ETHYLENE-OCTENE COPOLYMERS WITH IMPROVED PROPERTY PROFILE

Abstract

Ethylene-1-octene copolymer characterized by a density in the range of 850 kg/m.sup.3 to 930 kg/m.sup.3 measured according to ISO 1183-187, a melt flow rate MFR2 (190° C., 2.16 kg) in the range of from 0.3 g/10 min to 100 g/10 min measured according to ISO 1133, a MFR.sub.10/MFR.sub.2 of from 5.0 to 15.0, a Mw/Mn of from 2.0 to 5.0, 1.0 to below 20 vinyl unsaturation units/100,000 C atoms, more than 5.0 to 35 vinylidene unsaturation units/100,000 C atoms, more than 5.0 to 30 vinylene unsaturation units/100,000 C atoms, more than 15.0 to 60 trisubstituted unsaturation units/100,000 C atoms, 26 to 150 total unsaturation units/100,000 C atoms, wherein the total unsaturation units/100,000 C atoms is the sum of vinyl unsaturation units/100,000 C atoms, vinylidene unsaturation units/100,000 C atoms, vinylene unsaturation units/100,000 C atoms and trisubstituted unsaturation units/100,000 C atoms, an unsaturation degree for unsaturation types e) to h) according to formula (I) wherein a vinyl unsaturation degree is in the range of from 5.0 to 15.0%, a vinylene unsaturation degree is in the range of from 20.0 to 30.0%, and wherein the sum of the vinyl unsaturation degree and vinylidene unsaturation degree is at least 30.0% and up to 50.0%.

[00001]$\begin{array}{cc}{\mathrm{unsaturation}}_{\mathrm{Type}}\mathrm{degree}\left(\%\right)=\frac{{\mathrm{unsaturation}}_{\mathrm{Type}}\mathrm{units}/100,000C\mathrm{atoms}}{\mathrm{total}\mathrm{unsaturation}\mathrm{units}/100,000C\mathrm{atoms}}*100& \left(I\right)\end{array}$

Claims

1. Ethylene-1-octene copolymer having a) a density in the range of 850 kg/m.sup.3 to 930 kg/m.sup.3 measured according to ISO 1183-187, b) a melt flow rate MFR.sub.2 (190° C., 2.16 kg) in the range of from 0.8 g/10 min to 100 g/10 min measured according to ISO 1133, c) a MFR.sub.10/MFR.sub.2 of from 5.0 to 15.0 measured according to ISO 1133, d) a Mw/Mn of from 2.0 to 5.0 determined by Gel Permeation Chromatography, characterized by e) 1.0 to below 20.0 vinyl unsaturation units/100,000 C atoms measured by 1H NMR, f) more than 5.0 to 35.0 vinylidene unsaturation units/100,000 C atoms measured by 1H NMR, g) more than 5.0 to 30.0 vinylene unsaturation units/100,000 C atoms measured by 1H NMR, h) more than 15.0 to 60.0 trisubstituted unsaturation units/100,000 C atoms measured by .sup.1H NMR, i) 26 to 150 total unsaturation units/100,000 C atoms, wherein the total unsaturation units/100,000 C atoms is the sum of vinyl unsaturation units/100,000 C atoms, vinylidene unsaturation units/100,000 C atoms, vinylene unsaturation units/100,000 C atoms and trisubstituted unsaturation units/100,000 C atoms, all measured by 1H NMR, j) an unsaturation degree according to formula ${\mathrm{unsaturation}}_{\mathrm{Type}}\mathrm{degree}\left(\%\right)=\frac{{\mathrm{unsaturation}}_{\mathrm{Type}}\mathrm{units}/100,000C\mathrm{atoms}}{\mathrm{total}\mathrm{unsaturation}\mathrm{units}/100,000C\mathrm{atoms}}*100$ wherein a vinyl unsaturation degree is in the range of from 5.0 to 20%, a vinylene unsaturation degree is in the range of from 12.0 to 30.0%, and k) wherein the sum of the vinyl unsaturation degree and vinylidene unsaturation degree is at least 30.0% up to 50.0%.

