ZIEGLER-NATTA CATALYSTS FOR OLEFIN POLYMERIZATION

Abstract

The present invention relates to optionally substituted 1,3-dimethoxypropanes and 3-methoxypropylamines, and more particularly to their use 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 substituted 1,3-dimethoxypropanes and 3-methoxypropylamines, 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. A compound of formula (I-c) ##STR00020## wherein R.sub.1 is selected from a group consisting of tetrahydrofuryl and furyl; and R.sub.2 is selected from H and methyl.

2. (canceled)

3. (canceled)

4. A Ziegler-Natta catalyst component for olefin polymerization, comprising an internal donor selected from compounds of formula (I) ##STR00021## wherein X.sub.1 and X.sub.2 are each independently selected from O and N(R.sub.5); R.sub.1 is selected from a group consisting of H, C.sub.1-3-alkyl, and oxygen-containing heterocyclic ring; R.sub.2 is selected from H and methyl, with the provisio that only one of R.sub.1 and R.sub.2 may be H, if X.sub.1 and X.sub.2 are O; R.sub.3 and R.sub.4 are independently selected from C.sub.1-4-alkyl; R.sub.5 is selected from a group consisting of H, a linear, branched or cyclic C.sub.1-8-alkyl group.

5. The Ziegler-Natta catalyst component according to claim 4, wherein the compound of formula (I) is selected from compounds of formula (I-a) ##STR00022## wherein R.sub.1 is selected from a group consisting of H, C.sub.1-3-alkyl, and oxygen-containing heterocyclic ring; and R.sub.2 is selected from H and methyl, with the provisio that only one of R.sub.1 and R.sub.2 may be H.

6. The Ziegler-Natta catalyst component according to claim 4, further comprising: (ii) a compound of a transition metal of Group 4 to 6 of the Periodic Table (IUPAC, Nomenclature of Inorganic Chemistry, 2005); (iii) a compound of a metal of Group 1 to 3 of the Periodic Table (IUPAC, 2005); and (iv) optionally, a compound of an element of Group 13 of the Periodic Table (IUPAC, 2005).

7. 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 0.0 wt % to 3.0 wt % of the total weight of the Ziegler-Natta catalyst component.

8. The Ziegler-Natta catalyst component according to claim 4, wherein the Ziegler-Natta catalyst component is obtained 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 compound of a transition metal of Group 4 to 6; and (M-d) recovering the Ziegler-Natta catalyst component; wherein the solid support is contacted with an internal donor selected from compounds of formula (I) or mixtures therefrom before treating the solid support in step (M-c).

9. A method for producing a Ziegler-Natta catalyst component, comprising adding an internal donor selected from compounds of formula (I) ##STR00023## wherein X.sub.1 and X.sub.2 are each independently selected from O and N(R.sub.5); R.sub.1 is selected from a group consisting of H, C.sub.1-3-alkyl, and oxygen-containing heterocyclic ring; R.sub.2 is selected from H and methyl, with the provisio that only one of R.sub.1 and R.sub.2 may be H, if X.sub.1 and X.sub.2 are O; R.sub.3 and R.sub.4 are independently selected from C.sub.1-4-alkyl; R.sub.5 is selected from a group consisting of H, a linear, branched or cyclic C.sub.1-8-alkyl group to a process of preparing the Ziegler-Natta catalyst component.

10. The method according to claim 9, 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 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 donor selected from compounds of formula (I) or mixtures therefrom before treating the solid support in step (M-c).

11. The method according to claim 10, wherein the Ziegler-Natta catalyst component is the Ziegler-Natta catalyst component as defined in claim 4.

12. A Ziegler-Natta catalyst for olefin polymerization, comprising: (A) the Ziegler-Natta catalyst component as defined in claim 4 or prepared by the method as defined in claim 9; (B) a cocatalyst selected from compounds of element of Group 13 of the Periodic Table (IUPAC, 2005); and (C) optionally, an external donor.

