US008471085B2

(12) United States Patent (10) Patent No.: US 8.471,085 B2 Sydora (45) Date of Patent: Jun. 25, 2013

(54) OLIGOMERIZATION CATALYST SYSTEM (56) References Cited AND PROCESS FOR OLGOMERIZING OLEFNS U.S. PATENT DOCUMENTS 2.935,495 A 5/1960 Kennedy (75) Inventor: Orson L. Sydora, Houston, TX (US) 3,100,764 A 8, 1963 Jezlet al. 3,231,550 A 1/1966 Manyik et al. (73) Assignee: YoshiyiphysicompanyO O 3,300,4583,242,099 A 3/19661/1967 Manyik et al. , The Woodlands, TX (US) 3,347,840 A 10/1967 Manyik et al. - 3,534,006 A 10/1970 Kamaishi et al. (*) Notice: Subject to any disclaimer, the term of this 3,558,676 A 1/1971 Doherty et al. patent is extended or adjusted under 35 3,635,869 A 1/1972 Steele et al. U.S.C. 154(b) by 281 days. 3,819,746 A 6, 1974 Katzakian, Jr. et al. (Continued) (21) Appl. No.: 12/771,122 FOREIGN PATENT DOCUMENTS (22) Filed: Apr. 30, 2010 CA 2087578 T 1994 CN 12.56968 6, 2000 (65) Prior Publication Data (Continued) US 2010/O274O65A1 Oct. 28, 2010 OTHER PUBLICATIONS International Application PCT/2001/033431 Search Report dated Related U.S. ApplicationO O Data Jun. 22, 2011. (63) Continuation-in-part of application No. 12/609,272, (Continued) filed on Oct. 30, 2009. Primary Examiner — Yun Qian (60) Provisional application No. 61/110,396, filed on Oct. (74) Attorney, Agent, or Firm — Merchant & Gould P.C. 31, 2008, provisional application No. 61/110,407, (57) ABSTRACT filed on Oct. 31, 2008, provisional application No. 61/110,476, filed on Oct. 31, 2008. Among other things, this disclosure provides an olefin oligo merization system and process, the system comprising: a) a (51) Int. Cl. transition metal compound; b) a pyrrole compound having a CD7C2/24 (2006.01) hydrogenatom on at the 5-position or the 2- and 5-position of C07C2/02 (2006.01) apyrrole compound and having a bulky Substituent located on BOI 3/14 (2006.01) each carbon atom, adjacent to the carbon atom bearing a (52) U.S. Cl. hydrogen atom at the 5-position or the 2- and 5-position of a USPC ...... ssss 13.502/102, so2/103.502/256: pyrrole compound. These catalyst system have significantly 5O2/167: 502/123585/604 improved productivities, selectivities to 1-hexene, and pro (58)58) tField OSSOof Classification SeaS h s s videslyst Systems higher purityusing 2,4-dimethyl1-hexene within pyrrole. the C fraction than cata See application file for complete search history. 28 Claims, 2 Drawing Sheets

120,000 --2,5-DMP -o-2,5-DBP --2,4-DMP -e-pyrrole sar 2,5-DEP a -2-M-A-LPP

100,000

80,000

60,000

40,000

20,000

40 60 80 OO 20 40 18O Oligomerization Temperature (°C) US 8,471,085 B2 Page 2

U.S. PATENT DOCUMENTS 2002/0182124 A1 12/2002 Woodard et al. 2004/0236163 A1 11/2004 Ewert et al. 3,838,101 9, 1974 Steele et al. 2005/0187391 A1 8/2005 Knudsen et al. 3,873,602 3, 1975 Katzakian, Jr. et al. 2005/O197521 A1 9, 2005 Kreischer 3,932.285 1, 1976 Ceprini et al. 2005/0222350 A1 10/2005 Small et al. 3,962, 182 6, 1976 Steele et al. 2005/0255987 A1 11/2005 McDaniel et al. 3,968, 135 7, 1976 Steele et al. 2006, O247483 A1 11/2006 McConville et al. 3,977,996 8, 1976 Katzakian, Jr. et al. 2007,0185361 A1 8/2007 Buchanan et al. 3,978,026 8, 1976 Katzakian, Jr. et al. 2007,0185.364 A1 8/2007 Buchanan et al. 4.017.429 4, 1977 Steele et al. 2008/0051545 A1 2/2008 McDaniel et al. 4,224, 181 9, 1980 Langer, Jr. 2008/0058534 A1 3/2008 Knudsen et al. 4,603, 184 T. 1986 Sato et al. 2008/O177122 A1 7/2008 Knudsen et al. 4,668,808 5, 1987 Smith 2008/0293899 A1 11/2008 McConville et al. 4,668,838 5, 1987 Briggs 2010.0030000 A1 2/2010 Emoto et al. 4,716,206 12, 1987 Fujita et al. 2010.0113852 A1 5/2010 Sydora 4,721,762 1, 1988 Commereuc et al. 2010.0137669 A1* 6/2010 Han et al...... 585,514 4,806,513 2, 1989 McDaniel et al. 4,814,308 3, 1989 Konrad et al. FOREIGN PATENT DOCUMENTS 5, 198,563 3, 1993 Reagen et al. 5,288,823 2, 1994 Reagan et al. EP O194596 A2 9, 1986 5,331,070 T. 1994 Pettijohn et al. EP 0207220 A2 1, 1987 5,331, 104 T. 1994 Reagen et al. EP O416304 A2 3, 1991 5,340,785 8, 1994 Reagen et al. EP O608447 A1 8, 1994 5,360,879 11, 1994 Reagen et al. EP O78O353 A1 6, 1997 5,376,612 12, 1994 Reagen et al. EP 0608447 B1 10, 2001 5,382,738 1, 1995 Reagen et al. FR 2253029 6, 1975 5,393,719 2, 1995 Pettijohn et al. WO WO97,11082 3, 1997 5,399,539 3, 1995 Reagen et al. WO WO 2006,109 194 A2 10, 2006 5.438,027 8, 1995 Reagen et al. WO WO, 2008/088178 * 7/2008 5,451,645 9, 1995 Reagen et al. OTHER PUBLICATIONS 5,470,926 11, 1995 Reagen et al. 5,523,507 6, 1996 Reagen et al. Briggs, J., Chem. Commun., Selective Trimerization of Ethylene to 5,543,375 8, 1996 Lashier et al. 5,563,312 10, 1996 Knudsen et al. Hex-1-ene, J. Chem. Soc., 1989, pp. 674-675. 5,689,028 11, 1997 Lashier et al. Hart, Robert et al., “Synthesis and Structures of Metal Carboxylate 5,763,723 6, 1998 Reagen et al. Liquids.” Shepherd Chemical Company, Mar. 23, 2009, National 5,786,431 7, 1998 Reagen et al. Meeting of the American Chemical Society. 5,814,575 9, 1998 Reagen et al. Mehrotra, R.C. et al., “Metal Carboxylates.” Jaipur 302004, 1983, 5,856.257 1, 1999 Freeman et al. Academic Press, pp. 22-27. 5,856,612 1, 1999 Araki et al. Mehrotra, R.C. et al., “Metal Carboxylates.” Jaipur 302004, 1983, 5,859,303 1, 1999 Lashier Academic Press, pp. 233-317. 5,910,619 6, 1999 Urata et al. Tille, D., Z. Anorg. Alleg. Chem. Organometal Compounds of Nitro 5,919,996 7, 1999 Freeman et al. gen Systems, 1971, 384, pp. 136-146. 5,986,153 11, 1999 Kallenbach Tille, D., Zeitschrift fur Naturforschung, Pyrrolylchromium Com 6,043,401 3, 2000 Bagheri et al. 6,133,495 10, 2000 Urata et al. pounds, 1966, 21b, p. 1239. 6, 191,076 2, 2001 Gee International Search Report and Written Opinion for PCT/US2009/ 6,380.451 4, 2002 Kreischer et al. 062700, Jan. 28, 2010. 6,455,648 9, 2002 Freeman et al. U.S. Appl. No. 61/110,396, filed Oct. 31, 2008, entitled “System and 6,521,806 2, 2003 Tamura et al. Method for Diluting Metal Precursors for Oligomerization Catalyst 7,045,632 5, 2006 Small Systems”. 7,129,304 10, 2006 Small et al. U.S. Appl. No. 61/110,407, filed Oct. 31, 2008, entitled “System and 7,157,612 1/2007 Ewert et al. Method for Deactivating and Quenching an Oligomerization Cata 7,259,284 8, 2007 Hope et al. lyst”. 7,268,096 9, 2007 Small et al. U.S. Appl. No. 61/110,476, filed Oct. 31, 2008, entitled 7,271,121 9, 2007 Small et al. “Oligomerization Catalyst System and Process for Oligomerizing 7,297,832 11/2007 Blann et al...... 58.5/527 Olefins. 7,309,805 12, 2007 Hope et al. 7,351,780 4, 2008 Hope et al. International Preliminary Report on Patentability for PCT/US2009/ 7,378,537 5/2008 Small et al. 062700 mailed May 12, 2011, The International Bureau of WIPO, 7 7,384,886 6, 2008 Knudsen et al. pageS. 7,396,970 T/2008 Battiste U.S. Official Action dated Jun. 20, 2012 in U.S. Appl. No. 7,425,661 9, 2008 McConville et al. 12/609,272, 17 pages. 7,456,284 11, 2008 Small 7,476,775 B2 1/2009 Kreischer * cited by examiner U.S. Patent US 8471,085 B2 U.S. Patent Jun. 25, 2013 Sheet 2 of 2 US 8471,085 B2

( US 8,471,085 B2 1. 2 OLGOMERIZATION CATALYST SYSTEM In one aspect, this disclosure provides for a catalyst system AND PROCESS FOR OLGOMERIZING comprising: a) a transition metal compound; b) a pyrrole OLEFNS compound having i) a hydrogen atom located on at least one pyrrole ring carbonatom adjacent to the nitrogen atom of the CROSS REFERENCE TO RELATED pyrrole ring, and ii) a bulky Cs to Cs organyl group or a bulky APPLICATIONS C. to Co. silyl group located on a pyrrole ring carbon atom adjacent to any pyrrole ring carbon atom bearing the hydro This application is a Continuation-In-Part application to gen atom adjacent to the nitrogen atom of the pyrrole ring; U.S. patent application Ser. No. 12/609,272 filed Oct. 30, and c) a metal alkyl. In an embodiment, the bulky substituent 2009 which in turn claims priority to and the benefit of U.S. 10 located on pyrrole ring carbon atom adjacent to any pyrrole Provisional Patent Application No. 61/110,396 filed Oct. 31, ring carbon atom bearing the hydrogen atom adjacent to the 2008, U.S. Provisional Patent Application No. 61/110,407, nitrogen atom of the pyrrole ring may have a structure Such filed Oct. 31, 2008, and U.S. Provisional Patent Application that i) the carbon atom of the bulky Cs to Cs organyl group No. 61/110,476, filed Oct. 31, 2008. Each of these provisional attached to the pyrrole ring carbonatom is attached to three or patent applications is hereby incorporated by reference in its 15 four carbon atoms, ii) the carbon atom of the bulky Cs to Cs entirety. organyl group adjacent to the carbon atom attached to pyrrole ring carbon atom is attached to three or four carbon atoms, or TECHNICAL FIELD OF THE INVENTION iii) the silicon atom of the bulky Cs to Cosilyl group attached to the pyrrole ring carbon atom is attached to four carbon This disclosure relates to an oligomerization catalyst sys atOmS. tem, methods for preparing the oligomerization catalyst sys In another aspect, the present disclosure provides for cata tem, and methods for using the oligomerization catalyst sys lyst Systems comprising a pyrrole compound having Formula tem for preparing an oligomerization product. P2, P3, or P4:

BACKGROUND 25 P2 R12p The chromium-catalyzed synthesis of 1-hexene from eth R13p ylene constitutes a commercially significant process for the e selective preparation of this alpha olefin, which in turn is N-H useful for preparing a range of polyolefins when employed as 30 S. a comonomer with ethylene. A widely reported chromium R 14p catalyst system for the selective production of 1-hexene com H prises chromium(III) carboxylates (e.g. tris(2-ethylhex P3 anoate) chromium(III) (Cr(EH))), a pyrrole compound, and R22p a metal alkyl. 35 H Many oligomerization catalyst Systems for the selective e N-H production of 1-hexene contain a chromium compound, a S. pyrrole compound, at least one metal alkyl, optionally a sol R24p vent, and optionally additional components, which can be H combined in various ways and in various ratios to afford the 40 P4 catalyst system. Some catalyst system preparative methods H appear to rely on the presence of particular solvent to stabilize R33p the catalyst system. Typically, any method of preparing, acti e Vating, and using a catalyst system may present challenges N-H with respect to its particular preparation, activation, and sta S. bility, as well as to the activity and selectivity provided by the 45 R34p catalyst system. H Therefore, it would be useful to discover and develop new oligomerization catalyst systems, new methods for preparing wherei) R'? and Rp of Formula P2 and RPP of Formula P3 the oligomerization catalyst systems, and new methods for independently area C, to Cls hydrocarbyl group; and ii) R' using the oligomerization catalyst systems for preparing an 50 in Formula P2, R in Formula P3, and RP and R in oligomerization product that might provide greater efficiency Formula P4 independently are a bulky Cs to Cs hydrocarbyl and cost effectiveness. New oligomerization catalyst systems group or a bulky Cs to Cassilyl group. In an embodiment, the and methods for preparing the oligomerization catalyst sys R" group in Formula P2, RP group in Formula P3, and tems that might afford greater activity, increased efficiency, RP and RP group in Formula P4 are attached such that i) lower costs, increased selectivity to C products (or to 1-hex 55 the carbon atom attached to the pyrrole ring is attached to ene), and/or increased 1-hexene in the C product fraction three or four carbonatoms, ii) the carbonatom adjacent to the would be desirable. carbon atom attached to pyrrole ring is attached to three or SUMMARY OF THE INVENTION four carbon atoms, or iii) the C to Cassilyl group has For mula Sil: 60 Among other things, this disclosure provides for olefin S1 oligomerization catalyst systems, methods for preparing the Rls olefin oligomerization catalyst systems, and methods for using the olefin oligomerization catalyst system for preparing Re-si : an oligomerization product. In one aspect, the oligomeriza tion catalyst systems described here and prepared according 65 to the various disclosed embodiments may allow for achiev wherein R. R. and R independently are a C to Cs ing good catalyst activity and selectivity. hydrocarbyl group. US 8,471,085 B2 3 4 In an aspect, the present disclosure provides for an oligo atoms, ii) the carbon atom adjacent to the carbon atom merization process comprising: A) contacting a feedstock attached to pyrrole ring is attached to three or four carbon olefin with a catalyst System comprising i) a transition metal atoms, or iii) the C to Cassilyl group has Formula Sil: compound; ii) a pyrrole compound having (a) a hydrogen atom located on at least one pyrrole ring carbonatom adjacent to the nitrogenatom of the pyrrole ring, and (b) a bulky Cs to S1 Cs organyl group or a bulky Cs to Cosilyl group located on RIs a pyrrole ring carbonatom adjacent to any pyrrole ring carbon Re-si : atom bearing the