ZIEGLER-NATTA CATALYSTS FOR OLEFIN POLYMERIZATION

Abstract

The present invention relates to use of optionally monosubstituted 2,2-di(tetrahydrofuryl)methanes, as internal donors in Ziegler-Natta catalysts to obtain polymers with desirable properties. The present disclosure further concerns Ziegler-Natta catalyst components comprising said optionally monosubstituted 2,2-di(tetrahydrofuryl)methanes and Ziegler-Natta catalysts for olefin polymerization comprising said Ziegler-Natta catalyst components as well as a method for preparing the same and their use in providing polyolefins.

Claims

1.-2. (canceled)

3. A Ziegler-Natta catalyst component for olefin polymerization, comprising: (i) an internal donor selected from compounds of formula (I) ##STR00027## wherein R.sub.1 is selected from a group consisting of H, a linear or branched C.sub.1-7-alkyl, CH.sub.2OR.sub.2 and oxygen-containing heterocyclic ring; and R.sub.2 is selected from a group consisting of a linear or branched or cyclic C.sub.1-8-alkyl group.

4. The Ziegler-Natta catalyst component according to claim 3, wherein the compound of formula (I) is selected from compounds of formula (I-a) and (I-b) ##STR00028## ##STR00029## wherein in (I-a) R.sub.1a is selected from a group consisting of H, C.sub.1-3-alkyl and CH.sub.2OR.sub.2; and R.sub.2 is selected from a group consisting of a linear or branched or cyclic C.sub.1-8-alkyl group, and wherein in (I-b) R.sub.1b is selected from a group consisting oxygen-containing heterocyclic ring.

5. The Ziegler-Natta catalyst component according to claim 3, 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).

6. The Ziegler-Natta catalyst component according to claim 3, 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 0.0 wt % to 3.0 wt % of the total weight of the Ziegler-Natta catalyst component.

7. A method for producing a Ziegler-Natta catalyst component, comprising adding an internal donor selected from compounds of formula (I) ##STR00030## wherein R.sub.1 is selected from a group consisting of H, a linear or branched C.sub.1-7-alkyl, CH.sub.2OR.sub.2 and oxygen-containing heterocyclic ring; and R.sub.2 is selected from a group consisting of a linear or branched or cyclic C.sub.1-8-alkyl group, to a process of preparing the Ziegler-Natta catalyst component.

8. A method for producing a Ziegler-Natta catalyst component according to claim 3, wherein the method comprises: (M-a) providing a solid support; (M-b) pre-treating the solid support of step (M-a) with a compound of Group .sub.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).

9. The method according to claim 7, wherein the Ziegler-Natta catalyst component is the Ziegler-Natta catalyst component according to claim 3.

10. A Ziegler-Natta catalyst for olefin polymerization comprising a catalyst component comprising an internal donor selected from compounds of formula (I) ##STR00031## wherein R.sub.1 is selected from a group consisting of H, C.sub.1-3-alkyl, CH.sub.2OR.sub.2 and oxygen-containing heterocyclic ring; and R.sub.2 is selected from a group consisting of a linear, branched or cyclic C.sub.1-8-alkyl group; or the internal donor is selected from compounds of formula (I-a) or (I-b) ##STR00032## wherein in (I-a) R.sub.1a is selected from a group consisting of H, C.sub.1-3-alkyl and CH.sub.2OR.sub.2; and R.sub.2 is selected from a group consisting of a linear or branched or cyclic C.sub.1-8-alkyl group, and wherein in (I-b) R.sub.1b is selected from a group consisting oxygen-containing heterocyclic ring.

11. The Ziegler-Natta catalyst according to claim 10, comprising (A) the Ziegler-Natta catalyst component as defined in claim 3, or produced according to the method according to claim 7; (B) a cocatalyst selected from element compounds of Group 13 of the Periodic Table (IUPAC, 2005); and (C) optionally, an external donor.

12. A method of olefin polymerization comprising: introducing into a polymerization reactor a Ziegler-Natta catalyst component according to claim 3 comprising an internal donor of formula (I) ##STR00033## wherein R.sub.1 is selected from a group consisting of H, a linear or branched C.sub.1-7-alkyl, CH.sub.2OR.sub.2 and oxygen-containing heterocyclic ring; and R.sub.2 is selected from a group consisting of a linear or branched or cyclic C.sub.1-8-alkyl group.

13. The method according to claim 12, wherein the internal donor of formula (I) is selected from compounds of formula (I-a) or (I-b) ##STR00034## wherein in (I-a) R.sub.1a is selected from a group consisting of H, C.sub.1-3-alkyl and CH.sub.2OR.sub.2; and R.sub.2 is selected from a group consisting of a linear or branched or cyclic C.sub.1-8-alkyl group, and wherein in (I-b) Rib is selected from a group consisting of oxygen-containing heterocyclic ring.

14. The method according to claim 12, 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).

15. The method according to claim 12, 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) an Al content (determined by ICP Analysis) in the range of 0.0 wt % to 3.0 wt % of the total weight of the Ziegler-Natta catalyst component.

