BIMODAL POLY(ETHYLENE-CO-1-ALKENE) COPOLYMER

Abstract

A bimodal poly(ethylene-co-1-alkene) copolymer comprising a higher molecular weight poly(ethylene-co-1-alkene) copolymer component and a lower molecular weight poly(ethylene-co-1-alkene) copolymer component. The copolymer is characterized by a unique combination of features comprising, or reflected in, its density; molecular weight distributions; component weight fraction amount; and viscoelastic properties; and at least one of environmental stress-cracking resistance and resin swell. Additional inventive embodiments include a method of making the copolymer, a formulation comprising the copolymer and at least one additive that is different than the copolymer, a method of making a manufactured article from the copolymer or formulation; the manufactured article made thereby, and use of the manufactured article.

Claims

1. A bimodal poly(ethylene-co-1-alkene) copolymer comprising a higher molecular weight poly(ethylene-co-1-alkene) copolymer component (HMW copolymer component) and a lower molecular weight poly(ethylene-co-1-alkene) copolymer component (LMW copolymer component), the copolymer being characterized by a combination of features comprising each of features (a) to (e) and features (f1) and (g): (a) a density greater than 0.955 gram per cubic centimeter (g/cm.sup.3) measured according to ASTM D792-13 (Method B, 2-propanol); (b) a first molecular weight distribution that is a ratio of M.sub.w/M.sub.n from 13 to 25, wherein M.sub.w is weight-average molecular weight and M.sub.n is number-average molecular weight, both measured by Gel Permeation Chromatography (GPC); (c) a second molecular weight distribution that is a ratio of M.sub.z/M.sub.w greater than 8, wherein M.sub.z is z-average molecular weight and M.sub.w is weight-average molecular weight, both measured by GPC; (d) a component weight fraction amount wherein the HMW copolymer component is less than 28 weight percent (wt %) of the combined weight of the HMW and LMW copolymer components; and (e) a high load melt index (HLMI or I.sub.21) from 20 to 45 grams per 10 minutes (g/10 min.) measured according to ASTM D1238-13 (190° C., 21.6 kg); and (f1) an environmental stress-cracking resistance (ESCR) (10% Igepal, F50) of greater than or equal to 150 hours, measured according to ASTM D1693-15, Method B; and (g) a resin swell t1000 of greater than 7.7 seconds, measured according to the Resin Swell t1000 Test Method.

2. A bimodal poly(ethylene-co-1-alkene) copolymer comprising a higher molecular weight poly(ethylene-co-1-alkene) copolymer component (HMW copolymer component) and a lower molecular weight poly(ethylene-co-1-alkene) copolymer component (LMW copolymer component), the copolymer being characterized by a combination of features comprising each of features (a) to (e) and feature (f2) and, optionally feature (g): (a) a density greater than 0.955 gram per cubic centimeter (g/cm.sup.3) measured according to ASTM D792-13 (Method B, 2-propanol); (b) a first molecular weight distribution that is a ratio of M.sub.w/M.sub.n from 13 to 25, wherein M.sub.w is weight-average molecular weight and M.sub.n is number-average molecular weight, both measured by Gel Permeation Chromatography (GPC); (c) a second molecular weight distribution that is a ratio of M.sub.z/M.sub.w greater than 8, wherein M.sub.z is z-average molecular weight and M.sub.w is weight-average molecular weight, both measured by GPC; (d) a component weight fraction amount wherein the HMW copolymer component is less than 28 weight percent (wt %) of the combined weight of the HMW and LMW copolymer components; and (e) a high load melt index (HLMI or I.sub.21) from 20 to 45 grams per 10 minutes (g/10 min.) measured according to ASTM D1238-13 (190° C., 21.6 kg); and (f2) an environmental stress-cracking resistance in hours as a function of melt flow ratio, wherein the function is defined by Equation 1: ESCR (10% Igepal, F50)>(10*MFR5*1 hour)−150 hours (Eq. 1), wherein > means greater than; * means multiplication; ESCR (10% Igepal, F50) is the number of hours to failure measured according to ASTM D1693-15, Method B; and MFR5 is a ratio of the (e) HLMI divided by a melt index I.sub.5 expressed in g/10 min. measured according to ASTM D1238-13 (190° C., 5.0 kg); and, optionally (g) a resin swell t1000 of greater than 7.7 seconds, measured according to the Resin Swell t1000 Test Method.

3. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 1 further characterized by any one of refined features (a) to (e), (f1) or (f2), respectively, and (g): (a) the density is from 0.956 to 0.962 g/cm.sup.3; (b) the M.sub.w/M.sub.n is from 14 to 21; (c) the M.sub.z/M.sub.w is from 11 to 15; (d) the HMW copolymer component weight fraction amount is from 17 to 27 wt %; (e) the HLMI is from 25 to 41; (f1) an ESCR (10% Igepal, F50) of from 150 to 500 hours or (f2) the ESCR (10% Igepal, F50) is a function of the MFR5 as defined by Equation 1a: ESCR (10% Igepal, F50)>(10*MFR5*1 hour)−100 hours (Eq. 1a); and (g) the resin swell t1000 is from 7.7 to 9.0 seconds.

4. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 1 further characterized by any one of features (h) to (q): (h) M.sub.w from 280,000 to 360,000 grams per mole (g/mol); (i) M.sub.n from 15,000 to 23,000 grams g/mol; (j) M.sub.z from 3,000,000 to 4,800,000 g/mol; (k) an MFR5 from 16 to 27; (l) feature (g) in combination with (f1); (m) a melt index I.sub.5 from 0.5 to 2.0 g/10 minutes; (n) feature (g) in combination with feature (f2); (o) feature (g) in combination with feature (f1) and (f2), respectively; (p) a combination of any seven of features (h) to (o); and (q) a combination of each of features (h) to (o).

5. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 1 further characterized by any one of features (r) to (w): (r) the LMW copolymer component has a M.sub.w from 45,000 to 55,000 g/mol; (s) the LMW copolymer component has a M.sub.n from 13,000 to 20,000 g/mol; (t) the LMW copolymer component has a M.sub.z from 85,000 to 115,000 g/mol; (u) the LMW copolymer component has a M.sub.w/M.sub.n ratio from 2.5 to 3.3; (v) any three of features (r) to (u); (w) each of features (r) to (u).

6. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 1 further characterized by any one of features (x) to (ac): (x) the HMW copolymer component has a M.sub.w from 1,000,000 to 1,400,000 g/mol; (y) the HMW copolymer component has a M.sub.n from 220,000 to 320,000 g/mol; (z) the HMW copolymer component has a M.sub.z from 2,000,000 to 4,700,000 g/mol; (aa) the HMW copolymer component has a M.sub.w/M.sub.n ratio from 4.0 to 4.4; (ab) any three of features (x) to (aa); and (ac) each of features (x) to (aa).

7. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 1 further characterized by feature (ad) a melt strength of greater than 7.0 centinewtons (cN).

8. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 1 wherein the 1-alkene is 1-hexene and the bimodal poly(ethylene-co-1-alkene) copolymer is bimodal poly(ethylene-co-1-hexene) copolymer.

9. A method of making the bimodal poly(ethylene-co-1-alkene) copolymer of claim 1, the method comprising contacting ethylene and 1-alkene with a bimodal catalyst system in a single polymerization reactor under effective polymerization conditions to give the bimodal poly(ethylene-co-1-alkene) copolymer; wherein the bimodal catalyst system consists essentially of a metallocene catalyst, a single-site non-metallocene catalyst that is a bis((alkyl-substituted phenylamido)ethyl)amine catalyst, optionally a host material, and optionally an activator; wherein the host material, when present, is selected from at least one of an inert hydrocarbon liquid and a solid support; wherein the metallocene catalyst is an activation reaction product of contacting an activator with a metal-ligand complex of formula (R.sub.1-2Cp)((alkyl).sub.1-3Indenyl)MX.sub.2, wherein R is hydrogen, methyl, or ethyl; each alkyl independently is a (C.sub.1-C.sub.4)alkyl; M is titanium, zirconium, or hafnium; and each X is independently a halide, a (C.sub.1 to C.sub.20)alkyl, a (C.sub.7 to C.sub.20)aralkyl, a (C.sub.1 to C.sub.6)alkyl-substituted (C.sub.6 to C.sub.12)aryl, or a (C.sub.1 to C.sub.6)alkyl-substituted benzyl; and wherein the bis((alkyl-substituted phenylamido)ethyl)amine catalyst is an activation reaction product of contacting an activator with a bis((alkyl-substituted phenylamido)ethyl)amine ZrR.sup.1.sub.2, wherein each R.sup.1 is independently selected from F, Cl, Br, I, benzyl, —CH.sub.2Si(CH.sub.3).sub.3, a (C.sub.1-C.sub.5)alkyl, and a (C.sub.2-C.sub.5)alkenyl.

10. The method of claim 9 having at least one of the following features: the single polymerization reactor is a single gas phase polymerization reactor; and the metal-ligand complex is of formula (I): ##STR00004## wherein R, M, and X are as defined therein.

11. A formulation comprising the bimodal poly(ethylene-co-1-alkene) copolymer of claim 1 and at least one additive that is different than the copolymer.

12. A method of making a manufactured article, the method comprising extruding-melt-blowing the bimodal poly(ethylene-co-1-alkene) copolymer of claim 1, under effective conditions so as to make the manufactured article.

13. The manufactured article made by the method of claim 12.

14. Use of the manufactured article of claim 13 in storing or transporting a material in need of storing or transporting.

15. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 2 further characterized by any one of refined features (a) to (e), (f1) or (f2), respectively, and (g): (a) the density is from 0.956 to 0.962 g/cm.sup.3; (b) the M.sub.w/M.sub.n is from 14 to 21; (c) the M.sub.z/M.sub.w is from 11 to 15; (d) the HMW copolymer component weight fraction amount is from 17 to 27 wt %; (e) the HLMI is from 25 to 41; (f1) an ESCR (10% Igepal, F50) of from 150 to 500 hours or (f2) the ESCR (10% Igepal, F50) is a function of the MFR5 as defined by Equation 1a: ESCR (10% Igepal, F50)>(10*MFR5*1 hour)−100 hours (Eq. 1a); and (g) the resin swell t1000 is from 7.7 to 9.0 seconds.

16. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 2 further characterized by any one of features (h) to (q): (h) M.sub.w from 280,000 to 360,000 grams per mole (g/mol); (i) M.sub.n from 15,000 to 23,000 grams g/mol; (j) M.sub.z from 3,000,000 to 4,800,000 g/mol; (k) an MFR5 from 16 to 27; (l) feature (g) in combination with (f1); (m) a melt index I.sub.5 from 0.5 to 2.0 g/10 minutes; (n) feature (g) in combination with feature (f2); (o) feature (g) in combination with feature (f1) and (f2), respectively; (p) a combination of any seven of features (h) to (o); and (q) a combination of each of features (h) to (o).

17. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 2 further characterized by any one of features (r) to (w): (r) the LMW copolymer component has a M.sub.w from 45,000 to 55,000 g/mol; (s) the LMW copolymer component has a M.sub.n from 13,000 to 20,000 g/mol; (t) the LMW copolymer component has a M.sub.z from 85,000 to 115,000 g/mol; (u) the LMW copolymer component has a M.sub.w/M.sub.n ratio from 2.5 to 3.3; (v) any three of features (r) to (u); (w) each of features (r) to (u).

18. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 2 further characterized by any one of features (x) to (ac): (x) the HMW copolymer component has a M.sub.w from 1,000,000 to 1,400,000 g/mol; (y) the HMW copolymer component has a M.sub.n from 220,000 to 320,000 g/mol; (z) the HMW copolymer component has a M.sub.z from 2,000,000 to 4,700,000 g/mol; (aa) the HMW copolymer component has a M.sub.w/M.sub.n ratio from 4.0 to 4.4; (ab) any three of features (x) to (aa); and (ac) each of features (x) to (aa).

19. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 2 further characterized by feature (ad) a melt strength of greater than 7.0 centinewtons (cN).

20. The bimodal poly(ethylene-co-1-alkene) copolymer of claim 2 wherein the 1-alkene is 1-hexene and the bimodal poly(ethylene-co-1-alkene) copolymer is bimodal poly(ethylene-co-1-hexene) copolymer

Description

EXAMPLES

[0065] Deconvoluting Test Method: Fit a GPC chromatogram of a bimodal polyethylene into a high molecular weight (HMW) component fraction and low molecular weight (LMW) component fraction using a Flory Distribution that was broadened with a normal distribution function as follows. For the log M axis, establish 501 equally-spaced Log(M) indices, spaced by 0.01, from Log(M) 2 and Log(M) 7, which range represents molecular weight from 100 to 10,000,000 grams per mole. Log is the logarithm function to the base 10. At any given Log(M), the population of the Flory distribution is in the form of the following equation:

[00001]${\mathrm{dW}}_f={\left(\frac{2}{M_w}\right)}^3\left(\frac{M_w}{0.868588961964}\right)M^2{e}^{\left(-2M/M_w\right)},$

wherein M.sub.w is the weight-average molecular weight of the Flory distribution; M is the specific x-axis molecular weight point, (10{circumflex over ( )}[Log(M)]); and dW.sub.f is a weight fraction distribution of the population of the Flory distribution. Broaden the Flory distribution weight fraction, dW.sub.f, at each 0.01 equally-spaced log(M) index according to a normal distribution function, of width expressed in Log(M), σ; and current M index expressed as Log(M), μ.

[00002]$f_{\left(\mathrm{LogM},\mu ,\sigma \right)}=\frac{e^{-\frac{{\left(\mathrm{LogM}-\mu \right)}^2}{2{\sigma }^2}}}{\sigma \sqrt{2\pi }}.$

Before and after the spreading function has been applied, the area of the distribution (dW.sub.f/d Log M) as a function of Log(M) is normalized to 1. Express two weight-fraction distributions, dW.sub.f-HMW and dW.sub.f-LMW, for the HMW copolymer component fraction and the LMW copolymer component fraction, respectively, with two unique M.sub.w target values, M.sub.w-HMW and M.sub.w-LMW, respectively, and with overall component compositions A.sub.HMW and A.sub.LMW, respectively. Both distributions were broadened with independent widths, σ(i.e., σ.sub.HMW and σ.sub.LMW, respectively). The two distributions were summed as follows: dW.sub.f=A.sub.HMW dW.sub.fHMW+A.sub.LMW dW.sub.fLMW, wherein A.sub.HMW+A.sub.LMW=1. Interpolate the weight fraction result of the measured (from conventional GPC) GPC molecular weight distribution along the 501 log M indices using a 2.sup.nd-order polynomial. Use Microsoft Excel™ 2010 Solver to minimize the sum of squares of residuals for the equally-spaces range of 501 Log M indices between the interpolated chromatographically determined molecular weight distribution and the three broadened Flory distribution components (σ.sub.HMW and σ.sub.LMW), weighted with their respective component compositions, A.sub.HMW and A.sub.LMW. The iteration starting values for the components are as follows: Component 1: Mw=30,000, σ=0.300, and A=0.500; and Component 2: Mw=250,000, σ=0.300, and A=0.500. The bounds for components σ.sub.HMW and σ.sub.LMW are constrained such that σ>0.001, yielding an M.sub.w/M.sub.n of approximately 2.00 and σ<0.500. The composition, A, is constrained between 0.000 and 1.000. The M.sub.w is constrained between 2,500 and 2,000,000. Use the “GRG Nonlinear” engine in Excel Solver™ and set precision at 0.00001 and convergence at 0.0001. Obtain the solutions after convergence (in all cases shown, the solution converged within 60 iterations).

[0066] Density is measured according to ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, e.g., in liquid 2-propanol). Report results in units of grams per cubic centimeter (g/cm.sup.3).

[0067] Environmental Stress-Cracking Resistance (ESCR) Test Method: ESCR measurements are conducted according to ASTM D1693-15, Standard Test Method for Environmental Stress-Cracking of Ethylene Plastics, Method B and ESCR (10% Igepal, F50) is the number of hours to failure of a bent, notched, compression-molded test specimen that is immersed in a solution of 10 weight percent Igepal in water at a temperature of 50° C.