hydrogen atom adjacent to the nitrogen R3s atom of the pyrrole ring; and iii) a metal alkyl and B) oligo 10 merizing the olefin under oligomerization condition to form wherein R. R. and R independently are a C to Cs an oligomerization product. In an embodiment, a bulky Sub hydrocarbyl group. In other embodiments, the trimerization stituent located on pyrrole ring carbon atom adjacent to any process may have a higher productivity (g Ce/g transition pyrrole ring carbonatom bearing the hydrogenatom adjacent 15 to the nitrogen atom of the pyrrole ring may have a structure metal—e.g. Cr) than the process using 2,4-dimethylpyrrole as Such that i) the carbon atom of the bulky Cs to Cs organyl the pyrrole compound, provide a higher selectivity to C group attached to the pyrrole ring carbon atom is attached to products than the process using 2,4-dimethylpyrrole as the three or four carbonatoms, ii) the carbonatom of the bulky C. pyrrole compound, and/or provide a higher purity 1-hexene to Cs organyl group adjacent to the carbon atom attached to product than the process using 2,4-dimethylpyrrole as the pyrrole ring carbon atom is attached to three or four carbon pyrrole compound. atoms, or iii) the silicon atom of the bulky Cs to Co. silyl In yet another aspect, this disclosure provides for a process group attached to the pyrrole ring carbon atom is attached to for preparing a catalyst System, comprising contacting, a) a four carbon atoms. transition metal compound; b) a pyrrole compound having i) In another aspect, the present invention provides for an a hydrogen atom located on at least one pyrrole ring carbon trimerization process comprising: A) contacting a feedstock 25 atom adjacent to the nitrogen atom of the pyrrole ring, and ii) olefin comprising ethylene and a catalyst System comprising a bulky Cs to Cs organyl group or a bulky C to Co. silyl i) a transition metal compound comprising a chromium(II) or group located on a pyrrole ring carbon atom adjacent to any chromium(III) carboxylate wherein each carboxylate is a C, pyrrole ring carbonatom bearing the hydrogenatom adjacent to Co. carboxylate, ii) a pyrrole compound having Formula 30 to the nitrogen atom of the pyrrole ring; and c) a metal alkyl. P2, P3, or P4: In a further aspect, this disclosure provides for a process for preparing a catalyst System, comprising contacting, a) a tran sition metal compound comprising a chromium(II) or chro P2 mium(III) carboxylate wherein each carboxylate is a C to R12p Co. carboxylate; b) a pyrrole compound having Formula P2, R13p 35 e P3, or P4: N-H S. R 14p P2 R12p H 40 P3 R13p R22p e N-H H S. e R 14p N-H S. 45 H R24p P3 R22p H P4 H H e R33p N-H e 50 S. N-H R24p S. H R34p P4 H H R33p 55 e where (a) R'? and RP of Formula P2 and RPP of Formula N-H P3 independently are a C to Cs hydrocarbyl group and (b) S. R" in Formula P2, RP in Formula P3, and RandR in R34p Formula P4 independently are a bulky Cs to Cs hydrocarbyl H group or a bulky Cs to Cassilyl group, and iii) an metal alkyl 60 comprising a mixture of triethylaluminum and diethylalumi wherei) R'? and Rp of Formula P2 and RPP of Formula P3 num chloride; and B) trimerizing the feedstock olefin under independently area C, to Cls hydrocarbyl group and ii) R' trimerization conditions to form an trimerization product in Formula P2, RP in Formula P3, and Re and RP in comprising 1-hexene. In an embodiment, the R'' group in Formula P4 independently are a bulky Cs to Cs hydrocarbyl Formula P2, RP group in Formula P3, and RP and R' 65 group or a bulky Cs to Cassilyl group; and c) a metal alkyl group in Formula P4 are attached such that i) the carbonatom comprising a mixture of triethylaluminum and diethylalumi attached to the pyrrole ring is attached to three or four carbon num chloride, US 8,471,085 B2 5 6 BRIEF DESCRIPTION OF THE FIGURES example a method can comprises several recited steps (and other non-recited Steps) but utilize a catalyst system prepara FIG. 1 is a plot of the C catalyst productivity as a function tion consisting of specific steps but utilize a catalyst system of the oligomerization temperature for chromium-based cata comprising recited components and other non-recited com lyst systems containing certain pyrrole compounds. ponents. FIG. 2 is a bar chart of the C selectivity and 1-hexene While compositions and methods are described in terms of purity for chromium-based catalyst systems containing cer “comprising various components or steps, the compositions tain pyrrole compounds. and methods can also “consist essentially of or “consist of the various components or steps. DETAILED DESCRIPTION OF THE INVENTION 10 The term “consists essentially of” or variations thereof, whenever used in this specification and claims in connection General Description with a commercial product (e.g. a feedstock olefin Such as ethylene) refers to a commercially available product. The According to various aspects and embodiments of this commercially available product can contain impurities which disclosure, there is provided olefin oligomerization catalyst 15 are not the named product which are not removed during the systems, methods for their preparation, and methods for their commercial product’s product process. One of ordinary skill use for preparing an olefin oligomerization product. In one in the art will recognize that the identity and quantity of the aspect, the oligomerization catalyst systems described here specific impurities present in the commercial product will and prepared according to the various disclosed embodiments depend upon the source of, and/or the manufacturing process can allow for achieving good catalyst System activity, catalyst used to produce the commercial product. Consequently, the system productivity, product selectivity, and/or product term “consists essentially of and its variants when used in purity by selection of the pyrrole compound used in the cata conjunction with a commercial is not intended to limit the lyst system. amount/quantity of the non-named product impurities any more stringently than the amounts/quantities present in a DEFINITIONS 25 particular commercial product. The terms “a,” “an and “the are intended, unless specifi To define more clearly the terms used herein, the following cally indicated otherwise, to include plural alternatives, e.g., definitions are provided. Unless otherwise indicated, the fol at least one. For instance, the disclosure of “a chromium lowing definitions are applicable to this disclosure. If a term carboxylate' is meant to encompass chromium carboxylate, is used in this disclosure but is not specifically defined herein, 30 or mixtures or combinations of more than one chromium the definition from the IUPAC Compendium of Chemical carboxylate unless otherwise specified. Terminology, 2" Ed (1997) can be applied, as long as that In one aspect, a chemical 'group' can be defined or definition does not conflict with any other disclosure or defi described according to how that group is formally derived nition applied herein, or render indefinite or non-enabled any from a reference or “parent compound, for example, by the claim to which that definition is applied. To the extent that any 35 number of hydrogen atoms that are formally removed from definition or usage provided by any document incorporated the parent compound to generate the group, even if that group herein by reference conflicts with the definition or usage is not literally synthesized in this manner. These groups can provided herein, the definition or usage provided herein con be utilized as substituents or coordinated or bonded to metal trols. atoms. By way of example, an “alkyl group' formally can be Regarding claim transitional terms or phrases, the transi 40 derived by removing one hydrogen atom from an alkane, tional term “comprising, which is synonymous with “includ while an “alkylene group” formally can be derived by remov ing.” “containing.” or "characterized by is inclusive or open ing two hydrogen atoms from an alkane. Moreover, a more ended and does not exclude additional, unrecited elements or general term can be used to encompass a variety of groups method steps. The transitional phrase “consisting of that formally are derived by removing any number ("one or excludes any element, step, or ingredient not specified in the 45 more’) hydrogen atoms from a parent compound, which in claim. The transitional phrase “consisting essentially of lim this example can be described as an "alkane group, and its the scope of a claim to the specified materials or steps and which encompasses an “alkyl group, an “alkylene group.” those that do not materially affect the basic and novel char and materials having three or more hydrogens atoms, as acteristic(s) of the claimed invention. A "consisting essen needed for the situation, removed from an alkane. Through tially of claim occupies a middle ground between closed 50 out, the disclosure that a Substituent, ligand, or other chemical claims that are written in a “consisting of format and fully moiety may constitute a particular 'group' implies that the open claims that are drafted in a "comprising format. Absent well-known rules of chemical structure and bonding are fol an indication to the contrary, when describing a compound or lowed when that group is employed as described. By way of composition "consisting essentially of is not to be construed example, if a Subject compound is disclosed in which Sub as “comprising.” but is intended to describe the recited com 55 stituent X can be an “alkyl group, an “alkylene group.’ oran ponent that includes materials which do not significantly alter "alkane group, the normal rules of Valence and bonding are composition or method to which the term is applied. For followed. When describing a group as being "derived by.” example, a feedstock consisting of a material A can include "derived from.” “formed by,” or “formed from,” such terms impurities typically present in a commercially produced or are used in a formal sense and are not intended to reflect any commercially available sample of the recited compound or 60 specific synthetic methods or procedure, unless specified oth composition. When a claim includes different features and/or erwise or the context requires otherwise. feature classes (for example, a method step, feedstock fea Also, unless otherwise specified, any carbon-containing tures, and/or product features, among other possibilities), the group for which the number of carbon atoms is not specified transitional terms comprising, consisting essentially of and can have, according to proper chemical practice, 1, 2, 3, 4, 5, consisting of apply only to feature class to which is utilized 65 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, and it is possible to have different transitional terms or 24, 25, 26, 27, 28, 29, or 30 carbon atoms, or any range or phrases utilized with different features within a claim. For combination of ranges between these values. For example, US 8,471,085 B2 7 8 unless otherwise specified, any carbon-containing group can saturated or unsaturated, and/or linear or branched organic have from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, compound. Aliphatic compounds and aliphatic groups may from 1 to 20 carbon atoms, from 1 to 15 carbon atoms, from contain organic functional group(s) and/or atom(s) other than 1 to 10 carbon atoms, or from 1 to 5 carbon atoms, and the carbon and hydrogen. like. Moreover, other identifiers or qualifying terms may be The term “alkane' whenever used in this specification and utilized to indicate the presence of, or absence of a particular claims refers to a saturated hydrocarbon compound. Other Substituent, a particular regiochemistry, and/or stereochem identifiers may be utilized to indicate the presence of particu istry, or the presence of absence of a branched underlying lar groups in the alkane (e.g. halogenated alkane indicates structure or backbone. Any specific carbon-containing group that the presence of one or more halogen atoms replacing an is limited according to the chemical and structural require 10 equivalent number of hydrogen atoms in the alkane). The ments for that specific group, as understood by one of ordi term “alkyl group' is used herein in accordance with the nary skill. For example, unless otherwise specified, an aryl definition specified by IUPAC: a univalent group formed by group can have from 6 to 30 carbon atoms, from 6 to 25 removing a hydrogen atom from an alkane. Similarly, an carbonatoms, from 6 to 20 carbonatoms, from 6 to 15 carbon “alkylene group' refers to a group formed by removing two atoms, or from 6 to 10 carbon atoms, and the like. Thus, 15 hydrogen atoms from an alkane (either two hydrogen atoms according to proper chemical practice and unless otherwise from one carbon atom or one hydrogen atom from two dif specified, an aryl group can have 6, 7, 8, 9, 10, 11, 12, 13, 14, ferent carbonatoms). An "alkane group' is a general term that 