2. The ethylene-1-octene copolymer according to claim 1, wherein the total unsaturation units/100,000 C of the copolymer follows the inequation (I)
y>−0.0002A+65.8   (I) wherein y is the total unsaturation/100 000 C atoms and A is the Mw of the copolymer in g/mol, and/or the total unsaturation units/100,000 C of the copolymer follows the inequation (II)
y>0.12B+39.38   (II) wherein y is the total unsaturation/100 000 C atoms and B is the 1-octene content of the copolymer in wt. %.

3. The ethylene-1-octene copolymer according to claim 1, wherein the ratio MFR.sub.10/MFR.sub.2 is in a range of from 6.0 to 13.0 measured according to ISO 1133.

4. The ethylene-1-octene copolymer according to claim 1, wherein the Mw/Mn is in the range of 2.4 up to 4.0 determined by Gel Permeation Chromatography.

5. The ethylene-1-octene copolymer according to claim 1, wherein the melt flow rate MFR.sub.2 (190° C., 2.16 kg) is in the range of from 0.8 g/10 min to 90 g/10 min measured according to ISO 1133.

6. The ethylene-1-octene copolymer according to claim 1, wherein a vinylidene unsaturation degree is in the range of from 20.0 to 32.0%.

7. The ethylene-1-octene copolymer according to claim 1, wherein the vinyl unsaturation degree is in the range of from 7.0 to 17.0%.

8. The ethylene-1-octene copolymer according to claim 1, wherein the 1-octene is present in an amount of 10 to 45 wt. % based on the weight of the total copolymer.

9. Process for producing the ethylene-1-octene copolymer according to claim 1 in a continuous high temperature solution process at a temperature from 120° C. to 250° C. and a pressure of 50 to 300 bar, the process comprising at least the steps of: (A) polymerizing in at least a first polymerization reactor in a first solvent ethylene monomer and 1-octene comonomer in the presence of a first polymerization catalyst and optionally a chain transfer agent for producing a first solution comprising a first ethylene-1 -octene copolymer and the first solvent; whereby the first solvent, ethylene monomer and 1-octene comonomer are provided in a first feed stream; and wherein the first polymerization reactor is operated under operating conditions which ensure that the reactor contents form a single homogenous phase, (B) withdrawing a first stream of the first solution from the first polymerization reactor, (C) separating the first ethylene-1-octene copolymer from the first stream of step (B), wherein the first polymerization catalyst comprises: (i) at least one metallocene complex of formula (I) ##STR00006## wherein M is Hafnium, R are the same or different from each other and can be a saturated linear or branched C1 to C10 alkyl, R.sup.1 is an unsubstituted C6 to C10 aryl, and R.sup.2 is a C4 to C20 cycloalkyl group or a C4 to C6 alkenyl group, X is a C1 to C6 alkyl, and (ii) a boron containing cocatalyst.

10. The process according to claim 9, further comprising the steps of (D) polymerizing in a second polymerization reactor in a second solvent ethylene monomer and 1-octene comonomer in the presence of a second polymerization catalyst and optionally a chain transfer agent for producing a second solution comprising a second ethylene-1-octene copolymer and the second solvent; whereby the second solvent, ethylene monomer and 1-octene comonomer are provided in a second feed stream; and wherein the second polymerization reactor is operated under operating conditions which ensure that the reactor contents form a single homogenous phase, (E) withdrawing a second stream of the second solution from the second polymerization reactor, (F) separating the second ethylene-1-octene copolymer from the second stream of step (E), and (G) combining the first ethylene-1 -octene copolymer of step (C) with the second ethylene-1-octene copolymer of step (F), wherein the second polymerization catalyst comprises: (i) at least one metallocene complex of formula (I) ##STR00007## wherein M is Hafnium, R are the same or different from each other and can be a saturated linear or branched C1 to C10 alkyl, R.sup.1 is a unsubstituted C6 to C10 aryl, and R.sup.2 is a C4 to C20 cycloalkyl group or a C4 to C6 alkenyl group, X is a C1 to C6 alkyl, and (ii) a boron containing cocatalyst, and wherein the first polymerization catalyst and the second polymerization catalyst can be the same or different from each other.