[0068] Gel permeation chromatography (GPC) Test Method: Use a PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with an internal IR5 infra-red detector (IR5, measurement channel). Set temperatures of the autosampler oven compartment at 160° C. and column compartment at 150° C. Use a column set of four Agilent “Mixed A” 30 cm 20-micron linear mixed-bed columns; solvent is 1,2,4 trichlorobenzene (TCB) that contains 200 ppm of butylated hydroxytoluene (BHT) sparged with nitrogen. Injection volume is 200 microliters. Set flow rate to 1.0 milliliter/minute. Calibrate the column set with at least 20 narrow molecular weight distribution polystyrene (PS) standards (Agilent Technologies) arranged in six “cocktail” mixtures with approximately a decade of separation between individual molecular weights with molecular weights ranging from 580 to 8,400,000 in each vial. Convert the PS standard peak molecular weights to polyethylene molecular weights using the method described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968) and equation 1: (M.sub.polyethylene=A×(M.sub.polystyrene).sup.B (EQ1), wherein M.sub.polyethylene is molecular weight of polyethylene, M.sub.polystyrene is molecular weight of polystyrene, A=0.4315, × indicates multiplication, and B=1.0; where MPE=MPS×Q, where Q ranges between 0.39 to 0.44 to correct for column resolution and band-broadening effects) based on a linear homopolymer polyethylene molecular weight standard of approximately 120,000 and a polydispersity of approximately 3, which is measured independently by light scattering for absolute molecular weight. Dissolve samples at 2 mg/mL in TCB solvent at 160° C. for 2 hours under low-speed shaking. Generate a baseline-subtracted infra-red (IR) chromatogram at each equally-spaced data collection point (i), and obtain polyethylene equivalent molecular weight from a narrow standard calibration curve for each point (i) from EQ1. Calculate number-average molecular weight (M.sub.n or M.sub.n(GPC)), weight-average molecular weight (M.sub.w or M.sub.w(GPC)), and z-average molecular weight (M.sub.z or M.sub.z(GPC)) based on GPC results using the internal IR5 detector (measurement channel) with PolymerChar GPCOne™ software and equations 2 to 4, respectively: equation 2:

[00003]$\begin{array}{cc}{\mathrm{Mn}}_{\left(\mathrm{GPC}\right)}=\frac{\stackrel{i}{.Math.}{\mathrm{IR}}_i}{\stackrel{i}{.Math.}\left({\mathrm{IR}}_i/M_{{\mathrm{polyethylene}}_i}\right)};& \left(\mathrm{EQ2}\right)\end{array}$

equation 3:

[00004]$\begin{array}{cc}{\mathrm{Mw}}_{\mathrm{GPC})}=\frac{\stackrel{i}{.Math.}\left({\mathrm{IR}}_i/M_{{\mathrm{polyethylene}}_i}\right)}{\stackrel{i}{.Math.}{\mathrm{IR}}_i};& \left(\mathrm{EQ3}\right)\end{array}$

and equation 4:

[00005]$\begin{array}{cc}{\mathrm{Mz}}_{\left(\mathrm{GPC}\right)}=\frac{\stackrel{i}{.Math.}\left({\mathrm{IR}}_i*M_{{\mathrm{polyethylene}}_i}^2\right)}{\stackrel{i}{.Math.}\left({\mathrm{IR}}_i*M_{{\mathrm{polyethylene}}_i}\right)}.& \left(\mathrm{EQ4}\right)\end{array}$

Monitor effective flow rate over time using decane as a nominal flow rate marker during sample runs. Look for deviations from the nominal decane flow rate obtained during narrow standards calibration runs. If necessary, adjust the effective flow rate of decane so as to stay within ±2% of the nominal flow rate of decane as calculated according to equation 5: Flow rate(effective)=Flow rate(nominal)*(RV.sub.(FM Calculated)/RV.sub.(FM Sample) (EQ5), wherein Flow rate(effective) is the effective flow rate of decane, Flowrate(nominal) is the nominal flow rate of decane, RV.sub.(FM Calibrated) is retention volume of flow rate marker decane calculated for column calibration run using narrow standards, RV.sub.(FM Sample) is retention volume of flow rate marker decane calculated from sample run, * indicates mathematical multiplication, and/indicates mathematical division. Discard any molecular weight data from a sample run with a decane flow rate deviation more than ±2%.

[0069] High Load Melt Index (HLMI) I.sub.21 Test Method: use ASTM D1238-13, Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Platometer, using conditions of 190° C./21.6 kilograms (kg). Report results in units of grams eluted per 10 minutes (g/10 min.).

[0070] Melt Index (“I.sub.2”) Test Method: for ethylene-based (co)polymer is measured according to ASTM D1238-13, using conditions of 190° C./2.16 kg, formerly known as “Condition E”.

[0071] Melt Index I.sub.5 (“I.sub.5”) Test Method: use ASTM D1238-13, using conditions of 190° C./5.0 kg. Report results in units of grams eluted per 10 minutes (g/10 min.).

[0072] Melt Flow Ratio MFR2: (“I.sub.21/I.sub.2”) Test Method: calculated by dividing the value from the HLMI I.sub.21 Test Method by the value from the Melt Index I.sub.2 Test Method.

[0073] Melt Flow Ratio MFR5: (“I.sub.21/I.sub.5”) Test Method: calculated by dividing the value from the HLMI I.sub.21 Test Method by the value from the Melt Index I.sub.5 Test Method.

[0074] Melt Strength Test Method: Carried out Rheotens (Göttfert) melt strength experiments at 190° C. Produced a melt by a Göttfert Rheotester 2000 capillary rheometer with a flat, 30/2 die at a shear rate of 38.2 s−1. Filled the barrel of the rheometer in less than one minute. Waited 10 minutes to ensure proper melting. Varied take-up speed of the Rheotens wheels with a constant acceleration of 2.4 mm/s.sup.2. Monitored tension in the drawn strand over time until the strand broke. Calculated melt strength by averaging the flat range of tension.

[0075] Resin Swell t1000 Test Method: Characterized resin swell in terms of extrudate swell. In this approach determined the time required by an extruded polymer strand to travel a pre-determined distance of 23 cm. The more the resin swells, the slower the free end of the strand travels, and the longer it takes to cover the 23 cm distance. Used a 12 mm barrel Göttfert Rheograph equipped with a 10 L/D capillary die for measurements. Carried out measurements at 190° C. at a fixed shear rate of 1000 sec-1. Reported the resin swell as t1000 value.