16. A process for producing ethylene homo- or copolymers, comprising: (P-a) introducing the Ziegler-Natta catalyst component according to claim 3, or produced according to the method according to claim 7 into a polymerization reactor; (P-b) introducing a cocatalyst capable of activating the said Ziegler-Natta catalyst component into the polymerization reactor; (P-c) introducing ethylene, optionally C.sub.3-C.sub.20 α-olefin comonomers, and optionally hydrogen into the polymerization reactor; and (P-d) maintaining said polymerization reactor in such conditions as to produce an ethylene homo- or copolymer.

17. The process according to claim 16, wherein olefin polymerization is accomplished in a multi-stage polymerization process comprising at least one gas phase reactor for producing olefin polymers.

18. The process according to claim 16, wherein olefin polymerization is accomplished in a multi-stage polymerization process comprising at least one slurry reactor and one gas phase reactor.

Description

[0198] The advantages of the present invention are shown in the experimental part and in the figures:

[0199] FIG. 1 shows the polydispersity index (PDI) vs. molecular weight of inventive examples (IE1-IE4) and comparative examples CE1-CE9.

[0200] FIG. 2 shows the melting temperature vs. comonomer content inventive examples (IE1-IE4) and comparative examples CE1-CE9.

[0201] FIG. 3 shows activity level vs. molecular weight of inventive examples (IE1-IE4) and of comparative examples CE1-CE9.

EXPERIMENTAL PART

[0202] Analytical Methods

[0203] Al, Mq, Ti Contents in a Catalyst Component by ICP-OES

[0204] 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.

[0205] 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% HNO.sub.3, 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.

[0206] 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 Al, Ti and Mg using a blank (a solution of 5% HNO.sub.3) and six standards of 0.5 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm and 300 ppm of Al, Ti and Mg in solutions of 5% HNO.sub.3 DI water. Curvelinear fitting and 1/concentration weighting is used for the calibration curve.

[0207] Immediately before analysis the calibration is verified and adjusted (instrument function named “re-slope”) using the blank and a 300 ppm Al, 100 ppm Ti, Mg standard. A quality control sample (QC; 20 ppm Al and Ti, 50 ppm Mg in a solution of 5% HNO.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.

[0208] 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 Al concentration in test portion is between 0-10 wt % and via the 396.152 nm line for Al concentrations above 10 wt %.

[0209] 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.

[0210] CI Content in a Catalyst Component by Potentiometric Titration

[0211] 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 HNO.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 0.1 M AgNO.sub.3 in a Mettler Toledo T70 automatic titrator. The titration end-point is determined using an Ag-electrode. The total chloride amount is calculated from the titration and related to the original sample weight.

[0212] Volatiles in a Catalyst Component by GC-MS

[0213] 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.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] 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.

[0218] Polymer Melting and Crystallization Properties by DSC

[0219] 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 (T.sub.c) 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.

[0220] Polymer Melt Flow Rate

[0221] 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.

[0222] MFR.sub.21: 190° C., 21.6 kg load

[0223] Molecular Weight Averages, Molecular Weight Distribution (M.sub.n, M.sub.w, M.sub.z, MWD, PDI)

[0224] 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:

[00001]$\begin{array}{cc}{M}_n=\frac{{\Sigma }_{i=1}^N{A}_i}{{\Sigma }_{i=1}^N\left(A_i/M_i\right)}& \left(1\right)\end{array}$$\begin{array}{cc}{M}_w=\frac{{\Sigma }_{i=1}^N\left(A_i\times M_i\right)}{{\Sigma }_{i=1}^N{A}_i}& \left(2\right)\end{array}$$\begin{array}{cc}{M}_z=\frac{{\Sigma }_{i=1}^N\left(A_i\times M_i^2\right)}{{\Sigma }_{i=1}^N\left(A_i/M_i\right)}& \left(3\right)\end{array}$

[0225] For a constant elution volume interval ΔV.sub.i, where A.sub.i, and M.sub.i 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.

[0226] A high temperature GPC instrument, equipped with either infrared (IR) detector (IR4 or IR5 from PolymerChar (Valencia, Spain) or differential refractometer (RI) from Agilent Technologies, equipped with 3× 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.

[0227] 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:

K.sub.PS=19×10.sup.−3 mL/g,η.sub.PS=0.655

K.sub.PE=39×10.sup.−3 mL/g,η.sub.PE=0.725

K.sub.PP=19×10.sup.−3 mL/g,η.sub.PP=0.725

[0228] A third order polynomial fit is used to fit the calibration data.

[0229] 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.

[0230] Polymer Comonomer Content (1-Butene) by FTIR

[0231] Comonomer content is determined based on Fourier transform infrared spectroscopy (FTIR) using Bruker Tensor 37 spectrometer together with OPUS software.

[0232] 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.

[0233] The butene comonomer content is determined from the absorbance at the wave number of approximately 1378 cm.sup.−1 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.

[0234] 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.

