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WO 2015/179628 Al 26 November 2015 (26.11.2015) P O P C T

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WO 2015/179628 Al 26 November 2015 (26.11.2015) P O P C T (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2015/179628 Al 26 November 2015 (26.11.2015) P O P C T (51) International Patent Classification: (81) Designated States (unless otherwise indicated, for every C08F 210/16 (2006.01) kind of national protection available): AE, AG, AL, AM, AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, (21) International Application Number: BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, PCT/US20 15/03 1952 DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, (22) International Filing Date: HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR, 2 1 May 2015 (21 .05.2015) KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM, (25) Filing Language: English PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC, (26) Publication Language: English SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (30) Priority Data: 14/284,689 22 May 2014 (22.05.2014) US (84) Designated States (unless otherwise indicated, for every kind of regional protection available): ARIPO (BW, GH, (71) Applicant: CHEVRON PHILLIPS CHEMICAL COM¬ GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, PANY LP [US/US]; 10001 Six Pines Drive, The Wood TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, lands, TX 77380 (US). TJ, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, (72) Inventors: YANG, Qing; 2917 Montrose Drive, Bartles- LV, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, ville, OK 74006 (US). GRECO, Jeffrey, F ; 4022 S SM, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, Columbia PL, Tulsa, OK 74105 (US). MCDANIEL, Max, GW, KM, ML, MR, NE, SN, TD, TG). P ; 1601 Melmart Drive, Bartlesville, OK 74006 (US). YU, Youlu; 1532 Whitney Lane, Bartlesville, OK 74006 (US). Published: GLASS, Gary, L.; 12600 N 3980 Road, Dewey, OK — with international search report (Art. 21(3)) 74029 (US). CRAIN, Tony, R ; 474 Rd 30, Niotaze, KS 67355 (US). — before the expiration of the time limit for amending the claims and to be republished in the event of receipt of (74) Agent: HUSEMAN, Cheryl, L (45392); Chevron Phillips amendments (Rule 48.2(h)) Chemical Company LP, 10001 Six Pines Drive, The Woodlands, TX 77380 (US). (54) Title: DUAL CATALYST SYSTEMS FOR PRODUCING POLYMERS WITH A BROAD MOLECULAR WEIGHT DISTRI BUTION AND A UNIFORM SHORT CHAIN BRANCH DISTRIBUTION 1.2 2 0 2 StC 1 1 2 16 2 14 0.8 12 © 0.6 10 8 0.4 s ¾ 4 0.2 2 0 0 5 LogM (57) Abstract: Disclosed herein are ethylene-based polymers having a melt index less than 50 g/10 min, a ratio of Mw/Mn from 4 to 20, a density from 0.90 to 0.945 g/cm 3, and a substantially constant short chain branch distribution. These polymers can be produced using a dual catalyst system containing a boron bridged metallocene compound with a cyclopentadienyl group and an indenyl group, and a single atom bridged metallocene compound with a fluorenyl group. DUAL CATALYST SYSTEMS FOR PRODUCING POLYMERS WITH A BROAD MOLECULAR WEIGHT DISTRIBUTION AND A UNIFORM SHORT CHAIN BRANCH DISTRIBUTION REFERENCE TO RELATED APPLICATION This application claims the benefit of U.S. Provisional Application Serial No. 61/905,894, filed on November 19, 2013, the disclosure of which is incorporated herein by reference in its entirety. BACKGROUND OF THE INVENTION Polyolefins such as high density polyethylene (HDPE) homopolymer and linear low density polyethylene (LLDPE) copolymer can be produced using various combinations of catalyst systems and polymerization processes. In some end-use applications, it can be beneficial to use a dual metallocene catalyst system to produce copolymers having broad and/or bimodal molecular weight distributions. Moreover, it can be beneficial for such copolymers to also have a flat or uniform comonomer distribution. Accordingly, it is to these ends that the present invention is directed. SUMMARY OF THE INVENTION This summary is provided to introduce a selection of concepts in a simplified form that are further described below in the detailed description. This summary is not intended to identify required or essential features of the claimed subject matter. Nor is this summary intended to be used to limit the scope of the claimed subject matter. The present invention generally relates to new catalyst compositions, methods for preparing catalyst compositions, methods for using the catalyst compositions to polymerize olefins, the polymer resins produced using such catalyst compositions, and articles produced using these polymer resins. In particular, aspects of the present invention are directed to catalyst compositions employing two metallocene catalyst components. The first catalyst component can comprise a boron bridged metallocene compound with a cyclopentadienyl group and an indenyl