt flow rates are measured in accordance with ISO 1133 at 190° C. and under given load and is indicated in units of grams/10 minutes. The melt flow rate is an indication of the molecular weight of the polymer. The higher the melt flow rate, the lower the molecular weight of the polymer.
[0209] MFR.sub.21: 190° C., 21.6 kg load
[0210] Molecular weight averages, molecular weight distribution (M.sub.n, Mw, Mz, MWD, PDI) Molecular weight averages (M.sub.Z-, M.sub.w and M.sub.n), Molecular Weight Distribution (MWD) and its broadness, described by polydispersity index PDI=M.sub.w/M.sub.n (wherein M.sub.n is the number average molecular weight and M.sub.w is the weight average molecular weight) are determined by Gel Permeation Chromatography (GPC) according to ISO 16014-1:2003, ISO 16014-2:2003, ISO 16014-4:2003 and ASTM D 6474-12 using the following formulas:
[0211] For a constant elution volume interval ΔV.sub.i where A, and M, are the chromatographic peak slice area and polyolefin molecular weight (MW), respectively associated with the elution volume, V.sub.i where N is equal to the number of data points obtained from the chromatogram between the integration limits.
[0212] A high temperature GPC instrument, equipped with either infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain) or differential refractometer (RI) from Agilent
[0213] Technologies, equipped with 3 x Agilent-PLgel Olexis and lx Agilent-PLgel Olexis Guard columns is used. As the solvent and mobile phase 1,2,4-trichlorobenzene (TCB) stabilised with 250 mg/L 2,6-Di-tert-butyl-4-methyl-phenol) is used. The chromatographic system is operated at 160° C. and at a constant flow rate of 1 mL/min. 200 μL of sample solution is injected per analysis. Data collection is performed using either Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.
[0214] The column set is calibrated using universal calibration (according to ISO 16014-2:2003) with 19 narrow MWD polystyrene (PS) standards in the range of 0.5 kg/mol to 11500 kg/mol. The PS standards are dissolved at room temperature over several hours. The conversion of the polystyrene peak molecular weight to polyolefin molecular weights is accomplished by using the Mark Houwink equation and the following Mark Houwink constants: [0215] Kps=19×10.sup.−3 mL/g, lips=0.655 [0216] KpE=39×10.sup.−3 mL/g, r.sub.ipE=0.725 [0217] Kpp=19×10.sup.−3 mL/g, r.sub.ipp=0.725
[0218] A third order polynomial fit is used to fit the calibration data.
[0219] All samples are prepared in the concentration range of 0.5−1 mg/mL and dissolved at 160° C. for 2.5 hours for PP or 3 hours for PE under continuous gentle shaking.
[0220] Polymer Comonomer Content (1-butene) by FTIR Comonomer content is determined based on Fourier transform infrared spectroscopy (FTIR) using Bruker Tensor 37 spectrometer together with OPUS software.
[0221] Approximately 0.3 grams of sample is compression-moulded into films with thickness of 250 μm. Silicone paper is used on both sides of the film. The films are not touched by bare hands to avoid contamination. The films are pressed by using Fontijne Press model LabEcon 300. The moulding is carried out at 160° C. with 2 min pre-heating+2 min light press+1 min under full press. The cooling is done under full press power for 4 minutes.
[0222] The butene comonomer content is determined from the absorbance at the wave number of approximately 1378 cm.sup.−l and the reference peak is 2019 cm.sup.−1. The analysis is performed using a resolution of 2 cm.sup.−1, wave number span from 4000 to 400 cm.sup.−1 and the number of sweeps of 128. At least two spectra are obtained from each film.
[0223] The comonomer content is determined from a spectrum from the wave number range of 1400 cm.sup.−1 to 1330 cm.sup.−1. The baseline is determined using the following method: within the set wavenumber range, the highest peak is located and then the minima to the left and to the right of this highest peak. The baseline connects these minima. The absorbance value at the highest peak is divided by the area of the reference peak.
[0224] The calibration plot for the method is produced for each comonomer type separately. The comonomer content of an unknown sample needs to be within the range of the comonomer contents of the calibration samples. The comonomer content in the calibration sample materials is pre-determined by NMR-spectrometry.