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 refers to a group formed by removing one or more hydrogen carbonatoms, or any range or combination of ranges between atoms (as needed for the particular group) from an alkane. An these values. “alkyl group.” “alkylene group.” and "alkane group' may be The term “substituted when used to describe a group, for linear or branched unless otherwise specified. Primary, sec example, when referring to a substituted analog of aparticular ondary, and tertiary alkyl group are derived by removal of a group, is intended to describe the compound or group wherein hydrogen atom from a primary, secondary, tertiary carbon any non-hydrogen moiety formally replaces hydrogen in that atom, respectively, of an alkane. The n-alkyl group derived by group or compound, and is intended to be non-limiting. A 25 removal of a hydrogen atom from a terminal carbon atom of compound or group may also be referred to herein as “unsub a linear alkane. The groups RCH (RzH), RCH(RzH), and stituted” or by equivalent terms such as “non-substituted.” RC(RzH) are primary, secondary, and tertiary alkyl groups, which refers to the original group or compound. “Substi respectively. The carbon atom by which indicated moiety is tuted' is intended to be non-limiting and include inorganic attached is a secondary, tertiary, and quaternary carbon atom, Substituents or organic Substituents as specified and as under 30 respectively. stood by one of ordinary skill in the art. The term “organyl group' is used herein in accordance A "halide” has its usual meaning. Examples of halides with the definition specified by IUPAC: an organic substituent include fluoride, chloride, bromide, and iodide. group, regardless of functional type, having one free Valence The term “hydrocarbon whenever used in this specifica at a carbon atom. Similarly, an “organylene group' refers to tion and claims refers to a compound containing only carbon 35 an organic group, regardless of functional type, derived by and hydrogen. Other identifiers may be utilized to indicate the removing two hydrogen atoms from an organic compound presence of particular groups in the hydrocarbon (e.g. halo (either two hydrogen atoms from one carbon atom or one genated hydrocarbon indicates that the presence of one or hydrogenatom from each of two different carbonatoms). An more halogen atoms replacing an equivalent number of "organic group' refers to a generalized group formed by hydrogen atoms in the hydrocarbon). The term “hydrocarbyl 40 removing one or more hydrogen atoms from carbonatoms of group' is used herein in accordance with the definition speci an organic compound. Thus, an “organyl group, an “orga fied by IUPAC: a univalent group formed by removing a nylene group, and an “organic group' can contain organic hydrogen atom from a hydrocarbon (that is, a group contain functional group(s) and/or atom(s) other than carbon and ing only carbon and hydrogen). Similarly, a “hydrocarbylene hydrogen, that is, an organic group that can comprise func group' refers to a group formed by removing two hydrogen 45 tional groups and/or atoms in addition to carbon and hydro atoms from a hydrocarbon, either two hydrogen atoms from gen. For instance, non-limiting examples of atoms other than one carbon atom or one hydrogen atom from each of two carbon and hydrogen include halogens, oxygen, nitrogen, different carbon atoms. Therefore, in accordance with the phosphorus, and the like. Non-limiting examples of func terminology used herein, a "hydrocarbon group' refers to a tional groups include ethers, aldehydes, ketones, esters, Sul generalized group formed by removing one or more hydrogen 50 fides, amines, and phosphines, and so forth. In one aspect, the atoms (as needed for the particular group) from a hydrocar hydrogen atom(s) removed to form the “organyl group.” bon. A “hydrocarbyl group,” “hydrocarbylene group, and "organylene group.” or “organic group' may be attached to a "hydrocarbon group' can be acyclic or cyclic groups, and/or carbonatom belonging to a functional group, for example, an may be linear or branched. A “hydrocarbyl group,” “hydro acyl group (-COO)R), a formyl group (-CO)H), a carboxy carbylene group, and “hydrocarbon group' can include 55 group ( C(O)OH), a hydrocarboxycarbonyl group ( C(O) rings, ring Systems, aromatic rings, and aromatic ring Sys OR), a cyano group (-C=N), a carbamoyl group (-COO) tems, which contain only carbon and hydrogen. “Hydrocar NH), a N-hydrocarbylcarbamoyl group (—C(O)NHR), or byl groups.” “hydrocarbylene groups.” and “hydrocarbon N,N'-dihydrocarbylcarbamoyl group ( C(O)NR), among groups' include, by way of example, aryl, arylene, arene other possibilities. In another aspect, the hydrogen atom(s) groups, alkyl, alkylene, alkane group, cycloalkyl, cycloalky 60 removed to form the “organyl group.” “organylene group.’ or lene, cycloalkane groups, aralkyl, aralkylene, and aralkane "organic group' may be attached to a carbonatom not belong groups, respectively, among other groups as members. ing to, and remote from, a functional group, for example, An aliphatic compound is a non-aromatic organic com —CHC(O)CH, —CHNR, and the like. An "organyl pound. An “aliphatic group' is a generalized group formed by group.” “organylene group, or “organic group' may be ali removing one or more hydrogen atoms (as needed for the 65 phatic or aromatic, cyclic or acyclic, and/or linear or particular group) from the carbon atoms of an aliphatic com branched. “Organyl groups.” “organylene groups, and pound. An aliphatic compound may be acyclic or cyclic, "organic groups' also encompass heteroatom-containing US 8,471,085 B2 10 rings, heteroatom-containing ring systems, heteroaromatic carbon-carbon double bond. The term “alkene' includes ali rings, and heteroaromatic ring systems. Finally, it is noted phatic or aromatic, cyclic or acyclic, and/or linear and that the “organyl group,” “organylene group.’ or “organic branched alkenes unless expressly stated otherwise. The term group' definitions include “hydrocarbyl group.” “hydrocar “alkene.” by itself, does not indicate the presence or absence bylene group,” “hydrocarbon group respectively, and “alkyl of heteroatoms and/or the presence or absence of other car group.” “alkylene group.” and "alkane group.’ respectively, bon-carbon double bonds unless explicitly indicated. The among others, as members. terms “hydrocarbon alkene' or “alkene hydrocarbon” refer to For the purposes of this application, the term or variations alkenes containing only hydrogen and carbon. Other identi of the term “organyl group consisting of inert functional fiers may be utilized to indicate the presence or absence of groups' refers to an organyl group wherein the organic func 10 particular groups within an alkene. Alkenes may also be fur tional groups and/or atoms other than carbon and hydrogen ther identified by the position of the carbon-carbon double present in the functional group are restricted to those func bond. Alkenes, having more than one Such multiple bond are tional groups and/or atoms other than carbon and hydrogen alkadienes, alkatrienes, and so forth. The alkene may be fur which are non-reactive under the process conditions defined ther identified by the position of the carbon-carbon double herein. Thus, the term or variation of the term “organyl groups 15 bond(s). consisting of inert functional groups' further defines the par An “alkenyl group' is a univalent group derived from an ticular organyl groups that can be present. Additionally, the alkene by removal of a hydrogenatom from any carbonatom term “organyl group consisting of inert functional groups” of the alkene. Thus, “alkenyl group' includes groups in which can refer to the presence of one or more inert functional the hydrogen atom is formally removed from an sphybrid groups within the organyl group. The term or variation of the ized (olefinic) carbonatom and groups in which the hydrogen "organyl group consisting of inert functional group' defini atom is formally removed from any other carbon atom. For tion includes the hydrocarbyl group, among others, as a mem example and unless otherwise specified, propen-1-yl ber. (—CH=CHCH), propen-2-yl (CH)C=CH), and pro For purposes of this application, an “inert functional pen-3-yl (-CH-CH=CH-)groups are all encompassed with group' is a group which does not substantially interfere with 25 the term “alkenyl group.’ Similarly, an “alkenylene group' any process described herein in which it takes part (e.g. inter refers to a group formed by formally removing two hydrogen fere with the oligomerization process). Non-limiting atoms from an alkene, either two hydrogen atoms from one examples of inert functional groups which may not Substan carbonatom or one hydrogenatom from two different carbon tially interfere with any process described herein can include atoms. An “alkene group' refers to a generalized group halogens (fluoro, chloro, bromo, and iodo), organoxy groups 30 formed by removing one or more hydrogenatoms (as needed (e.g. hydrocarboxy group or alkoxy group among others), for the particular group) from an alkene. When the hydrogen sulfidyl groups, and/or hydrocarbyl groups. atom is removed from a carbon atom participating in a car A cycloalkane is a saturated cyclic hydrocarbon, with or bon-carbon double bond, the regiochemistry of the carbon without side chains (e.g. cyclobutane or methylcyclobutane). from which the hydrogen atom is removed, and regiochem Unsaturated cyclic hydrocarbons having one endocyclic 35 istry of the carbon-carbon double bond may both be specified. double or one triple bond are called cycloalkenes and The terms “alkenyl group,” “alkenylene group, and “alkene cycloalkynes, respectively. Those having more than one Such group' by themselves do not indicate the presence or absence multiple bond are cycloalkadienes, cycloalkatrienes, and so of heteroatoms and/or the presence or absence of other car forth. bon-carbon double bonds unless explicitly indicated. The A “cycloalkyl group' is a univalent group derived by 40 terms “hydrocarbon alkenyl group,” “hydrocarbon alk removing a hydrogen atom from a ring carbon atom from a enylene group, and “hydrocarbon alkene group' refer to cycloalkane. For example, a 1-methylcyclopropyl group and alkene groups containing only hydrogen and carbon. Other a 2-methylcyclopropyl group are illustrated as follows. identifiers may be utilized to indicate the presence or absence of particular groups within an alkene group. Alkenyl groups 45 may also have more than one such multiple bond. The alkene group may also be further identified by the position of the carbon-carbon double bond(s). The term “alkyne' is used in this specification and claims to refer to a compound that has at least one carbon-carbon 50 triple bond. The term “alkyne' includes aliphatic or aromatic, cyclic or acyclic, and/or linear and branched alkynes unless Similarly, a “cycloalkylene group' refers to a group derived expressly stated otherwise. The term “alkyne.” by itself, does by removing two hydrogenatoms from a cycloalkane, at least not indicate the presence or absence of heteroatoms and/or one of which is a ring carbon. Thus, a “cycloalkylene group' the presence or absence of other carbon-carbon triple bonds includes both a group derived from a cycloalkane in which 55 unless explicitly indicated. The terms “hydrocarbon alkyne' two hydrogenatoms are formally removed from the same ring or “alkyne hydrocarbon refer to alkyne compounds contain carbon, a group derived from a cycloalkane in which two ing only hydrogen and carbon. Other identifiers may be uti hydrogenatoms are formally removed from two different ring lized to indicate the presence or absence of particular groups carbons, and a group derived from a cycloalkane in which a within an alkyne. Alkynes, having more than one Such mul first hydrogen atom is formally removed from a ring carbon 60 tiple bond are alkadiynes, alkatriynes, and so forth. The and a second hydrogen atom is formally removed from a alkyne group may also be further identified by the position of carbon atom that is not a ring carbon. A “cycloalkane group' the carbon-carbon triple bond(s). refers to a generalized group formed by removing one or more An “alkynyl group' is a univalent group derived from an hydrogen atoms (as needed for the particular group and at alkyne by removal of a hydrogenatom from any carbonatom least one of which is a ring carbon) from a cycloalkane. 65 of the alkyne. Thus, “alkynyl group' includes groups in The term “alkene' whenever used in this specification and which the hydrogen atom is formally removed from an Sp claims refers to a compound that has at least one non-aromatic hybridized (acetylenic) carbon atom and groups in which the US 8,471,085 B2 11 12 hydrogen atom is formally removed from any other carbon matic compounds) and "heteroarenes, also termed “hetare atom. For example and unless otherwise specified, 1-propyn nes’ (heteroaromatic compounds formally derived from are 1-yl ( C=CCH) and propyn-3-yl (HC=CCH2—) groups nes by replacement of one or more methine (-C=) carbon are all encompassed with the term “alkynyl group.’ Similarly, atoms by trivalent or divalent heteroatoms, in Such away as to an “alkynylene group' refers to a group formed by formally maintain the continuous pi-electron system characteristic of removing two hydrogen atoms from an alkyne, either two aromatic systems and a number of out-of-plane pi-electrons hydrogen atoms from one carbon atom if possible or one corresponding to the Hickel rule (4n+2). While arenes and hydrogenatom from two different carbon atoms. An “alkyne heteroarenes are mutually exclusive members of the group of group' refers to a generalized group formed by removing one aromatic compounds, a compound that has both an arene or more hydrogen atoms (as needed for the particular group) 10 group and a heteroarene group that compound generally is from an alkyne. The terms “alkynyl group,” “alkynylene considered a heteroarene compound. Aromatic compounds, group, and “alkyne group' by themselves do not indicate the arenes, and heteroarenes may be mono- or polycyclic unless presence or absence of heteroatoms and/or the presence or otherwise specified. Examples of arenes include, but are not absence of other carbon-carbon double bonds unless explic limited to, benzene, naphthalene, and toluene, among others. itly indicated. The terms “hydrocarbon alkynyl group.” 15 Examples of heteroarenes include, but are not limited to “hydrocarbon alkynylene group, and “hydrocarbon alkyne furan, pyridine, and methylpyridine, among others. As dis group' refer to olefin groups containing only hydrogen and closed herein, the term “substituted may be used to describe carbon. Other identifiers may be utilized to indicate the pres an aromatic group wherein any non-hydrogen moiety for ence or absence of particular groups within an alkyne group. mally replaces a hydrogen in that group, and is intended to be Alkyne groups may have more than one such multiple bond. non-limiting. Alkyne groups may also be further identified by the position An “aryl group' refers to a generalized group formed by of the carbon-carbon triple bond(s). removing a hydrogen atom from an aromatic hydrocarbon The term “alpha olefin” as used in this specification and ring carbon atom from an arene. One example of an “aryl claims refers to an olefin that has a double bond between the group' is ortho-tolyl (o-tolyl), the structure of which is shown first and second carbon atom of the longest contiguous chain 25 here. of carbon atoms. The term “alpha olefin' includes linear and branched alpha olefins unless expressly stated otherwise. In the case of branched alpha olefins, a branch may be at the 2-position (a vinylidene) and/or the 3-position or higher with CH3 respect to the olefin double bond. The term “vinylidene’ 30 whenever used in this specification and claims refers to an alpha olefin having a branch at the 2-position with respect to the olefin double bond. By itself, the term “alpha olefin' does not indicate the presence or absence of heteroatoms and/or the presence or absence of other carbon-carbon double bonds 35 Similarly, an “arylene group' refers to a group formed by unless explicitly indicated. The terms “hydrocarbon alpha removing two hydrogen atoms (at least one of which is from olefin' or “alpha olefin hydrocarbon” refer to alpha olefin an aromatic hydrocarbon ring carbon) from an arene. An compounds containing only hydrogen and carbon. "arenegroup' refers to a generalized group formed by remov The term “linear alpha olefin” as used herein refers to a ing one or more hydrogen atoms (as needed for the particular linear olefin having a double bond between the first and 40 group and at least one of which is an aromatic hydrocarbon second carbon atom. The term “linear alpha olefin' by itself ring carbon) from an arene. However, if a group contains does not indicate the presence or absence of heteroatoms separate and distinct arene and heteroarene rings or ring sys and/or the presence or absence of other carbon-carbon double tems (e.g. the phenyl and benzofuran moieties in 7-phenyl bonds, unless explicitly indicated. The terms “linear hydro benzofuran) its classification depends upon the particular ring carbon alpha olefin' or “linear alpha olefin hydrocarbon 45 or ring system from which the hydrogen atom was removed, refers to linear alpha olefin compounds containing only that is, an arenegroup if the removed hydrogen came from the hydrogen and carbon. aromatic hydrocarbon ring or ring system carbon atom (e.g. The term “normal alpha olefin' whenever used in this the 2 carbon atom in the phenyl group of 6-phenylbenzofu specification and claims refers to a linear hydrocarbon mono ran) and a heteroarenegroup if the removed hydrogen carbon olefin having a double bond between the first and second 50 came from a heteroaromatic ring or ring system carbonatom carbon atom. It is noted that “normal alpha olefin' is not (e.g. the 2 or 7 carbon atom of the benzofuran group of synonymous with “linear alpha olefin” as the term “linear 6-phenylbenzofuran). alpha olefin” can include linear olefinic compounds having a An “aralkyl group' is an aryl-substituted alkyl group hav double bond between the first and second carbon atoms and ing a free Valance at a non-aromatic carbon atom, for having heteroatoms and/or additional double bonds. 55 example, a benzyl group is an “aralkyl group. Similarly, an An 'aromatic group' refers to a generalized group formed “aralkylene group' is an aryl-substituted alkylene group hav by removing one or more hydrogen atoms (as needed for the ing two free Valances at a single non-aromatic carbonatom or particular group and at least one of which is an aromatic ring a free Valence at two non-aromatic carbon atoms while an carbon atom) from an aromatic compound. Thus, an “aro “aralkane group' is a generalized is an aryl-substituted alkane matic group’ as used herein refers to a group derived by 60 group having one or more free Valances at a non-aromatic removing one or more hydrogen atoms from an aromatic carbon atom(s). A "heteroaralkyl group' is a heteroaryl-sub compound, that is, a compound containing a cyclically con stituted alkyl group having a free Valence at a non-heteroaro jugated hydrocarbon that follows the Hickel (4n+2) rule and matic ring or ring system carbon atom. Similarly a "het containing (4n+2) pi-electrons, where n is an integer from 1 to eroaralkylene group' is a heteroaryl-substituted alkylene about 5. Aromatic compounds and hence 'aromatic groups” 65 group having a two free Valances at a single non-heteroaro may be monocyclic or polycyclic unless otherwise specified. matic ring or ring system carbon atom or a free Valences at Aromatic compounds include “arenes’ (hydrocarbon aro two non-heteroaromatic ring or ring system carbon atoms US 8,471,085 B2 13 14 while a "heteroaralkane group' is a generalized aryl-substi Oligomerization Catalyst System tuted alkane group having one or more free Valances at a The oligomerization catalyst system minimally comprises non-heteroaromatic ring or ring system carbon atom(s). a transition metal compound, a pyrrole compound, and a If a compound or group contains more than one moiety it is metal alkyl. In another aspect, the oligomerization catalyst formally a member of the group having the highest naming system may further comprise a halogen containing com priority as stipulated by IUPAC. For example 4-phenyl-pyri pound. The transition metal compound, pyrrole compound, dine is a heteroaromatic compound and a 4-(phen-2-ylene) metal alkyl, and optional halogen containing compound are pyridin-2-yl group is a hetero-aromatic group because the independent elements of the oligomerization catalyst system. highest naming groups is the pyridine group and the pyridin These elements of the oligomerization catalyst system are 2-yl group respectively. 10 independently described herein and the catalyst system may A silane is a compound containing a silicone atom. A 'silyl be further described utilizing any combination of the transi group' is a generalized group formed by removing a hydro tion metal described herein, the pyrrole compound described gen atom from the silicon atom of a silane. herein, metal alkyl described herein, and optional halogen An “organoaluminum compound is used to describe any 15 containing compound described herein. compound that contains an aluminum-carbon bond. Thus, Transition Metal Compound organoaluminum compounds include hydrocarbyl aluminum Generally, the transition metal compound for the oligomer compounds such as trialkyl-, dialkyl-, or monoalkylalumi ization catalyst system can comprise, consistessentially of, or num compounds; hydrocarbyl alumoxane compounds, and consist of a group 5, 6, 7, 8, 9, 10, or 11 transition metal. In aluminate compounds which contain an aluminum-organyl Some embodiments, the transition metal compound com bond such as tetrakis(p-tolyl)aluminate salts. prises, consists essentially of, or consists of chromium, The term “reactor effluent, and it derivatives (e.g. oligo nickel, cobalt, iron, molybdenum, or copper. In other embodi merization reactor effluent) generally refers to all the material ments, the transition metal compound comprises, consists which exits the reactor. The term “reactor effluent, and its essentially of, or consists of chromium. derivatives, may also be prefaced with other descriptors that 25 In some aspects, the transition metal compound for the limit the portion of the reactor effluent being referenced. For oligomerization catalyst System may be an inorganic transi example, while the term “reactor effluent” would refer to all tion metal compound. In other aspects, the transition metal material exiting the reactor (e.g. Product and solvent or dilu compound may contain ligands formally derived from an ent, among others), the term “olefin reactor effluent” refers to organic compound or moiety (e.g. a carboxylate, alkoxide, or the effluent of the reactor which contains an olefin (i.e. car 30 beta-dionate, among others). In an embodiment, Suitable bon-carbon) double bond. inorganic transition metal compounds include, but are not The term "oligomerization,” and its derivatives, refers to limited to, a transition metalhalide, a transition metal sulfate, processes which produce a mixture of products containing at a transition metal sulfite, a transition metal bisulfate, a tran least 70 weight percent products containing from 2 to 30 sition metal oxide, a transition metal nitrate, a transition metal monomer units. Similarly, an "oligomer is a product that 35 nitrite, a transition metal hydroxide, a transition metal chlo contains from 2 to 30 monomer units while an "oligomeriza rate, or any combinations thereof, alternatively, transition tion product includes all products made by the "oligomer metal halide, a transition metal Sulfate, a transition metal ization’ process including the "oligomers' and products pro oxide, or a transition metal nitrate. In an embodiment, the duced by the process which are not "oligomers' (e.g. product transition metal halide may be a transition metal chloride, a which contain more than 30 monomer units. It should be 40 transition metal bromide, or a transition metal iodide. In an noted that the monomer units in the "oligomer' or "oligomer embodiment, the transition metal compound may be a tran ization product” do not have to be the same. For example, an sition metal alkoxide, a transition metal aryloxide, a transi "oligomer' or "oligomerization product of an "oligomeriza tion metal carboxylate, a transition metal beta-dionate (such tion' process using ethylene and propylene as monomers may as an acetylacetonate), or a transition metal amide compound; contain both ethylene and/or propylene units. 