13. A method of olefin polymerization, comprising: introducing into a polymerization reactor a Ziegler-Natta catalyst comprising an internal donor selected from compounds of formula (I) ##STR00024## wherein X.sub.1 and X.sub.2 are each independently selected from O and N(R.sub.5); R.sub.1 is selected from a group consisting of H, C.sub.1-3-alkyl, and oxygen-containing heterocyclic ring; R.sub.2 is selected from H and methyl, with the provisio that only one of R.sub.1 and R.sub.2 may be H, if X.sub.1 and X.sub.2 are O; R.sub.3 and R.sub.4 are independently selected from C.sub.1-4-alkyl; R.sub.5 is selected from a group consisting of H, a linear, branched or cyclic C.sub.1-8-alkyl group.

14. The method according to claim 13, wherein the internal donor is comprised in the Ziegler-Natta catalyst component as defined in claim 4 or prepared by the method as defined in claim 9.

15. A process for producing ethylene homo- or copolymers, comprising: (P-a) introducing the Ziegler-Natta catalyst component according to claim 4 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.

16. The process according to claim 15, wherein olefin polymerization is accomplished in a multi-stage polymerization process comprising at least one gas phase reactor for producing olefin polymers.

17. The process according to claim 15, wherein olefin polymerization is accomplished in a multi-stage polymerization process comprising at least one slurry reactor, preferably two slurry reactors, and one gas phase reactor.

Description

[0212] The advantages of the present invention are shown in the experimental part and in the figures:

[0213] FIG. 1: In FIG. 1 polydispersity index (PDI) vs. molecular weight of polymers of inventive examples (IE1-IE8) and comparative examples CE1 and CE2 is disclosed.

[0214] FIG. 2: In FIG. 2 melting temperature vs. comonomer content of polymers of inventive examples (IE1-IE8) and comparative examples CE1 and CE2 is disclosed.

[0215] FIG. 3: In FIG. 3 activity vs. molecular weight of polymers of inventive examples (IE1-IE8) and comparative examples CE1 and CE2 is disclosed.

EXPERIMENTAL PART

[0216] Analytical Methods

[0217] Al, Mq, Ti Contents in a Catalyst Component by ICP-OES

[0218] 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.

[0219] 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.

[0220] 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.

[0221] 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.

[0222] 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 %.

[0223] 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.

[0224] Cl Content in a Catalyst Component by Potentiometric Titration

[0225] 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.

[0226] Volatiles in a Catalyst Component by GC-MS

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] Polymer Melting and Crystallization Properties by DSC

[0233] 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.

[0234] Polymer Melt Flow Rate

[0235] 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.

[0236] MFR.sub.21: 190° C., 21.6 kg load

[0237] Molecular Weight Averages, Molecular Weight Distribution (M.sub.n, M.sub.w, M.sub.z, MWD, PDI)

[0238] 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) were 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{{.Math.}_{i=1}^N{A}_i}{{.Math.}_{i=1}^N\left(A_i/M_i\right)}& \left(1\right)\end{array}$$\begin{array}{cc}{M}_w=\frac{{.Math.}_{i=1}^N\left(A_i{\mathrm{xM}}_i\right)}{{.Math.}_{i=1}^N{A}_i}& \left(2\right)\end{array}$$\begin{array}{cc}{M}_Z=\frac{{.Math.}_{i=1}^N\left(A_{i}x{M}_i^2\right)}{{.Math.}_{i=1}^N\left(A_i/M_i\right)}& \left(3\right)\end{array}$

[0239] 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.

[0240] A high temperature GPC instrument, equipped with either infrared (IR) detector (IR.sub.4 or IRS from PolymerChar (Valencia, Spain) or differential refractometer (RI) from Agilent Technologies, equipped with 3× Agilent-PLgel Olexis and 1× Agilent-PLgel Olexis Guard columns was used. As the solvent and mobile phase 1,2,4-trichlorobenzene (TCB) stabilized with 250 mg/L 2,6-Di tert butyl-4-methyl-phenol) was used. The chromatographic system was operated at 160° C. and at a constant flow rate of 1 mL/min. 200 μL of sample solution was injected per analysis. Data collection was performed using either Agilent Cirrus software version 3.3 or PolymerChar GPC-IR control software.

[0241] The column set was 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 were 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:

[0242] K.sub.PS=19×10.sup.−3 mL/g, η.sub.PS=0.655

[0243] K.sub.PE=39×10.sup.−3 mL/g, η.sub.PE=0.725

[0244] K.sub.PP=19×10.sup.−3 mL/g, η.sub.PP=0.725

[0245] A third order polynomial fit was used to fit the calibration data.