[0235] 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.

[0236] The comonomer content is calculated automatically by using calibration curve and the following formula:

W.sub.E=C.sub.1×A.sub.0+C.sub.0

[0237] where

[0238] W.sub.E=result in wt %

[0239] A.sub.0=absorbance of the measured peak (A.sub.Q) to the area of the reference peak (A.sub.R);

[0240] C.sub.1=slope of the calibration curve;

[0241] C.sub.0=offset of the calibration curve.

[0242] The comonomer content is determined from both of the obtained spectra and the value is calculated as the average of these results.

Examples

[0243] Comparative Internal Donors

CD1: Di(Furan-2-Yl)Methane(DFM)

[0244] ##STR00016##

[0245] Di(furan-2-yl)methane (CAS 1197-40-6), alternatively named Bis(2-furyl)methane, was prepared as described in [a) Chem. Eur. J., 2000, 6, 22, 4091; b) J. Appl. Polym. Sci., 2014, DOI: 10.1002/app.40179]. The product was isolated in 62% yield by vacuum distillation (b.p. 70° C./15 mbar).

[0246] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.33 (m, 2H), 6.31 (m, 2H), 6.08 (d, J=3.0 Hz, 2H), 4.00 (s, 2H)

[0247] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 151.5, 141.6, 110.4, 106.4, 27.4.

CD2: 1,1-Di(furan-2-yl)ethane (DFE)

[0248] ##STR00017##

[0249] 1,1-Di(furan-2-yl)ethane (CAS 51300-81-3), alternatively named 1,1-Bis(2-furyl)ethane or 2,2′-(Ethane-1,1-diyl)difuran, was prepared using slightly modified described method [J. Heterocyclic. Chem., 1991, 28, 991].

[0250] To an ice-cooled mixture of 85 mL of ethanol and 50 mL of 12 M HCl 175 g (2.57 mol) of furan was added, followed by 60 g (1.36 mol) of acetaldehyde. The resulting mixture was stirred at room temperature for 20 h, then poured into 500 mL of water and extracted with 3×250 mL of ether. The organic extracts were combined, washed with aqueous potassium bicarbonate, dried over sodium sulfate and volatiles were evaporated in vacuum. The residue was distilled in vacuum to give 60.5 g (29%) of 1,1-Di(furan-2-yl)ethane (b.p. 88-92° C./17 mm Hg) and 57.2 g (26%) of 2,5-bis[1-(2-furyl)ethyl]furan (b.p. 144-152° C./3 mm Hg).

[0251] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ7.32 (m, 2H), 6.29 (dd, J=3.1 Hz, J=1.9 Hz, 2H), 6.04 (d, J=3.1 Hz, 2H), 4.21 (q, J=7.2 Hz, 1H), 1.59 (d, J=7.2 Hz, 3H).

[0252] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 156.5, 141.3, 110.1, 104.9, 33.0, 17.9.

CD3: 2,2-Di(furan-2-yl)propane (DFP)

[0253] ##STR00018##

[0254] 2,2-Di(furan-2-yl)propane (CAS 17920-88-6), alternatively named 2,2-Bis(2-furyl)propane or 2,2′-(propane-2,2-diyl)difuran, was acquired from TCI EUROPE N.V.

CD4: Tri(furan-2-yl)methane (TFM)

[0255] ##STR00019##

[0256] To an ice-cooled mixture of 8.6 mL (103.8 mmol) of furfural and 200 mL of furan, 5 mL of trifluoroacetic acid was added dropwise and the resulting mixture was stirred at room temperature for 24 h. The reaction mixture was poured into solution of potassium bicarbonate in water, extracted with 250 mL of ether and the extract was dried over Na.sub.2SO.sub.4. All volatiles were removed in vacuum, and the residue was distilled in vacuum to give 3.2 g (14%) of Tri(furan-2-yl)methane (CAS 77616-90-1), alternatively named 2,2′,2″-Methanetriyltrifuran (b.p. 115° C./10 mm Hg).

[0257] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.40 (br.d, 3H), 6.36 (dd, J=3.1 Hz, J=1.9 Hz, 3H), 6.16 (d, J=3.1 Hz, 3H), 5.59 (s, 1H).

[0258] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 151.9, 142.0, 110.4, 107.3, 38.9.

CD5: 2,5-Bis[2-(tetrahydrofuran-2-yl)propan-2-yl]tetrahydrofuran (BTHFPT)

[0259] ##STR00020##

[0260] 2,5-Bis[2-(tetrahydrofuran-2-yl)propan-2-yl]tetrahydrofuran (CAS 89686-70-4), alternatively named 2,5-bis[2-(oxolan-2-yl)propan-2-yl]oxolane was acquired from Fluorochem Ltd.

CD6: 2,5-Bis[1-(furan-2-yl)ethan-1-yl]furan (BFEF)

[0261] ##STR00021##

[0262] 2,5-Bis[1-(furan-2-yl)ethan-1-yl]furan (CAS 61093-50-3) was prepared using slightly modified described method [J. Heterocyclic. Chem., 1991, 28, 991].