45 alternatively, a transition metal alkoxide or transition metal The term “trimerization, and it derivatives, refers to a aryloxide; alternatively, a transition metal carboxylate, a tran process which produces a product containing at least 70 sition metal beta-dionate; or alternatively, a transition metal weight percent products containing three and only three amide. Further, in another aspect, Suitable transition metal monomer units. A “trimer' is a product which contains three compounds can contain combinations of these recited and only three monomer units while a “trimerization product’ 50 ligands. In some embodiments, the transition metal com includes all products made by the trimerization process pound comprises, consists essentially of, or consists of a including trimer and products which are not trimer (e.g. transition metal carboxylate. dimers or tetramers). Generally, an olefin trimerization Alternatively, and in any aspect and embodiment, Suitable reduces number of olefinic bonds, i.e., carbon-carbon double transition metal compounds may comprise, consist essen bonds, by two when considering the number of olefin bonds 55 tially of, or consist of a transition metal halide; alternatively, in the monomer units and the number of olefin bonds in the a transition metal Sulfate; alternatively, a transition metal trimer. It should be noted that the monomer units in the sulfite; alternatively, a transition metal bisulfate; alterna “trimer' or “trimerization product” do not have be the same. tively, a transition metal oxide; alternatively, a transition For example, a “trimer of a “trimerization' process using metal nitrate; alternatively, a transition metal nitrite; alterna ethylene and butene as monomers may contain ethylene and/ 60 tively, a transition metal hydroxide; alternatively, a transition or butene monomer units. That is to say the “trimer' may metal alkoxide; alternatively, a transition metal aryloxide; include C, Cs, Co. and C2 products. In another example, a alternatively, a transition metal carboxylate; alternatively, a “trimer of a “trimerization' process using ethylene as the transition metal beta-dionate; alternatively, a transition metal monomer may contain ethylene monomerunits. It should also chlorate; or alternatively, a transition metal amide. In an be noted that a single molecule may contain two monomer 65 embodiment, the transition metal halide may be a transition units. For example, dienes such as 1,3-butadiene and 1,4- metal chloride; alternatively, a transition metal bromide; or pentadiene have two monomer units within one molecule. alternatively, a transition metal iodide. US 8,471,085 B2 15 16 According to a further aspect of this disclosure and in any chromium(III) fluoride; alternatively, chromium(III) chlo embodiment, each hydrocarboxy group (alkoxy or aryloxy), ride; alternatively, chromium(III) bromide; or alternatively, carboxylate group, beta-dionate group, or amide group of the chromium(III) iodide. transition metal compound may be a C to C, a Cato Co., or In yet an additional aspect of this disclosure and in any a Cs to Chydrocarboxy group (alkoxy oraryloxy), carboxy 5 embodiment, the transition metal compound for the oligo late group, beta-dionate group, oramide group. In an embodi merization catalyst system comprise, consistessentially of or ment, each carboxylate group of the transition metal com consist of a chromium(II) alkoxide, a chromium(II) carboxy pound may be a C to C. carboxylate group; alternatively, a late, a chromium(II) beta-dionate, a chromium(III) alkoxide, C to Co. carboxylate group; or alternatively, a C to C a chromium(III) carboxylate, or a chromium(III) beta-dion 10 ate; alternatively, a chromium(II) alkoxide or a chromium carboxylate group. In some embodiments, eachalkoxy group (III) alkoxide; alternatively, a chromium(II) carboxylate or a of the transition metal compound may be a C to Calkoxy chromium(III) carboxylate; alternatively, a chromium(II) group; alternatively, a C to Co alkoxy group; or alterna beta-dionate or a chromium(III) beta-dionate; alternatively, a tively, a Cs to Calkoxy group. In other embodiments, each chromium(II) alkoxide; alternatively, a chromium(II) car aryloxy group of the transition metal compound may be a C 15 boxylate; alternatively, a chromium(II) beta-dionate; alterna to C2a alkoxy group; alternatively, a C to Coalkoxy group: tively, a chromium(III) alkoxide; alternatively, a chromium or alternatively, a C to C2 alkoxy group. In yet other (III) carboxylate; or alternatively, a chromium(III) beta embodiments, each beta-dionate group of the transition metal dionate. In an embodiment, each carboxylate group of the compound may be a Cs to C beta-dionate group; alterna chromium compound may be a C to C. carboxylate group; tively, a Cs to Co. beta-dionate group; or alternatively, a Cs to alternatively, a C to Co. carboxylate group; or alternatively, C beta-dionate group. In further embodiments, amide group a Cs to C carboxylate group. In some embodiments, each of the transition metal compound may be a C to C amide alkoxy group of the chromium compound may be a C to Ca group; alternatively, a C to Camide group; or alternatively, alkoxy group; alternatively, a C to C alkoxy group; or a Cato C amide group. In some embodiments, the carboxy alternatively, a Cs to Calkoxy group. In other embodiments, late of the transition metal carboxylate may be monocarboxy 25 each aryloxy group of the chromium compound may be a C late. to C2a aryloxy group; alternatively, a C to Co aryloxy group: According to a further aspect of this disclosure and in any or alternatively, a C to C aryloxy group. In yet other embodiment, the transition metal of the transition metal com embodiments, each beta-dionate group of the chromium pound can have an oxidation state of 0, +1 (or 1), +2 (or 2), +3 compound may be a Cs to C beta-dionate group; alterna (or 3), +4 (or 4), +5 (or 5), or +6 (or 6), respectively. In another 30 tively, a Cs to Co. beta-dionate group; or alternatively, a Cs to aspect and in other embodiments, the transition metal com C beta-dionate group. In further embodiments, amide group pound can have an oxidation state of +2 or +3; or alternatively, of the chromium compound may be a C to Camide group: the transition metal compound can have an oxidation state of alternatively, a C to Camide group; or alternatively, a C to +3. Further to this aspect and in any embodiment, the transi C12 amide group. tion metal compound can have an oxidation state of 0; alter 35 Chromium carboxylates are particularly useful transition natively, +1; alternatively, +2; alternatively, +3, alternatively, metal compounds for the oligomerization catalyst system. +4; alternatively, +5; or alternatively, +6. Thus, in one aspect, the catalyst system and process accord In still a further aspect of this disclosure, the transition ing to this disclosure provides for the use of chromium car metal compound of the oligomerization catalyst system may boxylate compositions, including but are not limited to, chro comprise, consist essentially of, or consist of a chromium 40 mium carboxylate compositions in which the carboxylate is a compound. In this aspect, the chromium compound can have C. to C monocarboxylate; alternatively, a C to Co. mono a chromium oxidation state of 0 to 6. In some embodiments, carboxylate; or alternatively, a C to C monocarboxylate. the chromium within the chromium compound may have an Some widely employed chromium carboxylate composition oxidation state of 2 or 3 (i.e., a chromium(II) or chromium catalysts are those of chromium(III), for example, chromium (III) compound). In other embodiments, the chromium within 45 (III) compositions comprising 2-ethylhexanoate are effective the chromium compound can have an oxidation state of 2 (i.e. catalyst system components for selective 1-hexene synthesis. a chromium(II) compound); or alternatively, have an oxida In one aspect, the carboxylate group of the chromium tion state of 3 (i.e. a chromium(III) compound). For example, carboxylate may be a C to C monocarboxylate. In an chromium(II) compounds which may be used as the transi embodiment, the carboxylate group of the chromium car tion metal compound for the oligomerization catalyst system 50 boxylate may be an acetate, a propionate, a butyrate, a pen may comprise, consist essentially of, or consist of chromium tanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, (II) nitrate, chromium(II) sulfate, chromium(II) fluoride, a decanoate, an undecanoate, a dodecanoate, a tridecanoate, a chromium(II) chloride, chromium(II) bromide, or chromium tetradecanoate, a pentadecanoate, a hexadecanoate, a hepta (II) iodide. Also by way of example, the chromium(III) com decanoate, or an octadecanoate; or alternatively, a pen pounds which may be used as the transition metal compound 55 tanoate, a hexanoate, a heptanoate, a octanoate, a nonanoate, for the oligomerization catalyst system may comprise, con a decanoate, a undecanoate, or a dodecanoate. In some sist essentially of, or consist of chromium(III) nitrate, chro embodiments, the carboxylate group of the chromium car mium(III) sulfate, chromium(III) fluoride, chromium(III) boxylate may be acetate, propionate, n-butyrate, isobutyrate, chloride, chromium(III) bromide, or chromium(III) iodide. Valerate (n-pentanoate), neo-pentanoate, capronate (n-hex Alternatively, the chromium compounds that can be used as 60 anoate), n-heptanoate, caprylate (n-octanoate), 2-ethylhex the transition metal compound for the oligomerization cata anoate, n-nonanoate, caprate (n-decanoate), n-undecanoate, lyst system may comprise, consistessentially of, or consist of laurate (n-dodecanoate), or Stearate (n-octadecanoate); alter chromium(II) nitrate; alternatively, chromium(II) sulfate: natively, Valerate (n-pentanoate), neo-pentanoate, capronate alternatively, chromium(II) fluoride; alternatively, chromium (n-hexanoate), n-heptanoate, caprylate (n-octanoate), 2-eth (II) chloride; alternatively, chromium(II) bromide; alterna 65 ylhexanoate, n-nonanoate, caprate (n-decanoate), n-unde tively, chromium(II) iodide; alternatively, chromium(III) canoate, or laurate (n-dodecanoate); alternatively, acetate; nitrate; alternatively, chromium(III) sulfate; alternatively, alternatively, propionate; alternatively, n-butyrate; alterna US 8,471,085 B2 17 18 tively, isobutyrate; alternatively, Valerate (n-pentanoate); pyrrole compound is defined as a compound comprising a alternatively, neo-pentanoate, alternatively, capronate 5-membered, nitrogen-containing heterocycle. Such as for (n-hexanoate); alternatively, n-heptanoate; alternatively, example, pyrrole, derivatives of pyrrole, and mixtures caprylate (n-octanoate); alternatively, 2-ethylhexanoate; thereof. Broadly, the pyrrole compound may be pyrrole or any alternatively, n-nonanoate; alternatively, caprate (n-de heteroleptic or homoleptic metal complex or salt containing a canoate); alternatively, n-undecanoate; alternatively, laurate pyrrollide radical or ligand. (n-dodecanoate); or alternatively, Stearate (n-octadecanoate). Generally, the pyrrole compound may be a Cato Co., or C. In an aspect and in any embodiment, the transition metal to Co. pyrrole. Exemplary pyrrole compounds that may be compound for the oligomerization catalyst system may com used in the oligomerization catalyst system include, but are prise, consist essentially of, or consist of a chromium(II) 10 not limited to pyrrole-2-carboxylic acid, 2-acetylpyrrole, pyr carboxylate; or alternatively, a chromium(III) carboxylate. role-2-carboxaldehyde, tetrahydroindole, 2,5-dimethylpyr Exemplary chromium(II) carboxylates may include, but are role, 2,4-dimethyl-3-ethylpyrrole, 3-acetyl-2,4-dimethylpyr not limited to, chromium(II) acetate, chromium(II) propi role, ethyl-2,4-dimethyl-5-(ethoxycarbonyl)-3-pyrrole onate, chromium(II) butyrate, chromium(II) isobutyrate, proprionate, ethyl-3,5-dimethyl-2-pyrrollecarboxylate, chromium(II) neopentanoate, chromium(II) oxalate, chro 15 pyrrole, 2,5-dimethylpyrrole, 3,4-dimethylpyrrole, 3,4- mium(II) octanoate, chromium(II) (2-ethylhexanoate), chro dichloropyrrole, 2,5-diethylpyrrole, 2-methyl-5-ethylpyr mium(II) laurate, or chromium(II) Stearate; or alternatively, role, 2-methyl-5-propylpyrrole, 2,3,4,5-tetrachloropyrrole, chromium(II) acetate, chromium(II) propionate, chromium 2-acetylpyrrole, pyrazole, pyrrolidine, indole, and dipyrro (II) butyrate, chromium(II) isobutyrate, chromium(II) neo lomethane, and mixtures thereof, among others. Pyrrollides pentanoate, chromium(II) octanoate, chromium(II) (2-ethyl that may be used as the nitrogen compound include diethyla hexanoate), chromium(II) laurate, or chromium(II) Stearate. luminum 2,5-dimethylpyrrollide; ethylaluminum di(2,5-dim In an aspect and in any embodiment, the transition metal ethylpyrrollide); and aluminum tri(2,5-dimethylpyrrollide); compound utilized in the catalyst System may comprise, con among others. sist essentially of, or consist of chromium(III) acetate, chro In an aspect, the pyrrole compound may have Formula Pl mium(III) propionate, chromium(III) butyrate, chromium 25 or Formula I1. In an embodiment, the pyrrole compound may (III) isobutyrate, chromium(III) neopentanoate, chromium have Formula P1; or alternatively Formula I1. (III) oxalate, chromium(III) octanoate, chromium(III) 2-ethylhexanoate, chromium(III) 2.2.6,6-tetramethylhep tanedionate, chromium(III) naphthenate, chromium(III) lau P1 rate, or chromium(III) Stearate; or alternatively, chromium 30 (III) acetate, chromium(III) propionate, chromium(III) butyrate, chromium(III) isobutyrate, chromium(III) neopen tanoate, chromium(III) octanoate, chromium(III) 2-ethylhex anoate, chromium(III) 2.2.6.6-tetramethylheptanedionate, chromium(III) naphthenate, chromium(III) laurate, or chro 35