[0246] All samples were 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.

[0247] Polymer Comonomer Content (1-Butene) by FTIR

[0248] Comonomer content is determined based on Fourier transform infrared spectroscopy (FTIR) using Bruker Tensor 37 spectrometer together with OPUS software.

[0249] 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.

[0250] 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.

[0251] 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.

[0252] 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.

[0253] 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

[0254] where

[0255] W.sub.E=result in wt %

[0256] A.sub.0=absorbance of the measured peak (A.sub.Q) to the area of the reference peak (A.sub.R);

[0257] C.sub.1=slope of the calibration curve;

[0258] C.sub.0=offset of the calibration curve.

[0259] The comonomer content is determined from both of the obtained spectra and the value is calculated as the average of these results.

Examples

[0260] Comparative Internal Donor

CD1: 9,9-Di(methoxymethyl)fluorene (DMMF)

[0261] ##STR00011##

[0262] 9,9-Di(methoxymethyl)fluorene (CAS 182121-12-6), alternatively named 9,9-Bis(methoxymethyl)-9H-fluorene, was acquired from Hangzhou Sage Chemical Co.

[0263] Reference Internal Donors

RD1: 1,3-Dimethoxypropane (DMP)

[0264] ##STR00012##

[0265] 1,3-Dimethoxypropane (CAS 17081-21-9) was acquired from BOC Sciences.

[0266] Inventive Internal Donors

[0267] Inventive donors ID2 to ID7 were prepared according to the following procedures:

ID2: 1,3-Dimethoxy-2-methylpropane (DMMP)

[0268] ##STR00013##

[0269] To a suspension of 24.05 g (666.7 mmol, 2.5 eq.) of sodium hydride in 470 mL of THF a solution of 24.05 g (266.9 mmol) of 2-Methylpropane-1,3-diol and 95 g (669.3 mmol, 2.51 eq.) of methyl iodide in 200 mL of THF was added drop-wise for 2 h. After completion of the addition the reaction mixture was stirred overnight. Further on, the mixture was filtered through glass frit (G3), then 400 mL of water were added to the filtrate and the resulting mixture was extracted with 800 mL of n-hexane. The obtained organic extract was dried over sodium sulfate and distilled (b.p. 108-117° C.) under atmospheric pressure to give 20.36 g of 1,3-Dimethoxy-2-methylpropane contaminated with −5 mol % of THF. This fraction was distilled once again to give 17.5 g (56%) of 1,3-Dimethoxy-2-methylpropane (CAS 210528-98-6) as a colorless liquid (b.p. 115° C.).

[0270] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 3.37-3.31 (s and dd, sum 8H), 3.24 (dd, J=9.3 Hz, J=6.2 Hz, 2H), 2.09-1.95 (m, 1H), 0.94 (d, J=6.9 Hz, 3H).

[0271] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ75.3, 58.9, 34.0, 14.3.

ID3: 1,3-Dimethoxy-2,2-dimethylpropane (DMDMP)

[0272] ##STR00014##

[0273] To a suspension of 16 g (666.7 mmol, 2.48 eq.) of sodium hydride in 470 mL of THF a solution of 28 g (268.9 mmol) of 2,2-Dimethylpropane-1,3-diol and 95 g (669.3 mmol, 2.49 eq.) of methyl iodide in 200 mL of THF was added drop-wise for 2 h. After completion of the addition the reaction mixture was stirred overnight. Further on, the reaction mixture was filtered through glass frit (G3), then 600 mL of water were added to the filtrate and the resulting mixture was extracted with 3×250 mL of n-hexane. The organic extracts were combined, dried over sodium sulfate, and rectified under atmospheric pressure to give 24.2 g (68%) of 1,3-Dimethoxy-2,2-dimethylpropane (CAS 20637-32-5) as a colorless liquid, b.p. 121-122° C.

[0274] .sup.1H NMR (CDCl.sub.3, 400 MHz): 53.33 (s, 6H), 3.14 (s, 4H), 0.89 (s, 6H).

[0275] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ79.1, 59.3, 36.1, 22.1.