[0263] To an ice-cooled mixture of 85 mL of ethanol and 50 mL of 12 M HCl 175 g (2.57 mol) of furan was added, followed by 60 g (1.36 mol) of acetaldehyde. The resulting mixture was stirred at room temperature for 20 h, poured into 500 mL of water and extracted with 3×250 mL of ether. The organic extracts were combined, washed with aqueous potassium bicarbonate, dried over sodium sulfate and volatiles were evaporated in vacuum. The residue was distilled in vacuum to give 60.5 g (29%) of 2,2′-Ethane-1,1-diyldifuran (b.p. 88-92° C./17 mm Hg) and 57.2 g (26%) of 2,5-Bis[1-(furan-2-yl)ethan-1-yl]furan (b.p. 144-152° C./3 mm Hg).

[0264] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ7.31 (m, 2H), 6.27 (dd, J=3.1 Hz, J=1.9 Hz, 2H), 6.00 (d, J=3.1 Hz, 2H), 5.93 (s, 2H), 4.16 (q, J=7.2 Hz, 2H), 1.56 (d, J=7.2 Hz, 6H).

[0265] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 156.7, 155.2, 141.1, 110.0, 105.4, 104.9, 33.1, 18.01, 17.96.

CD7: 2,2,7,7,12,12,17,17-Octamethyl-21,22,23,24-tetraoxaperhydroquaterene (OMTOPQ)

[0266] ##STR00022##

[0267] 2,2,7,7,12,12,17,17-Octamethyl-21,22,23,24-tetraoxaquaterene

[0268] To a solution of 95.2 g (0.4 mol) of CoCl.sub.2(H.sub.2O).sub.6 in 200 mL of anhydrous ethanol, 93.2 g (1.6 mol) of acetone, 32 mL of 12 M HCl and, finally, 54.4 g (0.8 mol) of furan were successively added. After ca. 20 min, the reaction mixture became hot (60-70° C.) and turned deep-red. The reaction flask was immersed in a water bath and maintained there at 60° C. for 3 h. The reaction mixture was then stirred overnight at room temperature and poured into 500 mL of water. The resulting suspension was extracted with 3×150 mL of toluene. The combined extract's volatiles were evaporated in vacuum and the residue was triturated with 200 mL of anhydrous ethanol to give 11.1 g (13%, purity>95%) of desired product as a white powder. Re-crystallization of the crude product from hot toluene yielded analytically pure 2,2,7,7,12,12,17,17-Octamethyl-21,22,23,24-tetraoxaquaterene as a white solid.

[0269] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 5.88 (s, 1H), 1.47 (s, 3H).

2,2,7,7,12,12,17,17-Octamethyl-21,22,23,24-tetraoxaperhydroquaterene

[0270] A mixture of 2,2,7,7,12,12,17,17-Octamethyl-21,22,23,24-tetraoxaquaterene (5.0 g, 11.6 mmol), 5% Pd/C (710 g) and ethanol (170 mL) was placed in a 1000 mL autoclave which was then pressurized with hydrogen (100 bar). This mixture was stirred for 15 h at 125° C. After cooling to room temperature, the formed mixture was filtered through a pad of Celite 503 which was additionally washed with 100 mL of ethanol. The filtrate volatiles were evaporated in vacuum to dryness to give the first portion of the desired product (2.25 g) which was a mixture of 11 diastereomers (GC-MS). The filter cake was washed with 400 mL of dichloromethane, the filtrate volatiles were evaporated to dryness in vacuum to yield the second portion of the product (2.90 g) which was a mixture of two major diastereomers with a small amount of two minor diastereomers (GC-MS). The two portions of the product were combined. The total yield was 5.15 g (99%)) of 2,2,7,7,12,12,17,17-Octamethyl-21,22,23,24-tetraoxaperhydroquaterene (CAS 50451-63-3), alternatively named Octamethylperhydrocyclotetrafurfurylene, as a white solid.

[0271] .sup.1H NMR of the combined portions (CDCl.sub.3, 400 MHz): δ 4.20-3.20 (m, 8H), 2.55-1.28 (m, 16H), 1.26-0.60 (m, 24H).

CD8: 9,9-Di(methoxymethyl)fluorene (DMMF)

[0272] ##STR00023##

[0273] 9,9-Di(methoxymethyl)fluorene (CAS 182121-12-6), alternatively named 9,9-Bis(methoxymethyl)-9H-fluorene, was acquired from Hangzhou Sage Chemical Co.