mium(III) Stearate. In a further aspect and in any number of embodiments, the transition metal compound for the oligo merization catalyst System may comprise, consist essentially of or consist of chromium(II) acetate; alternatively, chro mium(II) propionate; alternatively, chromium(II) butyrate; 40 alternatively, chromium(II) isobutyrate; alternatively, chro mium(II) neopentanoate; alternatively, chromium(II) oxalate; alternatively, chromium(II) octanoate; alternatively, chromium(II) (2-ethylhexanoate); alternatively, chromium (II) laurate; alternatively, chromium(II) Stearate; alterna 45 tively, chromium(III) acetate; alternatively, chromium(III) In an aspect, Re, Re, R, and RP of Formula P1 and R', propionate; alternatively, chromium(III) butyrate; alterna R,R,R,R, and R7 of Formula I1 may independently be tively, chromium(III) isobutyrate; alternatively, chromium a hydrogen, a C to C1s organyl group, or a Cs to Cao silyl (III) neopentanoate; alternatively, chromium(III) oxalate; group; alternatively, hydrogen, a C to Cs organyl group, or alternatively, chromium(III) octanoate; alternatively, chro 50 a C to Cassilyl group; alternatively, hydrogen, a C to Co mium(III) 2-ethylhexanoate; alternatively, chromium(III) organyl group, or a C to Cosilyl group; alternatively, hydro 2.2.6.6-tetramethylheptane dionate; alternatively, chromium gen, a C to Cs organyl group, or a C to Cls silyl group: (III) naphthenate; alternatively, chromium(III) laurate; or alternatively, hydrogen or a C to Cs organyl group; alterna alternatively, chromium(III) Stearate. In some embodiments, tively, hydrogen or a C to Cs organyl group; alternatively, the transition metal compound for the oligomerization cata 55 hydrogen or a C to Co organyl group; or alternatively, lyst system may comprise, consistessentially of, or consist of hydrogenora C, to Cs organyl group. In an embodiment, R. chromium(II) 2-ethylhexanoate or chromium(III) 2-ethyl RP, RP, and RP of Formula P1 and R,R,R,R,R, and hexanoate; or alternatively chromium(III) 2-ethylhexanoate. R" of Formula I1 may independently be a hydrogen, a C, to Pyrrole Compound Cs hydrocarbyl group, or a C to Co. silyl group; alterna In an aspect, the pyrrole compound (also called the "pyr 60 tively, hydrogen, a C to Cs hydrocarbyl group, or a C to Cas role”) of the oligomerization catalyst System can comprise, silyl group; alternatively, hydrogen, a C to Co. hydrocarbyl consist essentially of, or consist of any pyrrole compound group, or a C to Cs silyl group; alternatively, hydrogen, a C that will react with a chromium source to form a transition to Cs hydrocarbyl group, or a C to Cs silyl group; alterna metal pyrrollide complex (e.g. chromium pyrrollide complex). tively, hydrogen or a C to Cs hydrocarbyl group; alterna As used in this disclosure, the term "pyrrole compound 65 tively, hydrogen or a C to Cs hydrocarbyl group; alterna refers to pyrrole (CHN), derivatives of pyrrole (e.g. indole), tively, hydrogen or a C to Co. hydrocarbyl group; or Substituted pyrroles, as well as metal pyrrollide complexes. A alternatively, hydrogen or a C to Cs hydrocarbyl group. US 8,471,085 B2 19 20 In an embodiment wherein the pyrrole compound has For butyl group; or alternatively, a neopentyl group. In an mula P1, RP and R may be hydrogen and RP and RP may embodiment, any of these alkyl groups may be substituted be any non-hydrogen pyrrole Substituent described herein; with a halide, or hydrocarboxy group to form the substituted alternatively, Rand R may be hydrogen and Rand R' alkyl group which may be utilized as a non-hydrogen R. may be any non-hydrogen pyrrole Substituent described RP, R, and/or RP group of Formula P1 or a non-hydrogen herein; or alternatively, RandR may behydrogen andR R. R. R. R. R. and/or R' group of Formula I1. Sub and R may be any non-hydrogen pyrrole substituent stituenthalides and hydrocarboxy groups are disclosed herein described herein. In some embodiments, R. R. and R' and may be utilized without limitation to further describe the may be hydrogen and R may be any non-hydrogen pyrrole Substituted alkyl group which may be utilized as a non-hy substituent described herein; alternatively, R. R. and R' 10 may be hydrogen and R may be any non-hydrogen pyrrole drogen R. R. R. and/or R group of Formula P1 or a substituent described herein; or alternatively, R may be non-hydrogen R. R. R. R. R', and/or R7 group of hydrogen and R. R', and R may be any non-hydrogen Formula I1. substituent described herein. In other embodiments, R. R. In an embodiment, the cycloalkyl group or Substituted R', and R may be any non-hydrogen pyrrole substituent 15 cycloalkyl group which may be utilized as a non-hydrogen described herein. R. R. R. and/or R group of Formula P1 or a non In an embodiment, each non-hydrogen group which may hydrogen R. R. R. R. R', and/or R group of Formula be utilized as RP, R,R, and/or RP of Formula P1 and R', Il may be a cyclobutyl group, a substituted cyclobutyl group, R,R,R,R, and/or R7 of Formula I1 may independently a cyclopentyl group, a Substituted cyclopentyl group, a cyclo be an alkyl group, a Substituted alkyl group, a cycloalkyl hexyl group, a Substituted cyclohexyl group, a cycloheptyl group, a Substituted cycloalkyl group, an aromatic group, a group, a Substituted cycloheptyl group, a cyclooctyl group, or Substituted aromatic group, an aryl group, a Substituted aryl a Substituted cyclooctyl group. In some embodiments, the group, an aralkyl group, a Substituted aralkyl group, or a silyl cycloalkyl group or Substituted cycloalkyl group which may group. In other embodiments, each non-hydrogen group be utilized as a non-hydrogen R,R,R, and/or R group which may be utilized as R,R,R, and/or R of Formula 25 of Formula P1 or non-hydrogen R. R. R. R. R. and/or P1 and R', R. R. R. R., and/or R7 of Formula I1 may R" group of Formula I1 may be a cyclopentyl group, a Sub independently be an alkyl group; alternatively, a Substituted stituted cyclopentyl group, a cyclohexyl group, or a substi alkyl group; alternatively, a cycloalkyl group; alternatively, a tuted cyclohexyl group. In other embodiments, the cycloalkyl Substituted cycloalkyl group; alternatively, an aromatic group or Substituted cycloalkyl group which may be utilized group; alternatively, a Substituted aromatic group; alterna 30 a non-hydrogen RP, R, R, and/or RP group of Formula tively, an aryl group; alternatively, a Substituted aryl group; P1 or non-hydrogen R,R,R,R,R, and/or R group of alternatively, an aralkyl group; alternatively, a substituted Formula Il may be a cyclobutyl group or a substituted aralkyl group; or alternatively a silyl group. Generally, the cyclobutyl group; alternatively, a cyclopentyl group or a Sub alkyl group, Substituted alkyl group, cycloalkyl group, Sub stituted cyclopentyl group; alternatively, a cyclohexyl group stituted cycloalkyl group, aromatic group, Substituted aro 35 ora Substituted cyclohexyl group; alternatively, a cycloheptyl matic group, aryl group, Substituted aryl group, aralkyl group, group or a Substituted cycloheptyl group; or alternatively, a Substituted aralkyl group, and/or silyl group which may be cyclooctyl group, or a substituted cyclooctyl group. In further utilized as a non-hydrogen R. R. R. and/or R group of embodiments, the cycloalkyl group or Substituted cycloalkyl Formula P1 or non-hydrogen R,R,R,R,R, and/or R' group which may be utilized as a non-hydrogen R. R. R. group of Formula I1 may have the same number of carbons as 40 and/or R group of Formula P1 or non-hydrogen R. R. the its respective organyl group, hydrocarbyl group, or silyl R", R. R', and/or R group of Formula I1 may be a cyclo group which may be utilized as a non-hydrogen R. R. R. pentyl group; alternatively, a substituted cyclopentyl group; a and/or R group of Formula P1 or non-hydrogen R. R. cyclohexyl group; or alternatively, a Substituted cyclohexyl R", R. R. and/or R' group of Formula I1 disclosed herein. group. Substituents which may be utilized for the substituted In an embodiment, each alkyl group which may be utilized 45 cycloalkyl groups are independently disclosed herein and as a non-hydrogen R,R,R, and/or R group of Formula may be utilized without limitation to further describe the P1 or a non-hydrogen R. R. R. R. R', and/or R7 group Substituted cycloalkyl group which may be utilized as a non of Formula I1 may be a methyl group, an ethyl group, a propyl hydrogen R. R. R. and/or R group of Formula P1 or group, a butyl group, a pentyl group, a hexyl group, a heptyl non-hydrogen R. R. R. R. R', and/or R7 group of group, an octyl group, anonyl group, a decyl group, a undecyl 50 Formula I1. group, a dodecyl group, a tridecyl group, a tetradecyl group, In an aspect, the aryl group(s) which may be utilized as a a pentadecyl group, a hexadecyl group, a heptadecyl group, non-hydrogen RP, R, R, and/or RP group of Formula P1 an octadecyl group, or a nonadecyl group; or alternatively, a or a non-hydrogen R. R. R. R. R', and/or R' group of methyl group, an ethyl group, a propyl group, abutyl group, Formula I1 may be a phenyl group, a Substituted phenyl a pentyl group, a hexyl group, a heptyl group, an octyl group. 55 group, a naphthyl group, or a Substituted naphthyl group. In a nonyl group, or a decyl group. In some embodiments, each an embodiment, the aryl group(s) which may be utilized as a alkyl group which may be utilized as a non-hydrogen R. non-hydrogen R. R. R. and/or R group of Formula P1 R. R. and/or R group of Formula P1 or a non-hydrogen or a non-hydrogen R. R. R. R. R', and/or R' group of R. R. R. R. R', and/or R group of Formula I1 may be Formula Il may be a phenyl group or a substituted phenyl a methyl group, an ethyl group, a n-propyl group, an iso 60 group; alternatively, a naphthyl group or a Substituted naph propyl group, a n-butyl group, an iso-butyl group, a sec-butyl thyl group; alternatively, a phenyl group or a naphthyl group; group, a tert-butyl group, an n-pentyl group, an iso-pentyl or alternatively, a Substituted phenyl group or a Substituted group, a sec-pentyl group, or a neopentyl group; alternatively, naphthyl group. Substituents which may be utilized for the a methyl group, an ethyl group, an iso-propyl group, a tert Substituted phenyl groups or Substituted naphthyl groups are butyl group, or a neopentyl group; alternatively, a methyl 65 independently disclosed herein and may be utilized without group; alternatively, an ethyl group; alternatively, a n-propyl limitation to further describe the substituted phenyl groups or group; alternatively, an iso-propyl group; alternatively, a tert Substituted naphthyl groups which may be utilized as a non US 8,471,085 B2 21 22 hydrogen R. R. R. and/or R group of Formula P1 or substituents described herein. In an embodiment, R', R, non-hydrogen R. R. R. R. R', and/or R group of and R of the silyl group having the Formula Sil may inde Formula I1. pendently be an alkyl group, a Substituted alkyl group, a In an embodiment, the Substituted phenyl group which may cycloalkyl group, a Substituted cycloalkyl group, an aromatic be utilized as a non-hydrogen R’P, RP, R, and/or RP group group, a Substituted aromatic group, an aryl group, a Substi of Formula P1 or a non-hydrogen R,R,R,R,R, and/or tuted aryl group, an aralkyl group, or a substituted aralkyl R" group of Formula I1 may be a 2-substituted phenyl group, group; alternatively, an alkyl group; alternatively, a Substi a 3-substituted phenyl group, a 4-substituted phenyl group, a tuted alkyl group; alternatively, a cycloalkyl group; alterna 2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl tively, a Substituted cycloalkyl group; alternatively, an aro group, 3,5-disubstituted phenyl group, or a 2.4.6-trisubsti 10 matic group; alternatively, a Substituted aromatic group; tuted phenyl group. In other embodiments, the substituted alternatively, an aryl group; alternatively, a Substituted aryl phenyl group which may be utilized a non-hydrogen R. R. group; alternatively, an aralkyl group; or alternatively, a Sub R', and/or R group of Formula P1 or a non-hydrogen R', stituted aralkyl group. Alkyl groups, Substituted alkyl groups, R. R. R. R', and/or R' group of Formula I1 may be a cycloalkyl groups, Substituted cycloalkyl groups, aromatic 2-substituted phenyl group, a 4-substituted phenyl group, a 15 groups, Substituted aromatic groups, aryl groups, Substituted 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl aryl groups, aralkyl groups, and Substituted aralkyl groups group; alternatively, a 3-substituted phenyl group or a 3.5- have been independently described herein as potential non disubstituted phenyl group; alternatively, a 2-substituted phe hydrogen pyrrole Substituents and may be utilized, without nyl group or a 4-substituted phenyl group; alternatively, a limitation, as R', R, and R of the silyl group having the 2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl Formula Sil. group; alternatively, a 2-substituted phenyl group; alterna In an embodiment, each non-hydrogen Substituent(s) for tively, a 3-substituted phenyl group; alternatively, a 4-substi the Substituted cycloalkyl group, Substituted aromatic group, tuted phenyl group; alternatively, a 2,4-disubstituted phenyl