ID4: 1,3-Dimethoxy-2-(2-tetrahydrofuryl)propane (DMTHFP)

[0276] ##STR00015##

Diethyl 2-(tetrahydrofuran-2-yl)malonate

[0277] A mixture of Diethyl (2-furyl)malonate (10.0 g, 44 mmol), 5% Pd/C (500 mg) and ethyl acetate (10 mL) was placed into a 200 mL autoclave which was purged with argon, pressurized with hydrogen (20 bar) and the mixture was stirred for 1 h at room temperature. After depressurization, the mixture was diluted with dichloromethane and filtered through a pad of Celite 503. The filtrate volatiles were evaporated in vacuum. The procedure afforded 9.9 g (97%) of Diethyl 2-(tetrahydrofuran-2-yl)malonate as a colorless liquid which was used in the next step without additional purification.

[0278] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 4.48-4.40 (m, 1H), 4.25-4.15 (m, 4H), 3.87-3.71 (m, 2H), 2.19-2.06 (m, 1H), 1.94-1.86 (m, 2H), 1.76-1.65 (m, 1H), 1.27-1.22 (m, 6H).

1,3-Dimethoxy-2-(2-tetrahydrofuryl)propane

[0279] To a suspension of lithium aluminum hydride (40.6 g, 1.07 mol) in anhydrous diethyl ether (2 L) Diethyl 2-(tetrahydrofuran-2-yl)malonate (54.0 g, 235 mmol) was added portion-wise at 0° C. The obtained solution was stirred for 2 h at room temperature and quenched carefully with 150 mL of water. The obtained suspension was filtered through a pad of Celite 503, and the solvent was removed in vacuum. The procedure yielded 12.8 g of crude 2-(Tetrahydrofuran-2-yl)propane-1,3-diol as a yellow oil which was used in the next step without additional purification.

[0280] To a suspension of sodium hydride (60 wt % in mineral oil, 10.6 g, 263 mmol) in anhydrous THF (300 mL) crude 2-(Tetrahydrofuran-2-yl)propane-1,3-diol (12.8 g) was added portion-wise at 0° C. The obtained mixture was stirred for 30 min at room temperature and methyl iodide (49.8 g, 351 mmol) was added at 0° C. The obtained mixture was stirred for 3 h at room temperature and quenched carefully with 200 mL of water. The crude product was extracted with 3×200 mL of diethyl ether. The combined extract was dried over Na.sub.2SO.sub.4 and the volatiles evaporated to dryness in vacuum. Fractional distillation of the crude product provided 11.0 g (71%) of a colorless oil (b.p. 85-90° C./15 mbar) of 1,3-Dimethoxy-2-(2-tetrahydrofuryl)propane, alternatively named 2-[2-Methoxy-1-(methoxymethyl)ethyl]tetrahydrofuran or 2-(1,3-dimethoxypropan-2-yl)tetrahydrofuran).

[0281] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 3.82-3.72 (m, 2H), 3.68-3.61 (m, 1H), 3.49-3.38 (m, 2H), 3.36 (d, J=5.5 Hz, 2H), 3.26 (s, 3H), 3.25 (s, 3H), 1.95-1.75 (m, 4H), 1.63-1.52 (m, 1H).

[0282] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 77.8, 71.1, 70.7, 67.5, 58.8, 44.2, 29.4, 25.6.

ID5: 1,3-Dimethoxy-2-(2-furyl)propane (DMFP)

[0283] ##STR00016##

Diethyl 2-furylmalonate

[0284] A mixture of furan (102 g, 1.50 mol), Diethyl malonate (432 g, 2.70 mol), methanol (2700 mL), water (300 mL), and of Ce(SO.sub.4).sub.2.4H.sub.2O (242 g, 0.60 mol) was stirred under an argon atmosphere for 12 h at room temperature. The obtained suspension was filtered through a pad of Celite 503. The filtrate was poured into 2 L of water. The crude product was extracted with 3×500 mL of dichloromethane. The combined extract was dried over Na.sub.2SO.sub.4 and the volatiles evaporated to dryness. Fractional distillation of the residue provided 55.6 g (82%) of Diethyl 2-furylmalonate as a yellow oil (b.p. 95-100° C./2 mbar).

[0285] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.40 (br.s, 1H), 6.41 (m, 2H), 4.76 (s, 1H), 4.24 (q, 4H, J=7.0 Hz), 1.28 (t, 6H, J=7.0 Hz).