[0225] The comonomer content is calculated automatically by using calibration curve and the following formula:
[0226] WE=C.sub.1 x A0+C0 where
[0227] WE=result in wt %
[0228] A0=absorbance of the measured peak (AQ) to the area of the reference peak (AR);
[0229] C1=slope of the calibration curve;
[0230] C0=offset of the calibration curve.
[0231] The comonomer content is determined from both of the obtained spectra and the value is calculated as the average of these results.
Examples
[0232] Comparative Internal Donors CD1: 9,9-Di(methoxymethyl)fluorene (DMMF)
##STR00010##
[0233] 9,9-Di(methoxymethyl)fluorene (CAS 182121-12-6), alternatively named 9,9-Bis(methoxymethyl)-9H-fluorene, was acquired from Hangzhou Sage Chemical Co.
[0234] CD2: 2,2-Dimethyl-1,3-diqlycidyloxypropane (DMDGP)
##STR00011##
[0235] 2,2-Dimethyl-1,3-diglycidyloxypropane (CAS 17557-23-2), alternatively named Diglycidyl ether of neo-pentyl glycol, was acquired from ABCR.
[0236] Inventive Internal Donors
[0237] I Dl: 2-(3-MethylbutyI)-2-isopropyl-1,3-dimethoxypropane (MBIP-DMP)
##STR00012##
[0238] 2-(3-Methylbutyl)-2-isopropyl-1,3-dimethoxypropane (CAS 129228-11-1), alternatively named 3,3-Bis(methoxymethyl)-2,6-dimethylheptane or 1,3-Dimethoxy-2-isoamyl-2-isopropylpropane, was prepared according to the following procedure:
[0239] Diethyl isopropylmalonate 45 g of Sodium hydride (1.12 mol, 1.2 eq.) were placed into an Argon-filled flask followed by 1 L of DMF. To this suspension, 150 g of Diethyl malonate (0.94 mol) were added dropwise at such a rate as to avoid violent hydrogen evolution (about 3 h). To an almost clear resultant solution, 191 g of Isopropyl iodide (1.12 mol, 1.2 eq.) were added drop-wise during 1 h. The temperature of the reaction mixture reached 50° C. and the mixture was cooled down to room temperature with water bath. At this moment, a thick suspension was formed due to precipitation of Sodium iodide. To provide effective stirring, 300 mL of DMF were added additionally and the reaction mixture was left stirring overnight with slow (one bubble a second) Argon flow to maintain inert atmosphere. 100 mL of 1M aq. HCl were added drop-wise to quench the reaction. The resultant solution was poured into additional 300 mL of 1M HCl and 1.5 L of water. The clear solution was separated on two 2 L portions and each was extracted with Hexane (200 mL, then 3×100 mL). Hexane extracts were combined, dried over Sodium sulphate, evaporated and distilled at reduced pressure to give 169 g (89%) of Diethyl isopropylmalonate as colourless oil.
[0240] Diethyl 2-isopentyl-2-isopropylmalonate
[0241] This stage was performed in a manner similar to the previous starting from Diethyl isopropylmalonate (174 g, 0.86 mol), Sodium hydride (45 g, 1.12 mol, 1.3 eq.) and Isoamyl bromide (182 g, 1.2 mol, 1.4 eq.) but without the addition of extra 300 mL of DMF.
[0242] A Vigreux column distillation at reduced pressure afforded 142 g (61%) of 2-Isopentyl-2-isopropylmalonate as colourless oil.
[0243] 2-Isopentyl-2-isopropylpropane-1,3-diol
[0244] To a 2 L Argon-filled flask, 30.4 g of Lithium aluminium hydride (0.8 mol, 2 eq.) were added, followed by 1 L of THF. To this stirred suspension, 108 g of Diethyl 2-isopentyl-2-isopropylmalonate (0.4 mol) were added drop-wise during 3 h. After completion of the addition, the mixture was gently refluxed for 1 h and left stirred overnight under slow flow of Argon.
[0245] Quenching was then performed by drop-wise addition of water (30 mL), 15% aq. NaOH (30 mL) and water again (90 mL). The suspension was was filtered; the filtrate volatiles were evaporated. Filtered aluminium material was dispersed in the solvent recovered from rotary evaporator, 100 mL of Methanol were added and the mixture was refluxed while stirring for 30 min, cooled to room temperature and filtered again. The filtrate was volatiles were removed and the resulting second portion of the product combined with the first portion.