11. The process according to any one of claim 9, wherein the at least one metallocene complex of formula (I) is a metallocene complex of formula (Ia) ##STR00008## and/or a metallocene complex of formula (Ib) ##STR00009##

12. The process according to any one of claim 9, wherein a comonomer reactivity according to formula (II)
Comonomer Reactivity=(C8/C2).sub.polymer/(C8/C2).sub.feed   (II) is >0.28 up to 0.65, wherein in the formula (II) (C8/C2).sub.polymer is the ratio of wt. % of 1-octene/wt. % of ethylene in the copolymer and (C8/C2).sub.feed is the ratio of wt. % of 1-octene/wt. % of ethylene in the first feed stream, or in the sum of first feed stream and the second feed stream.

13. The process according to clam 9 wherein the boron containing cocatalyst comprises an anion of formula (III)
(Z)4B-  (III) wherein Z is an optionally substituted phenyl derivative, said substituent being a halo-C.sub.1-6-alkyl or halo group.

14. The process according to claim 9, wherein the boron containing cocatalyst is a borate selected from the group consisting of triphenylcarbeniumtetrakis(pentafluorophen-yl)borate, N,N-dimethylcyclohexylammoniumtetrakis(pentafluorophenyl)borate, N,N-dimethylbenzylammoniumtetrakis(pentafluorophenyl)borate, and N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate.

15. A process, comprising grafting the ethylene-1-octene copolymer according to claim 1 with comonomer units comprising hydrolysable silane groups to obtain a grafted ethylene-1-octene copolymer comprising hydrolysable silane groups.

16. The ethylene-1-octene copolymer according to claim 1, wherein a trisubstituted unsaturation degree is in the range of from 35.0 to 50.0%.

17. The ethylene-1-octene copolymer according to claim 1, wherein the vinylidene unsaturation degree is in the range of from 22.0 to 28.0%.

18. The ethylene-1-octene copolymer according to claim 1, wherein the vinylene unsaturation degree is in the range of from 14.0 to 28.0%.

19. The ethylene-1-octene copolymer according to claim 1, wherein the trisubstituted unsaturation degree is in the range of from 36.0 to 45.5%.

Description

EXAMPLES

1. Measurement Methods

a) Melt Flow Rate (MFR) and Flow Rate Ratio (FRR)

[0159] The melt flow rate (MFR) is determined according to ISO1133—Determination of the melt mass-flow rate (MFR) and melt volume-flow rate (MVR) of thermoplastics—Part 1: Standard method, and is indicated in g/10min. The MFR is an indication of flowability, and hence processability, of the polymer. The higher the melt flow rate, the lower the viscosity of the polymer.

[0160] The MFR.sub.2 of polyethylene is determined at a temperature of 190° C. and a load of 2.16 kg.

[0161] The MFR.sub.10 of polyethylene is determined at a temperature of 190° C. and a load of 10 kg.

[0162] The flow rate ratio (FRR) is the MFR.sub.10/MFR.sub.2.

b) Density

[0163] The density of the polymer was measured according to ISO1183-187.

c) Cornonomer Content

[0164] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the comonomer content of the polymers.

[0165] Quantitative .sup.13C{.sup.1H} NMR spectra recorded in the molten-state using a Bruker Avance III 500 NMR spectrometer operating at 500.13 and 125.76 MHz for .sup.1H and .sup.13C respectively. All spectra were recorded using a .sup.13C optimised 7 mm magic-angle spinning (MAS) probehead at 150° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was packed into a 7 mm outer diameter zirconia MAS rotor and spun at 4 kHz. This setup was chosen primarily for the high sensitivity needed for rapid identification and accurate quantification. Standard single-pulse excitation was employed utilising the transient NOE at short recycle delays of 3 s and the RS-HEPT decoupling scheme. A total of 1024 (1 k) transients were acquired per spectrum.

[0166] Quantitative .sup.13C{.sup.1H} NMR spectra were processed, integrated and quantitative properties determined using custom spectral analysis automation programs. All chemical shifts are internally referenced to the bulk methylene signal (d+) at 30.00 ppm.

[0167] Characteristic signals corresponding to the incorporation of 1-octene were observed and all comonomer contents calculated with respect to all other monomers present in the polymer.