[0076] Antioxidant: 1. Pentaerythritol tetrakis(3-(3,5-di(1′,1′-dimethylethyl)-4-hydroxyphenyl)propionate); obtained as IRGANOX 1010 from BASF.

[0077] Antioxidant 2. Tris(2,4-di(1′,1′-dimethylethyl)-phenyl)phosphite. Obtained as IRGAFOS 168 from BASF.

[0078] CA-300: a continuity additive available from Univation Technologies, LLC.

[0079] Catalyst Neutralizer: 1. Calcium stearate.

[0080] 1-Alkene Comonomer: 1-hexene or H.sub.2C═C(H)(CH.sub.2).sub.3CH.sub.3.

[0081] Ethylene (“C.sub.2”): CH.sub.2═CH.sub.2.

[0082] ICA: a mixture consisting essentially of at least 95%, alternatively at least 98% of 2-methylbutane (isopentane) and minor constituents that at least include pentane (CH.sub.3(CH.sub.2).sub.3CH.sub.3).

[0083] Molecular hydrogen gas: H.sub.2.

[0084] Mineral oil: Sonneborn HYDROBRITE 380 PO White.

[0085] 10% Igepal means a 10 wt % solution of Igepal CO-630 in water, wherein Igepal CO-630 is an ethoxylated branched-nonylphenol of structural formula 4-(branched-C.sub.9H.sub.19)-phenyl-[OCH.sub.2CH.sub.2].sub.n—OH, wherein subscript n is a number such that the branched ethoxylated nonylphenol has a number-average molecular weight of about 619 grams/mole.

[0086] Preparation 1: synthesis of 3,6-dimethyl-1H-indene, of the formula

##STR00003##

In a glove box, a 250-mL two-neck container fitted with a thermometer (side neck) and a solids addition funnel, was charged with tetrahydrofuran (25 mL) and methylmagnesium bromide (2 equivalents, 18.24 mL, 54.72 mmol). The contents of the container were cooled in a freezer set at −35° C. for 40 minutes; when removed from the freezer, the contents of the container were measured to be −12° C. While stirring, indanone [5-Methyl-2,3-dihydro-1H-inden-1-one (catalog #HC-2282)] (1 equivalent, 4.000 g, 27.36 mmol) was added to the container as a solid in small portions and the temperature increased due to exothermic reaction; additions were controlled to keep the temperature at or below room temperature. Once the addition was complete, the funnel was removed, and the container was sealed (SUBA). The sealed container was moved to a fume hood (with the contents already at room temperature) and put under a nitrogen purge, then stirred for 3 hours. The nitrogen purge was removed, diethyl ether (25 mL) was added to the container to replace evaporated solvent, and then the reaction was cooled using an acetone/ice bath. A HCl (15% volume) solution (9 equivalents, 50.67 mL, 246.3 mmol) was added to the contents of the container very slowly using an addition funnel, the temperature was maintained below 10° C. Then, the contents of the container were warmed up slowly for approximately 12 hours (with the bath in place). Then, the contents of the container were transferred to a separatory funnel and the phases were isolated. The aqueous phase was washed with diethyl ether (3 times 25 mL). The combined organic phases were then washed with sodium bicarbonate (50 mL, saturated aqueous solution), water (50 mL), and brine (50 mL). The organic phase was dried over magnesium sulfate, filtered and the solvent removed by rotary evaporator. The resulting dark oil, confirmed as product by NMR, was dissolved in pentane (25 mL), then filtered through a short silica plug (pre-wetted with pentane) that was capped with sodium sulfate. Additional pentane (25-35 mL) was used to flush the plug, then were combined with the first. The solution was dried by rotary evaporator resulting in 2.87 g (74% yield) of 3,6-dimethyl-1H-indene that was confirmed as product by NMR. .sup.1H NMR (C.sub.6D.sub.6): δ 7.18 (d, 1H), 7.09 (s, 1H), 7.08 (d, 1H), 5.93 (m, 1H), 3.07 (m, 2H), 2.27 (s, 3H), 2.01 (q, 3H).

[0087] Preparation 2: synthesis of spray-dried, activated bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl on hydrophobic fumed silica. Slurried 1.5 kg of hydrophobic surface treated fumed silica (Cabosil TS-610) in 16.8 kg of toluene, then added a 10 wt % solution (11.1 kg) methylaluminoxane (MAO) in toluene and 54.5 g of HN5. Introduced the resulting mixture into an atomizing device, producing droplets that were then contacted with a hot nitrogen gas stream to evaporate the liquid and form a powder. The powder was separated from the gas mixture in a cyclone separator and discharged into a container. Spray-dried in a spray drier with dryer temperature set at 160° C. and outlet temperature at 70° to 80° C. Collected the spray-dried catalyst as a fine powder. Stirred the collected powder in n-hexane and mineral oil to give a non-metallocene single site catalyst formulation of 16 wt % solids in 10 wt % n-hexane and 74 wt % mineral oil and activated bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl. The bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl is a compound of formula (II) wherein M is Zr and each R.sup.1 is benzyl and may be made by procedures described in the art or obtained from Univation Technologies, LLC, Houston, Tex., USA, a wholly-owned entity of The Dow Chemical Company, Midland, Mich., USA.