[0246] Produced crude 2-Isopentyl-2-isopropylpropane-1,3-diol was purified by distillation at reduced pressure to give 60 g (80%) of 90+% purity material, which was used in subsequent methylation without additional purification.
[0247] 2-(3-Methylbutyl)-2-isopropyl-1,3-dimethoxypropane
[0248] Into a 2 L Argon-filled flask, 40 g of Sodium hydride (1 mol, 2.5 eq.) were added followed by 1 L of THF. To this suspension, a mixture of crude 2-lsopentyl-2-isopropylpropane-1,3-diol (0.4 mol, 1 eq.), Methyl iodide (144 g, 1 mol, 2.5 eq.) and THF (100 mL) was added drop-wise within 2 h. After completion of the addition, the reaction was left stirred overnight. 5 g of Sodium hydride and 20 g of Methyl iodide were added additionally and reaction was refluxed for 2 h.
[0249] 50 mL of concentrated aq. NH.sub.3 were added and left stirred for 1 h to quench unreacted Methyl iodide. The solvent was removed in vacuo and the residue dissolved in 200 mL of water and extracted with Hexane (100 mL, followed by 2×50 mL). Organic extracts were combined, dried over Sodium sulphate, Solvent evaporated and the product distilled under reduced pressure to give 60 g of 2-(3-MethylbutyI)-2-isopropyl-1,3-dimethoxypropane (80%) as colourless oil.
[0250] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 3.27 (s, 6H), 3.24 (d, 4H), 1.75 (m, 1H), 1.42 (m, 1H), 1.30 (m, 2H), 1.13 (m, 2H), 0.87 (d, 6H), 0.85 (d, 6H).
[0251] .sup.130{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ75.6, 59.1, 42.4, 32.6, 30.5, 29.3, 29,0, 22.7, 17.8.
[0252] 1D2: 2-(3-Methylbutyl)-2-isopropyl-1,3-diethoxypropane (MBIP-DEP)
##STR00013##
[0253] 2-(3-Methylbutyl)-2-isopropyl-1,3-diethoxypropane (CAS 180285-93-2), alternatively named 3,3-Bis(ethoxymethyl)-2,6-dimethylheptane, was acquired from SynphaBase AG.
[0254] 1D3:2-Nonyl-2-isopropyl-1,3-diethoxypropane (NIP-DEP)
##STR00014##
[0255] 2-Nonyl-2-isopropyl-1,3-diethoxypropane (CAS 1443990-95-1), alternatively named 3,3-Bis(ethoxymethyl)-2-methyldodecane, was acquired from Convertex Chemie GmbH.
[0256] Inventive and Comparative Catalyst components
[0257] Inventive catalyst components (IC1— 1C.sub.3) and comparative catalyst components (CC1-a, CC1-b and CC2) were prepared according to the Reference Example 2 of WO2016/124676 A1, but using inventive donors (ID1— 1D3) and comparative donors (CD1— CD2). Summary of donors used in catalyst component examples is disclosed in Table 1.
[0258] Comparative catalyst component CC3 is a catalyst commercially available from Grace under the trade name Lynx 200.
[0259] Raw Materials
[0260] The 10 wt % TEA (triethylaluminium) stock solutions in heptane were prepared by dilution of 100 wt % TEA-S from Chemtura.
[0261] MgCl.sub.2*3Et0H carriers were received from Grace.
[0262] TiCla was supplied by Aldrich (metallic impurities<1000 ppm, Metals analysis>99.9%).