[0168] Characteristic signals resulting from isolated 1-octene incorporation i.e. EEOEE comonomer sequences, were observed. Isolated 1-octene incorporation was quantified using the integral of the signal at 38.3 ppm. This integral is assigned to the unresolved signals corresponding to both *B6 and *bB6B6 sites of isolated (EEOEE) and isolated double non-consecutive (EEOEOEE) 1-octene sequences respectively. To compensate for the influence of the two *bB6B6 sites the integral of the bbB6B6 site at 24.6 ppm is used:

O=I.sub.*B6+*bB6B6−2*I.sub.bbB6B6

[0169] Characteristic signals resulting from consecutive 1-octene incorporation, i.e. EEOOEE comonomer sequences, were also observed. Such consecutive 1-octene incorporation was quantified using the integral of the signal at 40.4 ppm assigned to the aaB6B6 sites accounting for the number of reporting sites per comonomer:

OO=2*I.sub.aaB6B6

[0170] Characteristic signals resulting from isolated non-consecutive 1-octene incorporation, i.e. EEOEOEE comonomer sequences, were also observed. Such isolated non-consecutive 1 -octene incorporation was quantified using the integral of the signal at 24.6 ppm assigned to the bbB6B6 sites accounting for the number of reporting sites per comonomer:

OEO=2*I.sub.bbB6B6

[0171] Characteristic signals resulting from isolated triple-consecutive 1-octene incorporation, i.e. EEOOOEE comonomer sequences, were also observed. Such isolated triple-consecutive 1-octene incorporation was quantified using the integral of the signal at 41.2 ppm assigned to the aagB6B6B6 sites accounting for the number of reporting sites per comonomer:

OOO=3/2*I.sub.aagB6B6B6

[0172] With no other signals indicative of other comonomer sequences observed the total 1-octene comonomer content was calculated based solely on the amount of isolated (EEOEE), isolated double-consecutive (EEOOEE), isolated non-consecutive (EEOEOEE) and isolated triple-consecutive (EE000EE) 1-octene comonomer sequences:

O.sub.total=O+OO+OEO+OOO

[0173] Characteristic signals resulting from saturated end-groups were observed. Such saturated end-groups were quantified using the average integral of the two resolved signals at 22.9 and 32.23 ppm. The 22.84 ppm integral is assigned to the unresolved signals corresponding to both 2B6 and 2S sites of 1-octene and the saturated chain end respectively. The 32.2 ppm integral is assigned to the unresolved signals corresponding to both 3B6 and 3S sites of 1-octene and the saturated chain end respectively. To compensate for the influence of the 2B6 and 3B6 1-octene sites the total 1-octene content is used:

S=(½)*(I.sub.2S+2B6+I.sub.3S+3B6−2O.sub.total)

[0174] The ethylene comonomer content was quantified using the integral of the bulk methylene (bulk) signals at 30.00 ppm. This integral included the g and 4B6 sites from 1-octene as well as the d+sites. The total ethylene comonomer content was calculated based on the bulk integral and compensating for the observed 1-octene sequences and end-groups:

E.sub.total=(½)[I.sub.bulk+2*O+1*OO+3*OEO+0*OOO+3*S]

[0175] It should be noted that compensation of the bulk integral for the presence of isolated triple-incorporation (EEOOOEE) 1-octene sequences is not required as the number of under and over accounted ethylene units is equal.

[0176] The total mole fraction of 1-octene in the polymer was then calculated as:

fO=O.sub.total/(E.sub.total+.sub.total)

[0177] The total comonomer incorporation of 1-octene in weight percent was calculated from the mole fraction in the standard manner:

O[wt %]=100*(fO*112.21)/((fO*112.21)+((1−fO)*28.05))