[0274] Inventive Internal Donors

[0275] Inventive donors ID1 to ID4 were prepared according to the following procedures:

ID1: Di(tetrahydrofuran-2-yl)methane (DTHFM)

[0276] ##STR00024##

[0277] 2,2′-Methylenedifuran (19.2 g, 130 mmol; see preparation of CD1) and 5% Pd/C (0.95 g) were placed into a 450 mL autoclave which was purged with argon, pressurized with hydrogen (70 bar) and the mixture was stirred at 100° C. for 1 h. After cooling to room temperature and depressurization, the mixture was diluted with dichloromethane and filtered through a pad of Celite 503. The filtrate volatiles were evaporated in vacuum. Further on, acetic acid (20 mL) and water (80 mL) were added to the residue and the formed mixture was refluxed for 2 h under argon atmosphere. On cooling to room temperature, it was basified with a small excess of NaOH and thus obtained mixture was extracted with hexane. The extract was dried over Na.sub.2SO.sub.4, and the solvent was evaporated in vacuum. The residue was added drop-wise under stirring to 2.4 g of NaH under argon atmosphere. When formation of hydrogen ceased, the product was distilled off in vacuum (b.p. 54-70° C./1 mbar). Yield: 11.4 g (56%) of a colorless liquid. According to .sup.1H NMR the product was a ˜1: 1 mixture of diastereomers A and B of Di(tetrahydrofuran-2-yl)methane (CAS 1793-97-1), alternatively named 2,2′-Methylidenebis(tetrahydrofuran), of which A is a racemic mixture of (L) and (D) isomers and B is a meso-isomer.

[0278] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 3.95-3.79 (m, 4H in A and 4H in B), 3.72-3.65 (m, 2H in A and 2H in B), 2.05-1.93 (m, 2H in A and 2H in B), 1.92-1.76 (m, 4H in A and 5H in B), 1.69 (t, J=6.4 Hz, 2H in A), 1.59 (dt, J=13.6 Hz, J=5.8 Hz, 1H in B), 1.52-1.39 (m, 2H in A and 2H in B).

[0279] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 77.1, 76.9, 67.7, 67.5, 41.7, 41.1, 31.9, 31.6, 25.6, 25,5.

ID2: 1,1-Di(tetrahydrofuran-2-yl)ethane (DTHFE)

[0280] ##STR00025##

[0281] A mixture of 2,2′-(Ethane-1,1-diyl)difuran (20 g, 123 mmol; see CD2) and 5% Pd/C (1.00 g) was placed into a 450 mL autoclave which was then purged with argon and pressurized with hydrogen (70 bar). This mixture was stirred at 120° C. for 1 h. After cooling to room temperature and depressurization, the mixture was diluted with dichloromethane and filtered through a pad of Celite 503. The filtrate volatiles were evaporated in vacuum. Further on, acetic acid (20 mL) and water (80 mL) were added to the residue and the mixture was refluxed for 5 h under argon atmosphere. On cooling to room temperature, it was basified with a small excess of NaOH and then extracted with hexane. The extract was dried over Na.sub.2SO.sub.4 and the solvent was evaporated in vacuum. The residue was added drop-wise under stirring to 3 g of NaH under argon atmosphere. When formation of hydrogen ceased, the product was distilled off in vacuum (b.p. 75-90° C./4 mbar). Yield: 8.4 g (40%) of 1,1-Di(tetrahydrofuran-2-yl)ethane (CAS 84548-20-9), alternatively named 2,2′-Ethylidenebis(tetrahydrofuran), as a colorless liquid. According to .sup.1H NMR, the product was a ˜2.2: 1.1: 1 mixture of diastereomers A, B and C.

[0282] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ3.96-3.90 (m, 2H in B), 3.86-3.76 (m, 6H in A, 4H in B, 6H in C), 1.98-1.44 (m, 9H in A, B and C), 0.97 (d, J=6.9 Hz, 3H in B), 0.87 (d, J=6.8 Hz, 3H in A), 0.80 (d, J=6.9 Hz, 3H in C).

[0283] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 81.4, 81.1, 81.0, 80.1, 68.0, 67.9, 67.8, 67.7, 42.4, 42.0, 41.3, 29.4, 29.3 (two resonances), 27.9, 26.1, 25.9, 25.7 (two resonances), 10.6, 10.3, 10.2.

ID3 and ID4: Meso-tri(tetrahydrofuran-2-yl)methane (TTHFM-A) and Rac-tri(tetrahydrofuran-2-yl)methane (TTHFM-B), Respectively

[0284] ##STR00026##

Tri(furan-2-yl)methanol

[0285] To a solution of furan (87.3 g, 1.28 mol) in THF (1000 mL) n-BuLi (500 mL, 1.25 mol, 2.5 M in hexanes) was added drop-wise at −10° C. The reaction mixture was warmed to 10° C. and stirred for 4 h at this temperature. Further on, the 2-furyllithium suspension formed was cooled to −80° C. and dimethyl carbonate (28.8 g, 320 mmol) was added. The mixture was stirred at room temperature overnight, poured into 1 L of water and extracted with 3×300 mL of diethyl ether. The combined extract was washed with 200 mL of water, dried over Na.sub.2SO.sub.4, passed through a pad of silica gel 60 (40-63 μm) and the volatiles were evaporated to dryness in vacuum. This procedure afforded 62.0 g of Tri(furan-2-yl)methanol of 90% purity (76% yield) as a dark brown oil which was used in the next stage without further purification.