2-(2-Furyl)propane-1,3-diol

[0286] To a suspension of lithium aluminum hydride (53.8 g, 1.42 mol) in anhydrous diethyl ether (1800 mL) Diethyl 2-furylmalonate (80.0 g, 354 mmol) was added portion-wise at 0° C. The obtained solution was stirred for 2 h at room temperature and quenched carefully with 200 mL of water. The obtained suspension was filtered through a pad of Celite 503. The filtrate was evaporated to dryness. Fractional distillation of the residue yielded 5.8 g (12%) of 2-(2-Furyl)propane-1,3-diol as a colorless oil (b.p. 95° C./2 mbar).

[0287] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.34 (dd, 1H, J=1.7 Hz, J=0.7 Hz), 6.20 (dd, 1H, J=3.3 Hz, J=1.9 Hz), 6.15 (d, 1H, J=3.3 Hz), 3.55 (d, 4H, J=6.5 Hz), 3.26 (qv, 1H, J=6.5 Hz), 2.25 (br.s, 2H).

1,3-Dimethoxy-2-(2-furyl)propane

[0288] To a suspension of sodium hydride (60 wt % in mineral oil, 4.9 g, 123 mmol) in anhydrous THF (250 mL) 2-(2-Furyl)propane-1,3-diol (5.8 g, 40.8 mmol) was added portion-wise at 0° C. The obtained mixture was stirred for 30 min at room temperature, cooled to 0° C. and methyl iodide (10.2 g, 163 mmol) was added. The obtained mixture was stirred for 3 h at room temperature and quenched carefully with 100 mL of water. The crude product was extracted with 3×100 mL of diethyl ether. The combined extract was dried over Na.sub.2SO.sub.4 and the volatiles evaporated to dryness. Fractional distillation of the residue yielded 4.9 g (71%) of a colorless oil (b.p. 67° C./40 mbar) of 1,3-Dimethoxy-2-(2-furyl)propane, alternatively named 2-[2-Methoxy-1-(methoxymethyl)ethyl]furan or 2-(1,3-dimethoxypropan-2-yl)furan.

[0289] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.32 (dd, 1H, J=1.7 Hz, J=0.7 Hz), 6.29 (dd, 1H, J=3.1 Hz, J=1.9 Hz), 6.13 (d, 1H, J=3.2 Hz), 3.63 (d, 4H, J=6.2 Hz), 3.33 (s, 6H), 3.26 (qv, 1H, J=6.2 Hz).

[0290] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 154.3, 141.2, 110.2, 105.9, 72.0, 59.0, 40.0.

ID6: 1,3-Dimethoxy-2-methyl-2-(2-tetrahydrofuryl)propane (DMMTHFP)

[0291] ##STR00017##

[0292] A mixture of 2-(1,3-Dimethoxy-2-methylpropan-2-yl)furan (18.4 g, 0.100 mmol), 5% Pd/C (900 mg), and isopropanol (20 mL) was placed into a 200 mL autoclave which was purged with argon and pressurized with hydrogen (70 bar). This mixture was then stirred for 1 h at room temperature. After depressurization, the obtained mixture was diluted with dichloromethane and filtered through a pad of Celite 503. The filtrate volatiles were evaporated in vacuum and the residue was passed through a pad of silica gel 60 (40-63 um, eluent: hexane/ethyl acetate=3: 1, vol.). The solvent was removed in vacuum. This procedure afforded 14.5 g (77%) of 1,3-Dimethoxy-2-methyl-2-(2-tetrahydrofuryl)propane, alternatively named 2-(1,3-dimethoxy-2-methylpropan-2-yl)tetrahydrofuran, as a colorless liquid.

[0293] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 3.82-3.68 (m, 3H), 3.37-3.27 (m, 2H), 3.31 (s, 3H), 3.29 (s, 3H), 3.26-3.18 (m, 2H), 1.86-1.66 (m, 4H), 0.83 (s, 3H).

[0294] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 81.0, 75.7, 75.6, 68.1, 59.3, 42.1, 26.1, 26.0, 14.7.