[0178] Further information can be found in the following references: [0179] Klimke, K., Parkinson, M., Piel, C., Kaminsky, W., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2006; 207:382. [0180] Parkinson, M., Klimke, K., Spiess, H. W., Wilhelm, M., Macromol. Chem. Phys. 2007; 208:2128 [0181] NMR Spectroscopy of Polymers: Innovative Strategies for Complex Macromolecules, Chapter 24, 401 (2011) [0182] Pollard, M., Klimke, K., Graf, R., Spiess, H. W., Wilhelm, M., Sperber, O., Piel, C., Kaminsky, W., Macromolecules 2004; 37:813. [0183] Filip, X., Tripon, C., Filip, C., J. Mag. Resn. 2005, 176, 239 [0184] Griffin, J. M., Tripon, C., Samoson, A., Filip, C., and Brown, S. P., Mag. Res. in Chem. 2007 45, S1, S198 [0185] Castignolles, P., Graf, R., Parkinson, M., Wilhelm, M., Gaborieau, M., Polymer 50 (2009) 2373 [0186] Zhou, Z., Kuemmerle, R., Qiu, X., Redwine, D., Cong, R., Taha, A., Baugh, D. Winniford, B., J. Mag. Reson. 187 (2007) 225 [0187] Busico, V., Carbonniere, P., Cipullo, R., Pellecchia, R., Severn, J., Talarico, G., Macromol. Rapid Commun. 2007, 28, 1128 [0188] J. Randall, Macromol. Sci., Rev. Macromol. Chem. Phys. 1989, C29, 201 [0189] Qiu, X., Redwine, D., Gobbi, G., Nuamthanom, A., Rinaldi, P., Macromolecules 2007, 40, 6879 [0190] Liu, W., Rinaldi, P., McIntosh, L., Quirk, P., Macromolecules 2001, 34, 4757

d) Unsaturation

[0191] Quantitative nuclear-magnetic resonance (NMR) spectroscopy was used to quantify the content of unsaturated groups present in the polymers.

[0192] Quantitative .sup.1H NMR spectra recorded in the solution-state using a Bruker Avance III 400 NMR spectrometer operating at 400.15 MHz. All spectra were recorded using a .sup.13C optimised 10 mm selective excitation probehead at 125° C. using nitrogen gas for all pneumatics. Approximately 200 mg of material was dissolved in 1,2-tetrachloroethane-d.sub.2 (TCE-d.sub.2) using approximately 3 mg of Hostanox 03 (CAS 32509-66-3) as stabiliser. Standard single-pulse excitation was employed utilising a 30 degree pulse, a relaxation delay of 10 s and 10 Hz sample rotation. A total of 128 transients were acquired per spectra using 4 dummy scans. This setup was chosen primarily for the high resolution needed for unsaturation quantification and stability of the vinylidene groups. All chemical shifts were indirectly referenced to TMS at 0.00 ppm using the signal resulting from the residual protonated solvent at 5.95 ppm.

[0193] Characteristic signals corresponding to the presence of terminal aliphatic vinyl groups (R—CH═CH.sub.2) were observed and the amount quantified using the integral of the two coupled inequivalent terminal CH.sub.2 protons (Va and Vb) at 4.95, 4.98 and 5.00 and 5.05 ppm accounting for the number of reporting sites per functional group:

Nvinyl=IVab/2

[0194] When characteristic signals corresponding to the presence of internal vinylidene groups (RR′C═CH.sub.2) were observed the amount is quantified using the integral of the two CH.sub.2 protons (D) at 4.74 ppm accounting for the number of reporting sites per functional group:

Nvinylidene=ID/2

[0195] When characteristic signals corresponding to the presence of internal cis-vinylene groups (E-RCH═CHR′), or related structure, were observed the amount is quantified using the integral of the two CH protons (C) at 5.39 ppm accounting for the number of reporting sites per functional group:

Ncis=IC/2

[0196] When characteristic signals corresponding to the presence of internal trans-vinylene groups (Z-RCH═CHR′) were observed the amount is quantified using the integral of the two CH protons (T) at 5.45 ppm accounting for the number of reporting sites per functional group:

Ntrans=IT/2

[0197] When characteristic signals corresponding to the presence of internal trisubstituted-vinylene groups (RCH═CHR′R″), or related structure, were observed the amount is quantified using the integral of the CH proton (Tris) at 5.14 ppm accounting for the number of reporting sites per functional group:

Ntris=ITris

[0198] The Hostanox 03 stabiliser was quantified using the integral of multiplet from the aromatic protons (A) at 6.92, 6.91, 6.69 and at 6.89 ppm and accounting for the number of reporting sites per molecule:

H=IA/4

[0199] As is typical for unsaturation quantification in polyolefins the amount of unsaturation was determined with respect to total carbon atoms, even though quantified by .sup.1H NMR spectroscopy. This allows direct comparison to other microstructure quantities derived directly from .sup.13C NMR spectroscopy.