[0263] General Procedure for Catalyst Component Preparation
[0264] In an inert atmosphere glovebox a dry 100 mL, 4-neck round-bottom flask, equipped with two rubber septa, a thermometer and a mechanical stirrer, was charged with 3.1 mmol of a desired INTERNAL DONOR (INTERNAL DONOR and INTERNAL DONOR/Mg loading ratio is indicated in Tables 1 and 2) dissolved in 40 mL of heptane and with 7.01 g (30 mmol of Mg) of granular 17 μm (D.sub.05) MgCl.sub.2*2.93Et0H carrier. The flask was removed from the glovebox, a nitrogen inlet and an outlet were connected. The flask was placed in a cooling bath and tempered at 0° C. for approximately 10 min at 250 rpm. Triethylaluminium 10 wt % solution in heptane (107.55 g, 94.2 mmol A1; A1/Et0H=1.07 mol/mol) was added drop-wise to the stirred suspension within 1 h, keeping the reaction mixture temperature below 0° C. The obtained suspension was heated to 80° C. within 20 min and kept at this temperature for further 30 min at 250 rpm. The suspension was left to settle for 5 min at 80° C. and the supernatant was removed using a cannula. The obtained pre-treated support material was washed twice with 70 mL of toluene at room temperature (adding toluene, stirring at 250 rpm for 15-120 min, settling for 5 min and siphoning the liquid phase off).
[0265] At room temperature, 70 mL of toluene was added to the pre-treated support material. To this suspension stirred at 250 rpm, neat TiCla (3.31 mL, 30 mmol; Ti/Mg=1.0 mol/mol) was added drop-wise and the reaction mixture temperature was maintained between 25-35° C. The obtained suspension was heated to 90° C. within 20 min and stirred at this temperature for further 60 min at 250 rpm. The suspension was left to settle for 5 min at 90° C. and the supernatant was removed suing a cannula. The obtained catalyst was washed twice with 70 mL of toluene at 90° C. and once with 70 mL of heptane at room temperature (each wash involving adding toluene or heptane, stirring at 250 rpm for 15 min, settling for 5 min and siphoning the liquid phase off). The catalyst was dried in vacuo at 70° C. for 30 min.
TABLE-US-00001 TABLE 1 Summary of donors used in catalyst components CC1-a, CC1-b, CC2 and IC1-IC3 Catalyst Internal Donor Examples component Internal Donor short name Comparative CC1-a CD1 DMMF Comparative CC1-b CD1 DMMF Comparative CC2 CD2 DMDGP Inventive IC1 ID1 MBIP-DMP Inventive IC2 ID2 MBIP-DEP Inventive IC3 ID3 NIP-DEP
Comparative Examples
[0266] CC1-a Preparation
[0267] CC1-a was prepared using the above General Procedure, with a difference that 0.778 g (3.1 mmol) of CD1 (DMMF) were used as internal donor (ID/Mg=0.102).
[0268] 2.3 g (57.4% yield, Mg-basis) of CC1-a was isolated.
[0269] CC1-b preparation CC1-b was prepared using the above General Procedure, with a difference that 1.038 g (4.1 mmol) of CD1 (DMMF) were used as internal donor (ID/Mg=0.136).
[0270] 2.8 g (64.5% yield, Mg-basis) of CC1-b were isolated.
[0271] CC2 preparation CC2 was prepared using the above General Procedure, with a difference that 0.66 g (3.1 mmol) of CD2 (DMDGP) were used as internal donor (ID/Mg=0.102).
[0272] 5.4 g (89.6% yield, Mg-basis) of CC2 were isolated.
[0273] Inventive Examples IC1 preparation IC1 was prepared using the above General Procedure, with a difference that 0.66 g (3.1 mmol) of ID1 (MBIP-DMP) were used as internal donor (ID/Mg=0.102).
[0274] 3.8 g (80.8% yield, Mg-basis) of IC1 were isolated.
[0275] IC2 preparation 102 was prepared using the above General Procedure, with a difference that 0.75 g (3.1 mmol) of 1D2 (MBIP-DEP) were used as internal donor (ID/Mg=0.102).
[0276] 4.3 g (89.6% yield, Mg-basis) of IC2 were isolated.
[0277] IC3 preparation 103 was prepared using the above General Procedure, with a difference that 0.92 g (3.1 mmol) of 1D3 (NIP-DEP) were used as internal donor (ID/Mg=0.102).
[0278] 4.5 g (87.0% yield, Mg-basis) of IC3 were isolated.