ID7: 1,3-Dimethoxy-2-methyl-2-(2-furyl)propane 2-(1,3-dimethoxy-2-methylpropan-2-yl)furan (DMMFP)

[0295] ##STR00018##

Diethyl 2-furyl(methyl)malonate

[0296] A mixture of furan (68 g, 1.00 mol), Diethyl methyl malonate (313 g, 1.80 mol), methanol (1800 mL), water (200 mL), and Ce(SO.sub.4).sub.2.4H.sub.2O (162 g, 0.40 mol) was stirred under an argon atmosphere for 12 h at room temperature. The obtained suspension was filtered through a pad of Celite 503. The filtrate was poured into 2 L of water. The crude product was extracted with 3×300 mL of dichloromethane. The combined extract was dried over Na.sub.2SO.sub.4 and the volatiles evaporated to dryness. Fractional distillation of the residue yielded 34.4 g (72%) of Diethyl 2-furyl(methyl)malonate as a yellow oil (b.p. 97-100° C./2 mbar).

[0297] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.38 (s, 1H), 6.34 (s, 2H), 4.22 (q, 4H, J=7.1 Hz), 1.81 (s, 3H), 1.24 (t, 6H, J=7.1 Hz)

2-(2-Furyl)-2-methylpropane-1,3-diol

[0298] To a suspension of lithium aluminum hydride (43.5 g, 1.15 mol) in anhydrous diethyl ether (2 I) Diethyl 2-furyl(methyl)malonate (68.7 g, 354 mmol) was added portion-wise at 0° C. The obtained solution was stirred for 2 h at room temperature and then quenched carefully with 165 mL of water. The obtained suspension was filtered through a pad of Celite 503. The filtrate volatiles were evaporated to dryness. The residue was diluted with 100 mL diethyl ether and the precipitate was filtered off. This procedure afforded 26.0 g (58%) of 2-(2-Furyl)-2-methylpropane-1,3-diol as a white solid.

[0299] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.38-7.41 (m, 1H), 6.36 (dd, 1H, J=3.2 Hz, J=1.8 Hz), 6.22 (d, 1H, J=3.2 Hz), 3.86-3.92 (m, 2H), 3.76-3.80 (m, 2H), 2.25 (br.s, 2H), 1.28 (s, 3H)

1,3-Dimethoxy-2-methyl-2-(2-furyl)propane

[0300] To a suspension of sodium hydride (60 wt % in mineral oil, 13.0 g, 327 mmol) in anhydrous THF (400 mL) 2-(2-Furyl)-2-methyl-propane-1,3-diol (17.0 g, 109 mmol) was added portion-wise at 0° C. The obtained mixture was stirred for 30 min at room temperature, cooled to 0° C. and methyl iodide (20.5 mL, 327 mmol) was added. The obtained mixture was stirred for 3 h at room temperature and quenched carefully with 200 mL of water. The crude product was extracted with 3×200 mL of diethyl ether. The combined extract was dried over Na.sub.2SO.sub.4 and the volatiles evaporated to dryness. Fractional distillation of the residue yielded 18.9 g (94%) of 1,3-Dimethoxy-2-methyl-2-(2-furyl)propane, alternatively named 2-(1,3-Dimethoxy-2-methylpropan-2-yl)furan, as colorless oil (b.p. 72° C./40 mbar).

[0301] .sup.1H NMR (CDCl.sub.3, 400 MHz): δ 7.34-7.36 (m, 1H), 6.32 (dd, 1H, J=3.1 Hz, J=1.9 Hz), 6.13 (d, 1H, J=3.2 Hz), 3.51-3.58 (m, 4H), 3.31 (s, 6H), 1.28 (s, 3H).

[0302] .sup.13C{.sup.1H} NMR (CDCl.sub.3, 100 MHz): δ 158.2, 141.0, 110.0, 105.0, 76.5, 59.4, 41.9, 19.1.

ID8: (3-Methoxypropyl)dimethylamine (MPDMA)

[0303] ##STR00019##

[0304] (3-Methoxypropyl)dimethylamine (CAS 20650-07-1), alternatively named 3-Methoxy-N,N-dimethylpropan-1-amine, was acquired from UORSY.

[0305] Inventive and Comparative Catalyst Components

[0306] Inventive catalyst components (IC2-IC8), a reference catalyst component (RC1) and comparative catalyst components (CC1-a and CC1-b) were prepared according to the procedure of the Reference Example 2 of WO2016/124676 A1, but using inventive donors (ID2-ID8), reference donor (RD1) and comparative donor (CD1), respectively. Summary of donors used in catalyst component examples is disclosed in Table 1.