[0286] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.43 (d, 3H, J=1.8 Hz), 6.38-6.36 (dd, 3H, J=3.2 Hz, J=1.7 Hz), 6.23 (d, 3H, J=3.2 Hz), 3.38 (s, 1H).

2,2′-(Furan-2(5H)-ylidenemethylene)difuran

[0287] To a solution of aluminum trichloride (23.2 g, 174 mmol) in anhydrous diethyl ether (1000 mL) lithium aluminum hydride (16.0 g, 416 mmol) was added portion-wise at 0° C. To the obtained solution Tri(furan-2-yl)methanol (40.0 g, 174 mmol) was added drop-wise. The mixture was stirred at 0° C. for 2 h and quenched carefully with 100 mL of water. The obtained suspension was filtered through a pad of Celite 503, the filtrate was dried over Na.sub.2SO.sub.4 and the volatiles evaporated to dryness in vacuum. Fractional distillation of the residue afforded 26.1 g (70%) of 2,2′-(Furan-2(5H)-ylidenemethylene)difuran as a light-brown oil (b.p. 145° C./5 mbar), containing −5 mol % of 2,2′,2″-Methanetriyltrifuran according to .sup.1H NMR.

[0288] .sup.1H NMR (CDCl.sub.3, 400 MHz): 7.43 (m, 1H), 7.38 (m, 1H), 6.70 (dt, 1H, J=6.1 Hz, J=2.3 Hz), 6.63 (d, 1H, J=3.3 Hz), 6.49 (dt, 1H, J=6.1 Hz, J=2.3 Hz), 6.44 (m, 2H), 6.36 (d, 1H, J=3.1 Hz), 5.20 (m, 2H).

Meso-tri(tetrahydrofuran-2-yl)methane (TTHFM-A) and Rac-tri(tetrahydrofuran-2-yl)methane (TTHFM-B)

[0289] A mixture of 2,2′-(Furan-2(5H)-ylidenemethylene)difuran (3.6 g, 16.8 mmol), 5% Pd/C (180 mg) and 4 mL .sup.iPrOH was placed into a 100 mL autoclave which was purged with argon, pressurized with hydrogen (70 bar) and the mixture was stirred at 100° C. for 75 min. After cooling to room temperature and depressurization, the formed mixture was diluted with dichloromethane and filtered through a pad of Celite 503. The filtrate volatiles were evaporated in vacuum and the residue was purified by column chromatography on silica gel 60 (40-63 μm, eluent: hexane/ethyl acetate, 3: 1, vol.). The procedure afforded Tri(tetrahydrofuran-2-yl)methane in form of separated stereoisomers: 0.77 g of meso-diastereomer TTHFM-A and 0.28 g of rac-diastereomer TTHFM-B. The total yield of the two diastereomers was 1.05 g (28%). Beside that, 0.78 g (22%) of 3-[Di(tetrahydrofuran-2-yl)methyl]furan were isolated.

[0290] Diastereomer TTHFM-A. .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 4.06-3.96 (m, 2H), 3.92-3.86 (m, 1H), 3.86-3.77 (m, 3H), 3.70-3.63 (m, 3H), 2.10-2.05 (m, 1H), 2.01-1.66 (m, 12H).

[0291] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 78.1, 78.0, 77.9, 67.6, 67.4 (two resonances), 49.2, 30.4, 29.9, 29.0, 26.0, 25.8 (two resonances).

[0292] Diastereomer TTHFM-B. .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 3.98-3.94 (m, 3H), 3.86-3.79 (m, 3H), 3.69-3.62 (m, 3H), 2.00-1.62 (13H).

[0293] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 78.6, 62.7, 50.5, 30.6, 25.8.

[0294] INVENTIVE AND COMPARATIVE CATALYST COMPONENTS

[0295] Inventive catalysts components (IC1- IC4) and comparative catalysts components (CC1-CC8) were prepared according to the procedure of the Reference Example 2 of WO2016/124676 A1, but using inventive donors (ID1- ID4) and comparative donors (CD1-CD8). In CC8-a and CC8-b, the same internal donor CD8 was used. Summary of donors used in catalyst component examples is disclosed in Table 1.

[0296] Comparative catalyst component CC9 is a catalyst commercially available from Grace under the trade name Lynx 200.

[0297] Raw Materials

[0298] The 10 wt % TEA (triethylaluminium) stock solutions in heptane were prepared by dilution of 100 wt % TEA-S from Chemtura.

[0299] MgCl.sub.2*3EtOH carriers were received from Grace.

[0300] TiCl.sub.4 was supplied by Aldrich (Metallic impurities<1000 ppm, Metals analysis>99.9%).

[0301] General Procedure for Catalyst Component Preparation

[0302] 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 are 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*2.93EtOH 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 Al; Al/EtOH=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).