[0200] The total amount of carbon atoms was calculated from integral of the bulk aliphatic signal between 2.85 and −1.00 ppm with compensation for the methyl signals from the stabiliser and carbon atoms relating to unsaturated functionality not included by this region:

NCtotal =(Ibulk−42*H)/2+2*Nvinyl+2*Nvinylidene+2*Ncis+2*Ntrans+2*Ntris

[0201] The content of unsaturated groups (U) was calculated as the number of unsaturated groups in the polymer per thousand total carbons (kCHn):

U=1000*N/NCtotal

[0202] The total amount of unsaturated group was calculated as the sum of the individual observed unsaturated groups and thus also reported with respect per thousand total carbons:

Utotal =Uvinyl+Uvinylidene+Ucis+Utrans+Utris

[0203] The relative content of a specific unsaturated group (U) is reported as the fraction or percentage of a given unsaturated group with respect to the total amount of unsaturated groups:

[U]=Ux/Utotal

[0204] Further information can be found in the following references: [0205] He, Y., Qiu, X, and Zhou, Z., Mag. Res. Chem. 2010, 48, 537-542. [0206] Busico, V. et. al. Macromolecules, 2005, 38 (16), 6988-6996

e) Determination of the Molecular Weight Averages, Molecular Weight Distribution

[0207] Molecular weight averages (Mz, Mw and Mn), Molecular weight distribution (MWD) and its broadness, described by polydispersity index, PDI=Mw/Mn (wherein Mn is the number average molecular weight and Mw 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:

[00003]$\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}$$\begin{array}{cc}{M}_w=\frac{{.Math.}_{i=1}^N\left(A_i\times M_i\right)}{{.Math.}_{i=1}^N{A}_i}& \left(2\right)\end{array}$$\begin{array}{cc}{M}_z=\frac{{.Math.}_{i=1}^N\left(A_i\times M_i^2\right)}{{.Math.}_{i=1}^N\left(A_i/M_i\right)}& \left(3\right)\end{array}$

[0208] 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.

[0209] A high temperature GPC instrument, equipped with a multiple band infrared detector model IR5 (PolymerChar, Valencia, Spain), 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. at a constant flow rate of 1 mL/min. 200 μL of sample solution was injected per analysis. Data collection was performed by using PolymerChar GPC-one software.

[0210] 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 11 500 kg/mol. The PS standards were dissolved at room temperature over several hours. The conversion of the polystyrene peak molecular weight to polyethylene 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, a.sub.PS=0.655

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

[0211] A third order polynomial fit was used to fit the calibration data.

[0212] All samples were prepared in the concentration range of 0.5 to 1 mg/ml and dissolved at 160° C. for 3 hours under continuous gentle shaking.

2. Polymerization Catalysts

[0213] Catalyst A is (Phenyl)(cyclohexyl)methylene(cyclopentadienyl)(2,7-di-tert-butylfluoren-9-yl)hafnium dimethyl), produced according to WO2018/108918.

[0214] Catalyst B is (Phenyl)(3-buten-1-yl)methylene(cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dimethyl), produced according to WO2018/178152.

[0215] As cocatalyst N,N-Dimethylanilinium Tetrakis(pentafluorophenyl)borate (AB) (CAS 118612-00-3) was used, commercially available from Boulder.

3. Polymerization of ethylene-1-octene copolymers

[0216] Polymerization was done with Borealis proprietor Borceed™ solution polymerization technology, in the presence of metallocene catalyst (phenyl)(cyclohexyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) hafnium dimethyl (Catalyst A) or (Phenyl)(3-buten-1-yl)methylene(cyclopentadienyl) (2,7-di-tert-butylfluoren-9-yl) hafnium dimethyl) (Catalyst B) and N,N-Dimethylanilinium Tetrakis(pentafluorophenyl)borate (AB) (CAS 118612-00-3) as cocatalyst.

[0217] The polymerization conditions were selected in such a way that the reacting system is one liquid phase (temperature T between 120 and 220° C.; pressure between 50 to 300 bar).

[0218] Inventive examples IE1 to IE9 were produced using Catalyst A.

[0219] Inventive examples IE10 to IE12 were produced using Catalyst B.

[0220] Comparative example CE1 is Engage 8540 (commercially available from Dow), CE2 is Exact 9361 (commercially available from Exxon), CE3 is Engage 7467 (commercially available from Dow), and CE4 is LC170 (commercially available from LG Chem).

4. Results

[0221] The results are given below.