Substituted aryl group, or Substituted aralkyl group which group; alternatively, a 2,6-disubstituted phenyl group; alter may be utilized as a non-hydrogen R. R. R. and/or R natively, 3.5-disubstituted phenyl group; or alternatively, a 25 group of Formula P1 or a non-hydrogen R,R,R,R,R, 2,4,6-trisubstituted phenyl group. Substituents which may be and/or R group of Formula I1 may independently be a utilized for these specific Substituted phenyl groups are inde halide, a C to Cohydrocarbyl group, or a C to Cohydro pendently disclosed herein and may be utilized without limi carboxy group; alternatively, a halide or a C to Co. hydro tation to further describe these substituted phenyl groups carbyl group; alternatively, a halide or a C to Co. hydrocar which may be utilized as a non-hydrogen R. R. R. 30 boxy group; alternatively, a C to Cohydrocarbyl group or a and/or R group of Formula P1 or non-hydrogen R. R. C to Co. hydrocarboxy group; alternatively, a halide; alter R", R, R, and/or R group of Formula I1. natively, a C to Cohydrocarbyl group; or alternatively, a C In an aspect, the aralkyl group(s) which may be utilized as to Cohydrocarboxy group. In some embodiments, each non a non-hydrogen RP, R, R, and/or RP group of Formula hydrogen Substituent(s) for the Substituted cycloalkyl group, P1 or a non-hydrogen R. R. R. R. R. and/or R' group 35 Substituted aromatic group, Substituted aryl group, or Substi of Formula I1 may be a benzyl group, or a substituted benzyl tuted aralkyl group which may be utilized as a non-hydrogen group. In an embodiment, the aralkyl group(s) which may be R. R. R. and/or R group of Formula P1 or a non utilized as a non-hydrogen RP, RP, R, and/or RP group of hydrogen R. R. R. R. R', and/or R' group of Formula Formula P1 or a non-hydrogen R. R. R. R. R', and/or I1 may independently be a halide, a C to Cs hydrocarbyl R" group of Formula I1 may be a benzyl group; or alterna 40 group, or a C to Cs hydrocarboxy group; alternatively, a tively, a substituted benzyl group. Substituents which may be halide or a C to Cs hydrocarbyl group; alternatively, a halide utilized for the substituted aralkyl groups are independently or a C to Cs hydrocarboxy group; alternatively, a C to Cs disclosed herein and may be utilized without limitation to hydrocarbyl group or a C to Cs hydrocarboxy group; alter further describe the substituted aralkyl groups which may be natively, a halide; alternatively, a C to Cs hydrocarbyl group; utilized as a non-hydrogen RP, RP, R, and/or RP group of 45 or alternatively, a C to Cs hydrocarboxy group. Specific Formula P1 or non-hydrogen R,R,R,R,R, and/or R' Substituent halides, hydrocarbyl groups, and hydrocarboxy group of Formula I1. groups are independently disclosed herein and may be uti In an aspect, the silyl group(s) which may be utilized as a lized without limitation to further describe the substituents of non-hydrogen R. R. R. and/or R group of Formula P1 the Substituted cycloalkyl groups, Substituted aromatic or a non-hydrogen R. R. R. R. R', and/or R group of 50 groups, Substituted aryl groups, or Substituted aralkyl groups Formula I1 may have Formula Sil. Generally, R', R, and which may be utilized as a non-hydrogen R. R. R. R of the silyl group having the and/or R group of Formula P1 or a non-hydrogen R. R. R", R. R', and/or R' group of Formula I1. In an embodiment, any halide substituent of a substituted S1 55 alkyl group (general or specific), Substituted cycloalkyl group Rls (general or specific), Substituted aromatic group (general or : specific), Substituted aryl group (general or specific), or Sub stituted aralkyl group may be a fluoride, a chloride, a bro mide, or an iodide; alternatively, a fluoride or a chloride. In 60 some embodiments, any halide substituent of a substituted Formula Sil may independently be an organyl group or a alkyl group (general or specific), Substituted cycloalkyl group hydrocarbyl group; alternatively, an organyl group; or alter (general or specific), Substituted aromatic group (general or natively, a hydrocarbyl group. Generally, the organyl group specific), Substituted aryl group (general or specific), or Sub and/or the hydrocarbyl groups which may be utilized as R', stituted aralkyl group may be a fluoride; alternatively, a chlo R’, and R of the silyl group having the Formula Sil may 65 ride; alternatively, a bromide; or alternatively, an iodide. have any carbon number as the organyl groups and hydrocar In an embodiment, any hydrocarbyl substituent of a sub byl groups which may be utilized as the non-hydrogen pyrrole stituted cycloalkyl group (general or specific), Substituted US 8,471,085 B2 23 24 aromatic group (general of specific), Substituted aryl group embodiment, any aralkoxy substituent of a substituted alkyl (general or specific), or Substituted aralkyl group may be an group (general or specific), Substituted cycloalkyl group alkyl group, an aryl group, or an aralkyl group; alternatively, (general or specific), Substituted aromatic group (general of an alkyl group; alternatively, an aryl group; or alternatively, specific), Substituted aryl group (general or specific), or Sub an aralkyl group. Generally, the alkyl, aryl, and aralkyl Sub- 5 stituted aralkyl group may be benzoxy group. stituent groups may have the same number of carbonatoms as In an embodiment, each silyl group(s) which may be uti the hydrocarbyl Substituent group disclosed herein. In an lized as a non-hydrogen R’P, RP, R, and/or RP group of embodiment, any alkyl substituent of a substituted cycloalkyl Formula P1 or a non-hydrogen R. R. R. R. R', and/or group (general or specific). Substituted aromatic group (gen R" group of Formula I1 may be a trihydrocarbylsilyl group. eral of specific), Substituted aryl group (general or specific), 10 In some embodiments, each silyl group(s) which may be or Substituted aralkyl group may be a methyl group, an ethyl utilized as a non-hydrogen R. R. R. and/or R group of group, an n-propyl group, an isopropyl group, an n-butyl Formula P1 or a non-hydrogen R. R. R. R. R', and/or group, a sec-butyl group, an isobutyl group, a tert-butyl R" group of Formula I1 may be a trialkylsilyl group, a triph group, an n-pentyl group, a 2-pentyl group, a 3-pentyl group. enylsilyl group, or a tri(Substituted phenyl)silyl group; alter a 2-methyl-1-butyl group, a tert-pentyl group, a 3-methyl-1- 15 natively, a trialkylsilyl group; alternatively, a triphenylsilyl butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group; group; or alternatively, a tri(Substituted phenyl)silyl group. alternatively, a methyl group, an ethyl group, an isopropyl Hydrocarbyl groups, alkyl groups, and Substituted phenyl group, a tert-butyl group, or a neo-pentyl group; alternatively, groups have been independently described herein as potential a methyl group; alternatively, an ethyl group; alternatively, an non-hydrogen pyrrole Substituents and may be utilized, with isopropyl group; alternatively, a tert-butyl group; or alterna- 20 out limitation, as R', R, and R of the silyl group having tively, a neo-pentyl group. In an embodiment, any aryl Sub the Formula Sil. stituent of a substituted cycloalkyl group (general or specific), In an embodiment, the pyrrole compound may comprise, Substituted aromatic group (general of specific), Substituted consist essentially of, or consist of a pyrrole compound hav aryl group (general or specific), or Substituted aralkyl group ing a C to C group attached to the 2- and 5-positions of the may be phenyl group, a tolyl group, a xylyl group, or a 25 pyrrole. Unless otherwise specified, the pyrrole compound 2,4,6-trimethylphenyl group; alternatively, a phenyl group; having a C to Cs group attached to the 2- and 5-positions, alternatively, a tolyl group, alternatively, a xylyl group; or may have groups attached at the 1, 3, and/or 4 positions. In an alternatively, a 2,4,6-trimethylphenyl group. In an embodi embodiment, the pyrrole compound of the oligomerization ment, any aralkyl Substituent of a Substituted cycloalkyl catalyst system can be a 2.5-disubstituted pyrrole compound, group Substituted cycloalkyl group (general or specific), Sub- 30 that is, the pyrrole compound has substituents only at the 2 stituted aromatic group (general of specific). Substituted aryl and 5-positions. Regardless of whether or not the pyrrole group (general or specific), or substituted aralkyl group may compound has substituents present at the 1, 3, and/or 4 posi be benzyl group. tions, the groups attached to the 2- and 5-positions of the In an embodiment, any hydrocarboxy Substituent of a Sub pyrrole compound may be the same or different. For example, stituted alkyl group (general or specific), Substituted 35 2,5-dimethylpyrrole, 2-ethyl-5-methylpyrrole and 2-ethyl-5- cycloalkyl group (general or specific), Substituted aromatic propyl pyrrole are among the Suitable 2,5-disubstituted pyr group (general of specific), Substituted aryl group (general or roles for use in the catalyst system and methods of this dis specific), or Substituted aralkyl group may be an alkoxy closure. In other aspects and embodiments, the groups group, an aryloxy group, or an aralkoxy group; alternatively, attached to the 2- and 5-positions of the pyrrole compound an alkoxy group; alternatively, an aryloxy group; or alterna- 40 may be the same. Generally, the groups attached to the 2- and tively, an aralkoxy group. Generally, the alkoxy, aryloxy, and 5-position of the pyrrole compound may be any pyrrole Sub aralkoxy Substituent groups may have the same number of stituent group disclosed herein. carbon atoms as the hydrocarboxy Substituent group dis In a particular non-limiting embodiment, the pyrrole com closed herein. In an embodiment, any alkoxy Substituent of a pound may have C to Cs organyl groups attached at the 2 Substituted alkyl group (general or specific). Substituted 45 and 5-positions of the pyrrole ring. In other embodiments, the cycloalkyl group (general or specific), Substituted aromatic groups attached at the 2- and 5-positions of the pyrrole ring group (general of specific), Substituted aryl group (general or may independently be C to C organyl groups; or alterna specific), or Substituted aralkyl group may be a methoxy tively, C to Cs organyl groups. In other particular non-limit group, an ethoxy group, an n-propoxy group, an isopropoxy ing embodiments, the groups attached at the 2- and 5-posi group, an n-butoxy group, a sec-butoxy group, an isobutoxy 50 tions of the pyrrole ring may independently be C to Cs group, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy hydrocarbyl groups; alternatively, C to C2 hydrocarbyl group, a 3-pentoxy group, a 2-methyl-1-butoxy group, a tert groups; or alternatively, a C to Cs hydrocarbyl groups. In yet pentoxy group, a 3-methyl-1-butoxy group, a 3-methyl-2- other particular non-limiting embodiments, the groups butoxy group, or a neo-pentoxy group; alternatively, a meth attached at the 2- and 5-positions of the pyrrole ring may oxy group, an ethoxy group, an isopropoxy group, a tert- 55 independently be C to Cs alkyl groups; alternatively, C. to butoxy group, or a neo-pentoxy group; alternatively, a Calkyl groups; or alternatively, a C to Cs alkyl groups. methoxy group; alternatively, an ethoxy group; alternatively, In an aspect the groups attached to the 2- and 5-positions of an isopropoxy group; alternatively, a tert-butoxy group; or the pyrrole ring are attached to the pyrrole ring in Such a way alternatively, a neo-pentoxy group. In an embodiment, any that at least one carbonatomattached to the 2- and 5-positions aroxy Substituent of a Substituted alkyl group (general or 60 of the pyrrole ring is a secondary carbon atom; alternatively, specific), Substituted cycloalkyl group (general or specific), the groups attached to the 2- and 5-positions of the pyrrole Substituted aromatic group (general of specific), Substituted ring are attached to the pyrrole ring in Such away that both the aryl group (general or specific), or Substituted aralkyl group carbonatoms attached to the 2- and 5-positions of the pyrrole may be phenoxy group, a toloxy group, a xyloxy group, or a ring are secondary carbon atoms. That is, when the carbon 2,4,6-trimethylphenoxy group; alternatively, a phenoxy 65 atom of the group attached to the pyrrole ring is a secondary group; alternatively, a toloxy group, alternatively, a xyloxy carbon atom, that secondary carbon is attached to one, and group; or alternatively, a 2.4.6-trimethylphenoxy group. In an only one, other carbon atom besides the carbon atom of the US 8,471,085 B2 25 26 pyrrole ring. In some embodiments, the groups attached to the pyrrole compound may be a 2.5-dialkylpyrrole, a 2,3,5-tri 2- and 5-positions are attached in Such a way that the carbon ialkylpyrrole, a 2,4,5-trialkylpyrrole, a 2.3.4.5-tetraalkylpyr atoms attached to the 2- and 5-positions of the pyrrole ring are role, or any combination thereof, alternatively, a 2,5-dialky secondary carbon atoms, and the groups