[0088] Inventive Example 1 (IE1): synthesis of (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl, which is a compound of formula (I) wherein R is H and each X is methyl. In a glovebox under an anhydrous inert gas atmosphere (anhydrous nitrogen or argon gas), 3,6-dimethyl-1H-indene (1.000 g, 6.94 moles) in dimethoxyethane (10 mL) was added to a 120 mL (4-ounce (oz)) container, which was then capped, and the contents of the container were chilled to −35° C. n-butyllithium (1.6M hexanes, 4.3 mL, 0.0069 mole) was added to the container and the contents were stirred for approximately 3 hours while heat was removed to maintain the contents of the container near −35° C. Reaction progress was monitored by dissolving a small aliquot in d8-THF for .sup.1H NMR analysis; when the reaction was complete, solid cyclopentadienyl zirconium trichloride (CpZrCl.sub.3) (1.821 g) was added in portions to the contents of the container while stirring. Reaction progress was monitored by dissolving a small aliquot in d8-THF for .sup.1H NMR analysis; the reaction was complete after approximately 3 hours and the contents of the container were stirred for approximately 12 more hours. Then, methylmagnesium bromide (3.0M in ether, 4.6 mL) was added to the contents of the container, after the addition the contents of the container were stirred for approximately 12 hours. Then, solvent was removed in vacuo and the product was extracted into hexane (40 mL) and filtered through diatomaceous earth, washed with additional hexane (30 mL) and then dried in vacuo to provide the cyclopentadienyl(1,5-dimethylindenyl) zirconium dimethyl. (Cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl was confirmed by proton nuclear magnetic resonance spectroscopy (.sup.1H NMR) analysis. .sup.1H NMR (C.sub.6D.sub.6): δ 7.26 (d, 1H), 6.92 (d, 1H), 6.83 (dd, 1H), 5.69 (d, 1H), 5.65 (m, 1H), 5.64 (s, 5H), 2.18 (s, 3H), 2.16 (s, 3H), −0.34 (s, 3H), −0.62 (s, 3H).

[0089] Due to the rules of IUPAC nomenclature it is believed that the dimethyl numbering in the molecule 3,6-dimethyl-1H-indene becomes, after deprotonation thereof, becomes in the conjugate anion 1,5-dimethylindenyl.

[0090] Inventive Example 1A (IE1A): synthesis of (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dichloride, which is a compound of formula (I) wherein R is H and each X is Cl. In a glovebox, charged an eight-ounce jar with 3,6-dimethyl-1H-indene (5.00 g, 34.7 mmol) and hexane (100 mL). While stirring with magnetic stir bar, slowly added n-butyllithium (1.6M in hexanes, 23.8 mL, 38.1 mmol). After stirring overnight, filtered the resulting precipitated white solid, washed the filtercake thoroughly with hexane (3 times 20 mL), and dried in vacuo to yield 1,5-dimethylindenyllithium (4.88 g, 93.7% yield) as a white solid. In a glovebox, dissolved a portion of the 1,5-dimethylindenyllithium (2.315 g, 15.42 mmol) in dimethoxyethane (60 mL) in a four-ounce jar, and added CpZrCl.sub.3 (4.05 g, 15.42 mmol) in portions as a solid. After stirring overnight, removed solvents in vacuo, and took up the residue in toluene (110 mL) at 60° C., and filtered. NMR analysis of an aliquot of the filtrate showed the title product. In order to purify the product, decreased the volume of the filtrate in vacuo to 40 mL, and raised the temperature thereof to 80° C. to dissolve solids. Slowly cooled the resulting solution to room temperature, and held it in a freezer (−32° C.) to produce recrystallized product. Collected by filtration and washed with hexane (2 times 10 mL), then dried in vacuo to yield (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dichloride as a bright yellow solid (4.09 g, 71.6%). .sup.1H NMR (C.sub.6D.sub.6): δ 7.32 (m, 1H), 6.90 (dt, 1H), 6.75 (dd, 1H), 6.19 (dq, 1H), 5.76 (s, 5H), 5.73 (m, 1H), 2.35 (d, 3H), 2.08 (d, 3H).

[0091] Inventive Example 2 (IE2): prophetic synthesis of (methylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl, which is a compound of formula (I) wherein R is methyl and each X is methyl. Replicate the synthesis of Example 1 except used methylcyclopentadienyl zirconium trichloride (MeCpZrCl.sub.3) in place of the cyclopentadienyl zirconium trichloride (CpZrCl.sub.3), wherein the number of moles of MeCpZrCl.sub.3 was the same as that of CpZrCl.sub.3.

[0092] Inventive Example 2A (IE2A): synthesis of (methylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dichloride, which is a compound of formula (I) wherein R is CH.sub.3 and each X is Cl. Synthesized 1,5-dimethylindenyllithium as described in IE1A. In a glovebox, dissolved 1,5-dimethylindenyllithium (0.500 g, 3.33 mmol) in dimethoxyethane (30 mL) in a four-ounce jar, and added MeCpZrCl.sub.3 (0.921 g, 3.33 mmol) in portions as a solid. After stirring overnight, removed solvents in vacuo, and took up the residue in dichloromethane (40 mL), and filtered. NMR analysis of an aliquot of the filtrate showed the title product. In order to purify the product, decreased the volume of the filtrate in vacuo to 20 mL, added hexane (20 mL), and cooled the resulting solution in a glovebox freezer (−32° C.) to produce recrystallized product. Collected by filtration and washed with hexane (3 times 5 mL), then dried in vacuo to yield (methylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dichloride (0.527 g, 41.1%). .sup.1H NMR (C.sub.6D.sub.6): δ 7.32 (m, 1H), 6.93 (m, 1H), 6.75 (dd, 1H), 6.25 (dd, 1H), 5.76 (m, 2H), 5.58 (m, 1H), 5.52 (m, 1H), 5.38 (td, 1H), 2.37 (d, 3H), 2.09 (d, 3H), 2.01 (s, 3H).