TABLE-US-00002 TABLE 2 Summary of properties of catalyst components CC1-a, CC1-b, CC2 and IC1-IC3. ID/Mg loading Vola- Ti(IV) Mg/Ti Mg/Al Catalyst Internal ratio, Ti, Mg, Al, CI, tiles, proportion, ratio, ratio, component donor (ID) mol/mol wt % wt % wt % wt % wt % % mol/mol mol/mol CC1-a DMMF 0.102 3.54 18.2 0.23 56.3 4.7 40.0 10.13 87.85 CC1-b DMMF 0.136 4.00 16.8 0.37 55.2 5.4 26.2 8.27 50.41 CC2 DMDGP 0.102 9.16 12.1 1.56 55.3 7.0 15.2 2.60 8.61 IC1 MBIP-DMP 0.102 5.56 15.5 0.38 58.1 4.7 12.4 5.49 45.28 IC2 MBIP-DEP 0.102 6.37 15.2 0.49 56.1 6.1 13.5 4.70 34.44 IC3 NIP-DEP 0.102 6.39 14.1 0.41 57.5 3.4 4.5 4.35 38.18
[0279] Bench-scale ethylene copolymerization with 1-butene
[0280] The inventive catalyst components (101-103) and comparative catalyst components (CC1-a, CC1-b, CC2 and CC3) were tested in copolymerization with 1-butene (1E1-1E3 and CE1-a, CE1-b, CE2 and CE3-a). Triethylaluminum (TEA) was used as a cocatalyst with an A1/Ti molar ratio of 15. The polymerization reaction was carried out in a 3 L bench-scale reactor in accordance with the following procedure:
[0281] An empty 3 L bench-scale reactor was charged with 70 mL of 1-butene at 20° C. and stirred at 200 rpm. Then 1250 mL of propane was added to the reactor as a polymerization medium, followed by the addition of hydrogen gas (0.40 bar). The reactor was heated to 85° C., and ethylene (3.7 bar) was added batch-wise. The reactor pressure was kept at 0.2 bar of overpressure and stirring speed was increased to 550 rpm. The catalyst component and the cocatalyst were added together (a few seconds of pre-contact between catalyst component and TEA) to the reactor with additional 100 mL of propane. The total reactor pressure was maintained at 37.8 bar by continuous ethylene feed. The polymerization was stopped after 60 min by venting off the monomers and H.sub.2. The obtained polymer was left to dry in a fume hood overnight before weighing.
[0282] Additionally, the comparative catalyst component CC3 was tested in copolymerization also with 55 mL of 1-butene and 0.40 bar of hydrogen gas (CE3-b) and with 40 mL of 1-butene and 0.75 bar of hydrogen gas (CE3-c).
[0283] Polymerization Results
[0284] The results of the polymerization reactions are shown in Table 3. The activity of the catalysts was calculated based on catalyst component loading amount and the amount of polymer produced in one hour.
TABLE-US-00003 TABLE 3 Summary of polymerization results for comparative examples CE1-a, CE1-b, CE2, CE3-a-CE3-c and inventive examples IE1-IE3. 1-Butene Polymerization Catalyst Activity, content, MFR.sub.21 Mw, T.sub.M, Example component kg/(g * h) wt % g/10 min g/mol PDI ° C. CE1-a CC1-a 19.2 4.4 3.7 211500 4.61 122.9 CE1-b CC1-b 17.3 4.8 3.9 215500 4.52 123.2 CE2 CC2 20.0 5.2 10.6 163500 4.21 124.38 CE3-a CC3 55 6.2 5.3 200000 4.80 122.4 CE3-b CC3 54 4.8 3.0 220000 4.71 123.4 CE3-C CC3 58 3.9 8.3 160000 4.64 124.9 IE1 IC1 19.9 4.3 2.2 245000 4.12 122.2 IE2 IC2 23.5 3.7 2.0 242500 4.05 122.9 IE3 IC3 20.4 5.2 3.0 243500 4.18 122.4
[0285] As can be seen form the results of the Table 3 and as indicated in
[0286] Further (as shown in
[0287] In addition, as shown by the examples and in
[0288] Moreover, in all inventive examples (IE1-1E3) the desired balance of properties is achieved with ID/Mg loading ratios similar or lower than for comparative donor CD1.
[0289] To summarize the findings, all inventive examples IE1-1E3 demonstrate the highest (among the tested group of catalyst components/internal donors) M.sub.w combined with very narrow MWD and with low melting temperature at a given comonomer content. Thus, the inventive internal donors allow for “tailoring” of the properties of the produced polymers while maintaining catalyst productivity at an acceptably high level.