[0303] At room temperature, 70 mL of toluene was added to the pre-treated support material. To this suspension stirred at 250 rpm, neat TiCl.sub.4 (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-CC8 and IC1-IC4 Catalyst Internal Donor Examples component Internal Donor short name Comparative CC1 CD1 DFM Comparative CC2 CD2 DFE Comparative CC3 CD3 DFP Comparative CC4 CD4 TFM Comparative CC5 CD5 BTHFPT Comparative CC6 CD6 BFEF Comparative CC7 CD7 OMTOPQ Comparative CC8-a CD8 DMMF Comparative CC8-b CD8 DMMF Inventive IC1 ID1 DTHFM Inventive IC2 ID2 DTHFE Inventive IC3 ID3 TTHFM-A Inventive IC4 ID4 TTHFM-B

Comparative Examples

[0304] CC1 Preparation

[0305] CC1 was prepared using the above General Procedure, with a difference that 0.45 g (3.1 mmol) of CD1 (DFM) were used as internal donor (ID/Mg=0.102).

[0306] 3.8 g (94.8% yield, Mg-basis) of CC1 were isolated.

[0307] CC2 Preparation

[0308] CC2 was prepared using the above General Procedure, with a difference that 0.50 g (3.1 mmol) of CD2 (DFE) were used as internal donor (ID/Mg=0.102).

[0309] 3.6 g (82.4% yield, Mg-basis) of CC1 were isolated.

[0310] CC3 Preparation

[0311] CC3 was prepared using the above General Procedure, with a difference that 0.54 g (3.1 mmol) of CD3 (DFP) were used as internal donor (ID/Mg=0.102).

[0312] 3.0 g (68.3% yield, Mg-basis) of CC3 were isolated.

[0313] CC4 Preparation

[0314] CC4 was prepared using the above General Procedure, with a difference that 0.66 g (3.1 mmol) of CD4 (TFM) were used as internal donor (ID/Mg=0.102).

[0315] 3.8 g (78.2% yield, Mg-basis) of CC4 were isolated.

[0316] CC5 Preparation

[0317] CC5 was prepared using the above General Procedure, with a difference that 0.34 g (1.2 mmol) of CD5 (BTHFPT) were used as internal donor (ID/Mg=0.039).

[0318] 3.3 g (85.5% yield, Mg-basis) of CC5 were isolated.

[0319] CC6 Preparation CC6 was prepared using the above General Procedure, with a difference that 0.78 g (3.1 mmol) of CD6 (BFEF) were used as internal donor (ID/Mg=0.102).

[0320] 4.0 g (89.9% yield, Mg-basis) of CC6 were isolated.

[0321] CC7 Preparation

[0322] CC7 was prepared using the above General Procedure, with a difference that 1.37 g (3.1 mmol) of CD7 (OMTOPQ) were used as internal donor (ID/Mg=0.102).

[0323] 5.9 g (95.5% yield, Mg-basis) of CC7 were isolated.

[0324] CC8-a Preparation

[0325] CC8-a was prepared using the above General Procedure, with a difference that 0.778 g (3.1 mmol) of CD8 (DMMF) were used as internal donor (ID/Mg=0.102).

[0326] 2.3 g (57.4% yield, Mg-basis) of CC8-a were isolated.

[0327] CC8-b Preparation

[0328] CC8-b was prepared using the above General Procedure, with a difference that 1.038 g (4.1 mmol) of CD8 (DMMF) were used as internal donor (ID/Mg=0.136).

[0329] 2.8 g (64.5% yield, Mg-basis) of CC8-b were isolated.

Inventive Examples

[0330] IC1 Preparation

[0331] IC1 was prepared using the above General Procedure, with a difference that 0.48 g (3.1 mmol) of ID1 (DTHFM) were used as internal donor (ID/Mg=0.102).

[0332] 3.9 g (84.0% yield, Mg-basis) of 101 were isolated.

[0333] IC2 Preparation

[0334] IC2 was prepared using the above General Procedure, with a difference that 0.52 g (3.1 mmol) of ID2 (DTHFE) were used as internal donor (ID/Mg=0.102).

[0335] 4.7 g (93.4% yield, Mg-basis) of 102 were isolated.

[0336] IC3 Preparation

[0337] IC3 was prepared using the above General Procedure, with a difference that 0.69 g (3.1 mmol) of ID3 (TTHFM-A) were used as internal donor (ID/Mg=0.102).

[0338] 5.2 g (96.9% yield, Mg-basis) of 103 were isolated.

[0339] IC4 Preparation

[0340] IC4 was prepared using the above General Procedure, with a difference that 0.46 g (2.0 mmol) of ID4 (TTHFM-B) were used as internal donor (ID/Mg=0.068).

[0341] 4.7 g (96.7% yield, Mg-basis) of 104 were isolated.