[0307] Comparative catalyst component CC2 is a catalyst commercially available from Grace under the trade name Lynx 200.

[0308] Raw Materials

[0309] The 10 wt % TEA (triethylaluminium) stock solutions in heptane were prepared by dilution of 100 wt % TEA-S from Chemtura.

[0310] MgCl.sub.2*3EtOH carriers were received from Grace.

[0311] TiCl.sub.4 was supplied by Aldrich (metallic impurities <1000 ppm, Metals analysis >99.9%).

[0312] General Procedure for Catalyst Component Preparation

[0313] 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.v0.5) 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).

[0314] 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 using 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 component 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, reference component RC1, and IC2-IC8 Catalyst Internal Donor Examples component Internal Donor short name Comparative CC1-a CD1 DMMF Comparative CC1-b CD1 DMMF Reference RC1 RD1 DMP Inventive IC2 ID2 DMMP Inventive IC3 ID3 DMDMP Inventive IC4 ID4 DMTHFP Inventive IC5 ID5 DMFP Inventive IC6 ID6 DMMTHFP Inventive IC7 ID7 DMMFP Inventive IC8 ID8 MPDMA

Comparative Examples

[0315] CC1-a Preparation

[0316] 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).

[0317] 2.3 g (57.4% yield, Mg-basis) of CC1-a were isolated.

[0318] CC1-b Preparation

[0319] 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).

[0320] 2.8 g (64.5% yield, Mg-basis) of CC1-b were isolated.

Reference Catalyst Example

[0321] RC1 Preparation

[0322] RC1 was prepared using the above General Procedure, with a difference that 0.159 g (1.5 mmol) of ID1 (DMP) were used as internal donor (ID/Mg=0.051).

[0323] 2.6 g (67.7% yield, Mg-basis) of IC1 were isolated.

Inventive Catalyst Examples

[0324] IC2 Preparation

[0325] IC2 was prepared using the above General Procedure, with a difference that 0.24 g (2.0 mmol) of ID2 (DMMP) were used as internal donor (ID/Mg=0.068).

[0326] 2.8 g (75.3% yield, Mg-basis) of IC2 were isolated.

[0327] IC3 Preparation

[0328] IC3 was prepared using the above General Procedure, with a difference that 0.270 g (2.0 mmol) of ID3 (DMDMP) were used as internal donor (ID/Mg=0.068).

[0329] 2.4 g (61.5% yield, Mg-basis) of IC3 were isolated.

[0330] IC4 Preparation

[0331] IC4 was prepared using the above General Procedure, with a difference that 0.36 g (2.0 mmol) of ID4 (DMTHFP) were used as internal donor (ID/Mg=0.068).

[0332] 4.0 g (78.4% yield, Mg-basis) of IC4 were isolated.

[0333] IC5 Preparation

[0334] IC5 was prepared using the above General Procedure, with a difference that 0.52 g (3.1 mmol) of ID5 (DMFP) were used as internal donor (ID/Mg=0.102).

[0335] 3.5 g (80.6% yield, Mg-basis) of IC5 were isolated.

[0336] IC6 Preparation

[0337] IC6 was prepared using the above General Procedure, with a difference that 0.38 g (2.0 mmol) of ID6 (DMMTHFP) were used as internal donor (ID/Mg=0.068).

[0338] 4.3 g (95.5% yield, Mg-basis) of IC6 were isolated.

[0339] IC7 Preparation

[0340] IC7 was prepared using the above General Procedure, with a difference that 0.38 g (2.0 mmol) of ID7 (DMMFP) were used as internal donor (ID/Mg=0.068).

[0341] 3.3 g (82.4% yield, Mg-basis) of IC7 were isolated.

[0342] IC8 Preparation 108 was prepared using the above General Procedure, with a difference that 0.36 g (3.1 mmol) of ID8 (MPDMA) were used as internal donor (ID/Mg=0.102).

[0343] 4.3 g (89.1% yield, Mg-basis) of IC8 were isolated.