group. The second catalyst component can comprise a single atom bridged metallocene compound with a fluorenyl group. Such catalyst compositions can be used to produce, for example, ethylene-based copolymers for variety of end-use applications. The present invention also contemplates and encompasses olefin polymerization processes. Such processes can comprise contacting a catalyst composition with an olefin monomer and optionally an olefin comonomer under polymerization conditions to produce an olefin polymer. Generally, the catalyst composition employed can comprise any of the catalyst component I (boron bridged) cyclopentadienyl-indenyl metallocene compounds, any of the catalyst component II (single atom bridged) metallocene compounds with a fluorenyl group, and any of the activators and optional co-catalysts disclosed herein. For example, organoaluminum compounds can be utilized in the catalyst compositions and/or polymerization processes. Polymers produced from the polymerization of olefins, resulting in homopolymers, copolymers, terpolymers, etc., can be used to produce various articles of manufacture. A representative and non-limiting example of an olefin polymer (e.g., an ethylene copolymer) consistent with aspects of this invention can be characterized as having the following properties: a melt index of less than or equal to about 50 g/10 min, a ratio of Mw/Mn in a range from about 4 to about 20, a density in a range from about 0.90 g/cm to about 0.945 g/cm , and a substantially constant short chain branch distribution (SCBD). Another representative and non-limiting ethylene-based polymer described herein can have a melt index of less than or equal to about 10 g/10 min, a ratio of Mw/Mn in a range from about 4.1 to about 8, a density in a range from about 0.915 g/cm3 to about 0.945 g/cm3, and a substantially constant short chain branch distribution (SCBD). These polymers, in further aspects, can be characterized by low levels of long chain branches (LCB) and/or by a bimodal molecular weight distribution. Both the foregoing summary and the following detailed description provide examples and are explanatory only. Accordingly, the foregoing summary and the following detailed description should not be considered to be restrictive. Further, features or variations may be provided in addition to those set forth herein. For example, certain aspects and embodiments may be directed to various feature combinations and sub-combinations described in the detailed description. BRIEF DESCRIPTION OF THE FIGURES FIG. 1 presents a plot of the molecular weight distribution and short chain branch distribution of the polymer of Example 1. FIG. 2 presents a plot of the molecular weight distribution and short chain branch distribution of the polymer of Example 2. FIG. 3 presents a plot of the molecular weight distribution and short chain branch distribution of the polymer of Example 3. FIG. 4 presents a plot of the molecular weight distribution and short chain branch distribution of the polymer of Example 4. FIG. 5 presents a plot of the molecular weight distribution and short chain branch distribution of the polymer of Example 5. FIG. 6 illustrates the definitions of D85 and D15 on a molecular weight distribution curve. DEFINITIONS To define more clearly the terms used herein, the following definitions are provided. Unless otherwise indicated, the following definitions are applicable to this disclosure. If a term is used in this disclosure but is not specifically defined herein, the definition from the IUPAC Compendium of Chemical Terminology, 2nd Ed (1997), can be applied, as long as that definition does not conflict with any other disclosure or definition applied herein, or render indefinite or non-enabled any claim to which that definition is applied. To the extent that any definition or usage provided by any document incorporated herein by reference conflicts with the definition or usage provided herein, the definition or usage provided herein controls. While compositions and methods are described herein in terms of "comprising" various components or steps, the compositions and methods can also "consist essentially of or "consist of the various components or steps, unless stated otherwise. For example, a catalyst composition consistent with aspects of the present invention can comprise; alternatively, can consist essentially of; or alternatively, can consist of; (i) catalyst component I, (ii) catalyst component II, (iii) an activator, and (iv) optionally, a co-catalyst. The terms "a," "an," "the," etc., are intended to include plural alternatives, e.g., at least one, unless otherwise specified. For instance, the disclosure of "an activator- support" or "a metallocene compound" is meant to encompass one, or mixtures or combinations of more than one, activator-support or metallocene compound, respectively, unless otherwise specified.
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