[0093] Inventive Example 3 (IE3): prophetic synthesis of (ethylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl, which is a compound of formula (I) wherein R is ethyl and each X is methyl. Replicate the synthesis of Example 1 except used ethylcyclopentadienyl zirconium trichloride (EtCpZrCl.sub.3) in place of the cyclopentadienyl zirconium trichloride (CpZrCl.sub.3), wherein the number of moles of EtCpZrCl.sub.3 was the same as that of CpZrCl.sub.3.

[0094] Inventive Example 3A (IE3A): prophetic synthesis of (ethylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dichloride, which is a compound of formula (I) wherein R is CH.sub.2CH.sub.3 and each X is Cl. Replicate the procedure of IE2A except use EtCpZrCl.sub.3 instead of the MeCpZrCl.sub.3 to give (ethylcyclopentadienyl(1,5-dimethylindenyl)zirconium dichloride. Confirm structure by .sup.1H NMR.

[0095] Inventive Example 4 (IE4): preparation of a trim solution of (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl. Charge (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of IE1 and n-hexane into a first cylinder. Charge the resulting solution of cyclopentadienyl(1,5-dimethylindenyl) zirconium dimethyl solution in hexane from the first cylinder into a 106 liter (L; 28 gallons) second cylinder. The second cylinder contained 310 grams of 1.07 wt % (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl. Added 7.98 kg (17.6 pounds) of high purity isopentane to the 106 L cylinder to yield a trim solution of 0.04 wt % (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl in n-hexane.

[0096] Inventive Example 5 (IE5): prophetic preparation of a trim solution of methylcyclopentadienyl(1,5-dimethylindenyl) zirconium dimethyl. Replicate the procedure of IE4 except use (methylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of IE2 in place of the (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of IE1 to yield a trim solution of 0.04 wt % (methylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl in n-hexane.

[0097] Inventive Example 6 (IE6): prophetic preparation of a trim solution of (ethylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl. Replicate the procedure of IE4 except use (ethylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of IE3 in place of the (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of IE1 to yield a trim solution of 0.04 wt % (ethylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl in n-hexane.

[0098] Inventive Example 7 (IE7): Bimodal Catalyst System 1 (BMC1). In a pre-contacting embodiment, fed the slurry of non-metallocene single site catalyst formulation of 16 wt % solids in wt % n-hexane and 74 wt % mineral oil and activated bis(2-(pentamethylphenylamido)ethyl)amine zirconium dibenzyl made in Preparation 2 through a catalyst injection tube, wherein it is contacted with a stream of the trim solution of the (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of Example 4 to make the BMC1. The BMC1 is made outside of the GPP reactor and shortly thereafter enters the GPP reactor in the polymerization of Inventive Example A described below. Set the ratio feed of trim solution of (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of Example 4 to the feed of the non-metallocene single site catalyst formulation of Preparation 1 to adjust the HLMI of the produced bimodal poly(ethylene-co-1-hexene) copolymer in the reactor to approximately 30 g/10 min. Set the catalyst feeds at rates sufficient to maintain a production rate of about 16 to about 18 kg/hour (about 35 to about 40 lbs/hr) of the bimodal poly(ethylene-co-1-hexene) copolymer.

[0099] Inventive Example 8 (IE8): prophetic Bimodal Catalyst System 2 (BMC2): replicate the procedure of IE7 except use the trim solution of (methylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of Example 5 instead of the trim solution of (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of Example 4 to make the BMC2 outside the GPP reactor.

[0100] Inventive Example 9 (IE9): prophetic Bimodal Catalyst System 3 (BMC3): replicate the procedure of IE7 except use the trim solution of (ethylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of Example 6 instead of the trim solution of (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl of Example 4 to make the BMC3 outside the GPP reactor.

[0101] Inventive Example 10 (IE10): polymerization procedure. For each example, copolymerized ethylene and 1-hexene in a fluidized bed-gas phase polymerization (FB-GPP) reactor having a distribution grid to make an embodiment of the bimodal poly(ethylene-co-1-hexene) copolymer. The FB-GPP reactor had a 0.35 meter (m) internal diameter and 2.3 m bed height and a fluidized bed composed of polymer granules. Flowed fluidization gas through a recycle gas loop comprising sequentially a recycle gas compressor and a shell-and-tube heat exchanger having a water side and a gas side. The fluidization gas flows through the compressor, then the water side of the shell-and-tube heat exchanger, then into the FB-GPP reactor below the distribution grid. Fluidization gas velocity in the be is about 0.61 meter per second (m/s, 2.0 feet per second). The fluidization gas then exits the FB-GPP reactor through a nozzle in the top of the reactor, and is recirculated continuously through the recycle gas loop. Maintained a constant fluidized bed temperature of 105° C. by continuously adjusting the temperature of the water on the shell side of the shell-and-tube heat exchanger. Introduced feed streams of ethylene, nitrogen, and hydrogen together with 1-hexene comonomer into the recycle gas line. Operated the FB-GPP reactor at a total pressure of about 2413 kPA gauge, and vented reactor gases to a flare to control the total pressure. Adjusted individual flow rates of ethylene, nitrogen, hydrogen and 1-hexene to maintain their respective gas composition targets. Set ethylene partial pressure to 1.52 megapascal (MPa, 220 pounds per square inch (psi)), and set the C.sub.6/C.sub.2 molar ratio to 0.00125 and the H.sub.2/C.sub.2 molar ratio to 0.0009. Maintained isopentane (ICA) concentration at about 8.0 mol %. Measured concentrations of all gasses using an on-line gas chromatograph. Maintained the fluidized bed at constant height by withdrawing a portion of the bed at a rate equal to the rate of formation of particulate product bimodal poly(ethylene-co-1-hexene) copolymer. Recorded average copolymer residence time in hours, typically from 2 to 5 hours. Product was removed semi-continuously via a series of valves into a fixed volume chamber. A nitrogen purge removed a significant portion of entrained and dissolved hydrocarbons in the fixed volume chamber. After purging, the product was discharged from the fixed volume chamber into a fiber pack for collection. The product was further treated with a small stream of humidified nitrogen to deactivate any trace quantities of residual catalyst and cocatalyst.