TABLE-US-00001 TABLE 1 Process conditions and reactivity T, C8/C2 C8/C2 C8 Example ° C. Feed Polymer reactivity IE1 150.9 1.72 0.61 0.36 IE2 159.5 1.47 0.52 0.35 IE3 181 0.45 0.18 0.41 IE4 185 0.41 0.20 0.48 IE5 191 0.38 0.20 0.52 IE6 162 1.01 0.35 0.35

TABLE-US-00002 TABLE 2 Properties of Inventive Examples IE1 to IE12 and CE1 to CE4 octene, Density, MFR2, MFR10/ Example wt. % kg m.sup.−3 g/10 min MFR2 Mw/Mn IE1 39.1 860.3 0.9 8.8 2.8 IE2 33.8 869.0 1.4 8.5 2.7 IE3 16.1 902.3 0.9 10.2 2.7 IE4 16.4 902.3 2.4 9.4 2.9 IE5 16.7 902.9 9.7 8.8 3.1 IE6 26.8 882.8 0.8 9.4 2.8 IE7 17.02 901.9 29.7 7.2 2.54 IE8 26.90 881.7 23.4 7.3 2.46 IE9 31.65 870.6 6.6 7.9 2.54 IE10 16.93 900.9 10.2 8.0 2.62 IE11 25.46 884.1 29.60 7.3 2.52 IE12 32.56 869.9 10.8 7.5 2.45 CE1 13.4 902.0 1.0 9.4 2.2 CE2 27.3 864.0 3.4 7.4 1.9 CE3 30.6 862.0 1.2 7.4 2.7 CE4 34.1 868.8 1.1 8.8 2.7

TABLE-US-00003 TABLE 3 Unsaturation types of Inventive Examples IE1 to IE12 and CE1 to CE4 Total Trisub- unsaturation Vinylidene Vinyl stituted Vinylene units/ units/ units/ units/ units/ Example 100k C 100k C 100k C 100k C 100k C IE1 52.6 14.5 5.4 23.7 9.0 IE2 63.7 16.2 6.1 29.3 12.3 IE3 65.6 15.6 6.7 25.4 17.8 IE4 72.4 18.5 7.9 28.3 17.8 IE5 85.6 22.8 9.2 31.7 21.8 IE6 63.2 15.4 6.3 27.0 14.4 IE7 73.6 22.7 10.6 26.0 14.3 IE8 104.9 29.9 14.9 40.4 19.6 IE9 81.3 23.0 13.2 34.4 10.7 IE10 85.4 21.0 10.1 34.9 19.4 IE11 118.2 31.4 16.2 49.4 21.2 IE12 105.4 26.9 18.7 43.8 16.0 CE1 30.4 10.2 3.1 6.8 10.3 CE2 37.9 14.6 1.7 4.0 17.6 CE3 5.2 2.0 0.0 0.0 3.2 CE4 29.8 2.4 3.0 7.8 16.6

TABLE-US-00004 TABLE 4 Unsaturation levels of Inventive Examples IE1 to IE12 and CE1 to CE4 Trisub- Vinylidene + Vinylidene, Vinyl, stituted, Vinylene, vinyl, Example % % % % % IE1 27.6 10.3 45.1 17.1 37.9 IE2 25.4 9.6 46.0 19.3 34.9 IE3 23.8 10.2 38.7 27.1 34.0 IE4 25.6 10.9 39.1 24.6 36.5 IE5 26.6 10.7 37.0 25.5 37.4 IE6 24.4 10.0 42.7 22.8 34.3 IE7 30.8 14.4 35.3 19.4 45.2 IE8 28.5 14.2 38.5 18.7 42.7 IE9 28.3 16.2 42.3 13.2 44.5 IE10 24.6 11.8 40.9 22.7 36.4 IE11 26.6 13.7 41.8 17.9 40.3 IE12 25.5 17.7 41.6 15.2 43.3 CE1 33.5 10.2 22.4 33.9 43.7 CE2 38.5 4.5 10.5 46.4 43.0 CE3 38.5 0.0 0.0 61.5 38.5 CE4 8.0 10.1 26.2 55.7 18.1

[0222] As can be seen from the tables above, the inventive copolymers show improved unsaturation levels, Mw/Mn and MFR10/MFR2 ratio.