TABLE-US-00002 TABLE 2 Summary of properties of catalyst components CC1-CC8 and IC1-IC4 ID/Mg loading Mg/Ti Mg/Al Catalyst Internal ratio, Ti, Mg, Al, Cl, Volatiles, Ti(IV) ratio, ratio, component donor (ID) mol/mol wt % wt % wt % wt % wt % proportion, % mol/mol mol/mol CC1 DFM 0.102 5.63 18.2 0.98 60.5 4.1 38.5 6.37 20.62 CC2 DFE 0.102 5.26 16.7 0.93 62.0 1.8 27.8 6.25 19.93 CC3 DFP 0.102 6.33 16.6 1.21 60.8 5.5 39.5 5.16 15.23 CC4 TFM 0.102 4.06 15.0 0.80 57.2 7.7 38.6 7.28 20.82 CC5 BTHFPT 0.039 5.57 18.9 0.72 63.0 4.0 26.1 6.68 29.14 CC6 BFEF 0.102 5.09 16.4 0.91 60.1 3.5 25.4 6.35 20.01 CC7 OMTOPQ 0.102 7.38 11.8 1.13 51.2 7.4 7.7 3.15 11.59 CC8-a DMMF 0.102 3.54 18.2 0.23 56.3 4.7 40.0 10.13 87.85 CC8-b DMMF 0.136 4.00 16.8 0.37 55.2 5.4 26.2 8.27 50.41 IC1 DTHFM 0.102 5.34 15.7 0.64 59.4 5.4 6.2 5.79 27.23 IC2 DTHFE 0.102 4.65 14.5 0.75 52.0 16.9 9.3 6.14 21.46 IC3 TTHFM-A 0.102 7.75 13.7 1.48 58.2 6.1 17.4 3.48 10.28 IC4 TTHFM-B 0.068 6.37 15.0 1.09 55.5 10.3 21.7 4.64 15.28

[0342] Bench-Scale Copolymerization with 1-Butene

[0343] The inventive catalyst components (IC1-IC4) and comparative catalyst components (CC1-CC7, CC8-a-CC8-b and CC9) were tested in copolymerization with 1-butene (IE1-IE4, CE1-CE7, CE8-a, CE8-b and CE9-a-CE9-c). Triethylaluminum (TEA) was used as a cocatalyst with an Al/Ti molar ratio of 15. The polymerization reaction was carried out in a 3 L bench-scale reactor in accordance with the following procedure:

[0344] 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.

[0345] Additionally, the comparative catalyst component CC9 was tested in copolymerization also with 55 mL of 1-butene and 0.40 bar of hydrogen gas (CE9-b) and with 40 mL of 1-butene and 0.75 bar of hydrogen gas (CE9-c).

[0346] Polymerization Results

[0347] 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- CE7, CE8-a-CE8-b, CE9-a-CE9-c and inventive examples IE1-IE4. Polymerization Catalyst Activity, 1-Butene MFR.sub.21, M.sub.W, T.sub.M, Example component kg/(g*h) content, wt % g/10 min g/mol PDI ° C. CE1 CC1 26.6 7.1 16.9 145000 4.99 123.23 CE2 CC2 21.7 7.5 18.5 146000 5.01 122.53 CE3 CC3 8.6 heavy fouling n.a. n.a. n.a. n.a. CE4 CC4 19.0 6.0 8.8 164500 4.67 122.96 CE5 CC5 23.7 6.3 11.0 181500 4.81 122.92 CE6 CC6 24.4 6.3 13.4 155000 4.82 122.56 CE7 CC7 2.7 3.4 4.3 189000 4.96 124.05 CE8-a CC8-a 19.2 4.4 3.7 211500 4.61 122.85 CE8-b CC8-b 17.3 4.8 3.9 215500 4.52 123.16 CE9-a CC9 55 6.2 5.3 200000 4.80 122.4 CE9-b CC9 54 4.8 3.0 220000 4.71 123.4 CE9-c CC9 58 3.9 8.3 160000 4.64 124.9 IE1 IC1 18.7 3.5 1.7 251500 4.05 122.43 IE2 IC2 20.7 4.0 2.2 247500 4.13 122.47 IE3 IC3 9.0 3.4 1.5 267500 3.94 122.75 IE4 IC4 19.0 3.6 1.6 256000 4.00 123.07

[0348] As can be seen from the results of the Table 3 and as indicated in FIGS. 1 to 3, all inventive examples IE1-IE4 exhibit narrower MWD and higher M.sub.W than comparative examples CE1-CE9(a-c).

[0349] Further, all inventive examples IE1-IE4 demonstrate a lower melting temperature at a given comonomer content than comparative examples CE1-CE9(a-c).

[0350] All inventive examples IE1-IE4 possess an activity level similar to comparative examples CE1-CE8 but with a much higher M.sub.W capability.

[0351] Moreover, in all inventive examples IE1-IE4 the desired balance of properties is achieved with ID/Mg loading ratios similar or lower than those that have to be employed for the comparative internal donor CD8.

[0352] To summarize the findings, all inventive examples IE1-IE4 demonstrate the highest (among the tested group of catalyst components/internal donors) M.sub.W combined with a very narrow MWD and with the lowest melting temperatures at a given comonomer content. Thus, the inventive internal donors allow for tailoring of the properties of the produced polymers while maintaining the catalyst productivity at an acceptably high level.