TABLE-US-00002 TABLE 2 Summary of properties of catalyst components CC1-a, CC1-b, RC1 and IC2 -IC8. ID/Mg loading Vola- Mg/Ti Mg/AI Catalyst Internal ratio, Ti, Mg, Al, CI, tiles, Ti(IV) ratio, ratio, component donor (ID) mol/mol wt % wt % wt % wt % wt % proportion, % 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 RC1 DMP 0.051 4.94 19.0 0.42 64.6 4.1 18.3 7.57 50.22 IC2 DMMP 0.068 4.45 19.6 0.45 63.5 3.4 22.0 8.67 48.35 IC3 DMDMP 0.068 4.07 18.7 0.37 65.0 5.7 22.8 9.05 56.11 IC4 DMTHFP 0.068 7.35 14.3 1.18 60.2 5.3 84.1 3.83 13.45 IC5 DMFP 0.102 4.56 16.9 0.95 59.1 6.4 17.4 7.30 19.75 IC6 DMMTHFP 0.068 6.88 16.2 1.00 57.8 7.5 22.1 4.64 17.98 IC7 DMMFP 0.068 5.00 18.2 0.82 60.7 2.9 23.7 7.17 24.64 IC8 MPDMA 0.102 8.96 15.0 0.99 66.4 5.7 6.8 3.30 16.82

[0344] Bench-Scale Ethylene Copolymerization with 1-Butene

[0345] The inventive catalyst components (102-108), the reference catalyst component (RC1) and the comparative catalyst components (CC1-a, CC1-b and CC2) were tested in ethylene copolymerization with 1-butene (IE2-IE8, RE1, CE1-a, CE1-b and CE2-a). 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:

[0346] 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.

[0347] Additionally, the comparative catalyst component CC2 was tested in copolymerization also with 55 mL of 1-butene and 0.40 bar of hydrogen gas (CE2-b) and with 40 mL of 1-butene and 0.75 bar of hydrogen gas (CE2-c).

[0348] Polymerization Results

[0349] 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-a - CE2-c, reference example RE1 and inventive examples IE2-IE8. 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-a CC1-a 19.2 4.4 3.7 211500 4.61 122.85 CE1-b CC1-b 17.3 4.8 3.9 215500 4.52 123.16 CE2-a CC2 55 6.2 5.3 200000 4.80 122.4 CE2-b CC2 54 4.8 3.0 220000 4.71 123.4 CE2-C CC2 58 3.9 8.3 160000 4.64 124.9 RE1 RC1 29.1 4.8 2.9 228000 4.23 122.27 IE2 IC2 27.4 4.4 1.5 260500 4.01 121.97 IE3 IC3 22.1 5.6 3.1 217500 4.46 121.80 IE4 IC4 19.0 4.9 2.8 236000 4.47 123.09 IE5 IC5 14.0 4.2 1.2 276500 3.99 121.61 IE6 IC6 21.2 4.6 2.9 224000 4.42 122.57 IE7 IC7 20.4 4.7 2.2 243500 4.32 122.08 IE8 IC8 21.4 4.3 4.1 198000 3.92 123.26

[0350] As can be seen from the results and as also shown in FIG. 1, inventive examples (IE2-IE8) and reference example RE1 exhibit a narrower MWD (described by PDI) than comparative examples CE1 and CE2. While IE2-IE7 and reference example RE1 possesses similar or higher average M.sub.w and narrower MWD than CE1-CE2, IE8 possesses a similar average M.sub.w with a much narrower MWD compared to CE1-CE2.

[0351] Further (as shown in FIG. 2), all inventive examples (IE2-IE8) and reference example RE1 have a lower melting temperature Tm at a given comonomer content than comparative examples CE2 and a lower or similar melting temperature at a given comonomer content than comparative examples CE1.

[0352] In addition, as shown by the examples and in FIG. 3, all inventive examples (IE2-IE8) and reference example RE1 demonstrate an activity level which is similar to the comparative examples CE1 with a similar or higher M.sub.w capability.

[0353] Moreover, in all inventive examples (IE2-IE8) and reference example RE1 the desired balance of properties is achieved with similar or lower ID/Mg loading ratios.

[0354] To summarize the findings, while IE2 and IE5 have the highest M.sub.w combined with very narrow MWD and with lowest melting temperature at a given comonomer content, IE8 has lowest M.sub.w combined with narrowest MWD and with moderate 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 acceptably high level.