[0102] Inventive Examples 11 to 14 (IE11 to IE14): synthesized bimodal poly(ethylene-co-1-hexene) copolymer. Using the polymerization procedure of IE10, synthesized the bimodal poly(ethylene-co-1-hexene) copolymers of IE11 to IE14.

[0103] Inventive Examples 15 to 18 (IE15 to IE18): Formulation and Pelletization Procedure: Each of the different granular resins of the bimodal poly(ethylene-co-1-hexene) copolymer of IE11 to IE14 was separately mixed with 400 parts per million weight/weight (ppm) of Antioxidant 1 and 800 ppm Antioxidant 2 in a ribbon blender, and then compounded into strand cut pellets using a twin-screw extruder Coperion ZSK-40. The resulting pellets of each inventive formulation were tested for various properties according to the aforementioned respective test methods. Results are shown later in Tables 1a and 1b.

[0104] Comparative Examples 1 and 2 (CE1 and CE2): replicate the procedure of IE15 twice to make different poly(ethylene-co-1-hexene) copolymers, except use bis(butylcyclopentadienyl)zirconium dimethyl instead of (cyclopentadienyl)(1,5-dimethylindenyl) zirconium dimethyl in the preparation of a comparative bimodal catalyst system. Results are shown below in Tables 1a and 1b.

TABLE-US-00001 TABLE 1a Properties of formulations of IE15 to IE18 and CE1 and CE2. Overall Formulation Property IE15 IE16 IE17 IE18 CE1 CE2 Copolymer Density 0.959 0.958 0.959 0.958 0.957 0.957 (g/cm.sup.3) Copolymer M.sub.w/M.sub.n 17.1 17.1 16.9 17.3 14.9 19.5 Copolymer M.sub.z/M.sub.w 12.4 12.4 11.6 11.6 11.8 10.2 Copolymer I.sub.2 (g/10 min.) 0.2 0.2 0.2 0.1 0.2 0.1 Copolymer I.sub.5 (g/10 min.) 1.5 1.6 1.2 1.1 1.0 0.7 Copolymer I.sub.21 (g/10 min.) 34 37 30 28 28 29 Copolymer MFR2 (I.sub.21/I.sub.2) 179 163 192 197 169 244 Copolymer MFR5 (I.sub.21/I.sub.5) 23.7 22.8 25.2 26.1 27.8 39.3 Copolymer ESCR (10% 175 173 211 236 82 191 Igepal, F50) (hours) Copolymer ESCR (10% Yes Yes Yes Yes No No Igepal, F50) > (10 * MFRS * 1 hour) − 150 hours (Eq. 1) (Yes/no) Copolymer M.sub.w (g/mol) 317,043 317,043 322,101 329,181 290,027 285,758 Copolymer M.sub.n (g/mol) 18,579 18,579 19,045 19,046 19,416 14,670 Copolymer M.sub.z (kg/mol) 3,919 3,919 3,731 3,813 3,422 2,927 Copolymer Resin Swell 8.5 8.4 8.2 8.3 9.1 7.5 t1000 (seconds) Copolymer Melt 8.5 7.8 8.3 8.8 10.0 9.8 Strength (cN)

TABLE-US-00002 TABLE 1b Properties of copolymer components of formulations of IE15 to IE18 and CE1 and CE2. Component Property IE15 IE16 IE17 IE18 CE1 CE2 HMW copolymer 22.1 21.7 23.1 23.9 20.0 24.6 component amount (wt %) HMW copolymer 1,125 1,094 1,102 1,086 1,067 904 component M.sub.w (kg/mol) HMW copolymer 269,793 266,247 266,664 259,855 305,393 265,099 component M.sub.n (g/mol) HMW copolymer 2,808 2,734 2,755 2,737 2,477 2,127 component M.sub.z (kg/mol) HMW copolymer 4.2 4.1 4.1 4.2 3.5 3.4 component M.sub.w/M.sub.n LMW copolymer 77.9 78.3 76.9 76.1 80.0 75.4 component amount (wt %) LMW copolymer 49,714 49,891 50,140 50,204 59,047 46,494 component M.sub.w (g/mol) LMW copolymer 17,942 18,167 18,078 18,217 18,540 12,755 component M.sub.n (g/mol) LMW copolymer 104,146 103,568 105,135 104,586 142,293 128,988 component M.sub.z (g/mol) LMW copolymer 2.8 2.7 2.8 2.8 3.2 3.6 component M.sub.w/M.sub.n M.sub.wH/M.sub.wL 22.6 21.9 22.0 21.6 18.1 19.4

[0105] In Tables 1a and 1b, kg/mol means kilograms per mole. 1 kg/mol=1,000 grams per mole (g/mol).

[0106] As shown in Tables 1a and 1b, the bimodal poly(ethylene-co-1-alkene) copolymers have improved processability and resistance to cracking in harsh environments relative to the comparative bimodal poly(ethylene-co-1-alkene) copolymers. This enables melt-extruding and blow molding of the inventive copolymer into manufactured articles with improved resistance to cracking in harsh environments. The copolymer is also useful for making small-part manufactured articles such as sheets, fibers, coatings and molded articles. Molded articles may be made by processes such as injection molding, rotary molding, or blow molding.

[0107] The below claims are hereby incorporated here verbatim by reference.