are branched. In lpyrrole; alternatively, a 2,3,5-trialkylpyrrole; alternatively, a other embodiments the groups attached to the 2 and 5 position 2,4,5-trialkylpyrrole; or alternatively, a 2,3,4,5-tetraalky of the pyrrole ring may be linear. In an embodiment, an lpyrrole. ethylene trimerization process utilizing a catalyst system uti In some non-limiting embodiments wherein the groups lizing a pyrrole compound comprising or consisting of groups attached to the 2- and 5-positions are attached in Such a attached to the 2- and 5-positions of the pyrrole ring and manner that at least one (or alternatively both) of the carbon wherein the groups attached to the 2- and/or 5-positions are 10 attached to the pyrrole ring in Such a way that at least one atoms attached to the pyrrole ring are secondary carbons, the carbon atom attached to the 2- and 5-positions of the pyrrole pyrrole compound may be 2-methyl-5-ethylpyrrole, 2,5-di ring is a secondary carbon atom may provide a higher selec ethylpyrrrole, 2,5-di-n-propylpyrrole, 2,5-di-n-butylpyrrole, tivity to 1-hexene than the process using 2,5-dimethylpyrrole 2,5-di-n-pentylpyrrole, 2,5-di-n-hexylpyrrole, 2,5-di-n-hep as the pyrrole compound and/or provides a higher purity 15 tylpyrrole, 2,5-di-n-octylpyrrole, 2,3,5-triethylpyrrrole, 2.3, 1-hexene product than the process using 2,5-dimethylpyrrole 5-tri-n-butylpyrrrole, 2,3,5-tri-n-pentylpyrrrole, 2,3,5-tri-n- as the pyrrole compound. In another embodiment, an ethyl hexylpyrrrole, 2,3,5-tri-n-heptylpyrrrole, 2,3,5-tri-n- ene trimerization process utilizing a catalyst system utilizing octylpyrrrole, 2,3,4,5-tetraethylpyrrole, 2,3,4,5-tetra-n- a pyrrole compound comprising or consisting of groups butylpyrrole, 2,3,4,5-tetra-n-hexylpyrrole, 2.5-bis(2,2,2'- attached to the 2- and 5-positions of the pyrrole ring and trifluoroethyl)pyrrole, 2.5-bis(2-methoxymethyl)pyrrole, or wherein the groups attached to the 2- and/or 5-positions are any combination thereof; alternatively, 2-methyl-5-ethylpyr attached to the pyrrole ring in Such a way that at least one role, 2,5-diethylpyrrrole, 2,5-di-n-propylpyrrole, 2,5-di-n- carbon atom attached to the 2- and 5-positions of the pyrrole butylpyrrole, 2,5-di-n-pentylpyrrole, 2,5-di-n-hexylpyrrole, ring is a secondary carbon atom may provide a higher selec 2,5-di-n-heptylpyrrole, 2,5-di-n-octylpyrrole, or any combi tivity to 1-hexene than the process using 2,5-dimethylpyrrole 25 nation thereof; alternatively, 2-methyl-5-ethylpyrrole; alter as the pyrrole compound and/or provides a higher purity natively, 2,5-diethylpyrrrole; alternatively, 2,5-di-n-propy 1-hexene product than the process using 2,5-dimethylpyrrole lpyrrole; alternatively, 2,5-di-n-butylpyrrole; alternatively, as the pyrrole compound. 2,5-di-n-pentylpyrrole; alternatively, 2.5-n-hexylpyrrole; In an embodiment wherein the carbonatom of the either of alternatively, 2,5-di-n-heptylpyrrole; or alternatively, 2,5-di the groups attached to 2- and 5-position of the pyrrole ring is 30 n-octylpyrrole. a secondary carbon atom, the groups attached to 2-position In an aspect, the pyrrole compound may have a hydrogen and/or the 5-position may independently be an ethyl group, a atom located on at least one pyrrole ring carbonatom adjacent n-propyl group, a n-butyl group, a n-pentyl group, a n-hexyl to the nitrogen atom of the pyrrole ring and a bulky group group, a n-heptyl group, or a n-octyl group; alternatively, an located on a pyrrole ring carbon atom adjacent to any pyrrole ethyl group, a n-propyl group, a n-butyl group, or a n-pentyl 35 ring carbon atom bearing the hydrogen atom adjacent to the group; alternatively, an ethyl group; alternatively, a n-propyl nitrogen atom of the pyrrole ring; alternatively, has a hydro group; alternatively, a n-butyl group; alternatively, a n-pentyl genatom located on each pyrrole ring carbonatom adjacent to group; alternatively, a n-hexyl group; alternatively, a n-heptyl the nitrogenatom of the pyrrole ring and bulky group located group; or alternatively, a n-octyl group. For example, the on each pyrrole ring carbon atom adjacent to the pyrrole ring pyrrole compound may be a 2,5-disubstituted pyrrole, such as 40 carbon atoms bearing the hydrogen atom adjacent to the 2,5-diethyl pyrrole. nitrogen atom of the pyrrole ring. Generally, each group in In an aspect, the pyrrole can have the formula P1 wherein this aspect may be any group described herein and have any RandR independently are any group disclosed hereinand number of carbons described herein that meets the require wherein at least one of the groups attached to the 2- and ments of the pyrrole compound. For example, any non-hy 5-positions is attached in a manner wherein the carbon atom 45 drogen pyrrole group located on a pyrrole ring carbon atom attached to the pyrrole ring is a secondary carbon atom and adjacent to the pyrrole ring nitrogen atom and any non-hy Rand Rindependently are hydrogen and any non-hydro drogen pyrrole group located on a pyrrole ring carbon atom gen pyrrole substituent disclosed herein; alternatively, R adjacent to a pyrrole ring carbonatom bearing an non-hydro and R independently are any group disclosed herein and gen pyrrole group on a pyrrole ring carbon atom adjacent to wherein at least one of the groups attached to the 2- and 50 the pyrrole ring nitrogen atom may be any C to Cs. C to 5-positions is attached in a manner wherein the carbon atom Cs. C to Co., or C to Cs organyl group (alternatively any attached to the pyrrole ring is a secondary carbon atom and hydrocarbyl group) described herein while the group located R and R are hydrogen. In another aspect, R and R' on a pyrrole ring carbon atom adjacent to a the pyrrole ring independently are any group disclosed herein each of the carbonatom bearing the hydrogenatom that is adjacent to the groups attached to the 2- and 5-positions is attached in a 55 nitrogenatom of the pyrrole ring may be any bulky Cs to Cs. manner wherein the carbon atom attached to the pyrrole ring C. to Cs. C to Co., or C to Cs organyl group (alternatively is a secondary carbonatomand RandR'independently are any hydrocarbyl group) described herein. In an aspect, each hydrogen and any non-hydrogen pyrrole Substituent dis bulky substituent may be a triorganylsilyl group; or alterna closed herein; alternatively, R and R independently are tively, a trihydrocarbylsilyl group. Generally, the triorganyl any group disclosed herein wherein the groups attached to the 60 silyl and/or the trihydrocarbylsilyl group may have the same 2- and 5-positions is attached in a manner wherein the carbon number of carbon atoms as the silyl group which may be atom attached to the pyrrole ring are secondary carbonatoms utilized as a pyrrole substituent described herein. In an and Rand Rare hydrogen. embodiment, each bulky substituent may be a trialkylsilyl In some non-limiting embodiments wherein the groups group, a triphenylsilyl group, or a tri(Substituted phenyl)silyl attached to the 2- and 5-positions are attached in Such a 65 group; alternatively, a trialkylsilyl group; alternatively, a manner that at least one (or alternatively both) of the carbon triphenylsilyl group; or alternatively, a tri(Substituted phenyl) atoms attached to the pyrrole ring are secondary carbons, the silyl group. US 8,471,085 B2 27 28 In an aspect, the pyrrole compound may be a pyrrole com attached to the pyrrole ring carbon atom is a quaternary car pound having Formula P2. Formula P3, Formula P4, or a bonatom or one wherein the carbon atom of the bulky group combination thereof; alternatively, Formula P2; alternatively, that is adjacent to the carbon atom attached to pyrrole ring Formula P3; alternatively Formula P4. In an embodiment, carbon atom is a quaternary carbon atom; alternatively one R2P and RF of wherein the carbon atom of bulky group that is attached to the pyrrole ring carbon atom is a quaternary carbon atom; or alternatively one wherein the carbon atom of the bulky group P2 R12p that is adjacent to the carbon atom attached to pyrrole ring carbon atom is a quaternary carbonatom. In an embodiment, R13p 10 e a bulky silyl group is one wherein the silicon atom of the N-H bulky silyl group attached to the pyrrole ring carbon is S. attached to four carbon atoms. R 14p In an embodiment, the bulky pyrrole substituent may be H P3 15 defined as one wherein the carbon atom of bulky group that is R22p attached to the pyrrole ring carbon atom is attached to 3 or 4 H carbon atoms or one wherein the carbon atom of the bulky e group that is adjacent to the carbon atom attached to pyrrole N-H ring carbon atom is attached to 3 or 4 carbon atoms; alterna S. tively one wherein the carbon atom of bulky group that is R24p attached to the pyrrole ring carbon atom is attached to 3 or 4 H P4 carbon atoms; or alternatively, one wherein the carbon atom H of the bulky group that is adjacent to the carbonatom attached R33p to pyrrole ring carbonatom is attached to 3 or 4 carbonatoms. e 25 In some embodiments, the bulky pyrrole substituent may be N-H defined as one wherein the carbon atom of bulky group that is S. R34p attached to the pyrrole ring carbon atom is attached to 3 carbon atoms or one wherein the carbon atom of the bulky H group that is adjacent to the carbon atom attached to pyrrole ring carbon atom is attached to 3 carbon atoms; alternatively Formula P2 and R’P of Formula P3 may be any pyrrole 30 one wherein the carbon atom of bulky group that is attached substituent group disclosed herein while R'' of Formula P2, to the pyrrole ring carbon atom is attached to 3 carbon atoms; R’ of Formula P3, and R. and RP of Formula P4 may be or alternatively one wherein the carbon atom of the bulky any bulky pyrrole substituent disclosed herein. For example, group that is adjacent to the carbon atom attached to pyrrole R'? and R''P of Formula P2 and RP of Formula P3 may be 35 ring carbon atom is attached to 3 carbon atoms. In other any C to C1s, C to C1s, C to Co., or C to Cs organyl group embodiments, the bulky pyrrole substituent may be defined as (alternatively, any hydrocarbyl group) described herein while one wherein the carbon atom of bulky group that is attached RP of Formula P2, R’P of Formula P3, and RP and RP of to the pyrrole ring carbonatom is attached to 4 carbon atoms Formula P4 may be any bulky Cs to Cs C to Cs, C. to Co. or one wherein the carbon atom of the bulky group that is or C to Cs organyl group (alternatively, any hydrocarbyl 40 adjacent to the carbon atom attached to pyrrole ring carbon group) described herein. In an aspect, each bulky Substituent atom is attached to 4 carbonatoms; alternatively one wherein may be a triorganylsilyl group; or alternatively, a trihydrocar the carbonatom of bulky group that is attached to the pyrrole bylsilyl group. ring carbon atom is attached to 4 carbon atoms; or alterna In an embodiment, the bulky pyrrole substituent may be tively one wherein the carbon atom of the bulky group that is defined as one wherein the carbonatom of bulky group that is 45 adjacent to the carbon atom attached to pyrrole ring carbon attached to the pyrrole ring carbon atom is a tertiary or qua atom is attached to 4 carbon atoms. For illustration purposes. Formula E1 is used to illustrate ternary carbon atom or one wherein the carbon atom of the the carbon atom attached to the pyrrole ring and the carbon bulky group that is adjacent to the carbon atom attached to atom adjacent to the carbon atom attached to the pyrrole ring pyrrole ring carbon atom is a tertiary or quaternary carbon carbon atom. atom; alternatively one wherein the carbon atom of bulky 50 group that is attached to the pyrrole ring carbon atom is a tertiary or quaternary carbon atom; or alternatively one wherein the carbonatom of the bulky group that is adjacent to the carbon atom attached to pyrrole ring carbon atom is a tertiary or quaternary carbonatom. In some embodiments, the 55 bulky pyrrole substituent may be defined as one wherein the carbonatom of bulky group that is attached to the pyrrole ring carbon atom is a tertiary carbon atom or one wherein the carbon atom of the bulky group that is adjacent to the carbon atom attached to pyrrole ring carbon atom is a tertiary carbon 60 atom; alternatively one wherein the carbon atom of bulky group that is attached to the pyrrole ring carbon atom is a Using Formula E1, the carbon atom labeled 1 within the tertiary carbon atom; or alternatively one wherein the carbon group attached to the pyrrole ring represents the carbonatom atom of the bulky group that is adjacent to the carbon atom attached to the pyrrole ring carbon atom while the carbon attached to pyrrole ring carbonatom is a tertiary carbonatom. 65 atom labeled 2 within the group attached to the pyrrole ring In other embodiments, the bulky pyrrole substituent may be represents the carbon atom adjacent to the carbon atom defined as one wherein the carbonatom of bulky group that is attached to the pyrrole ring carbon atom. In an embodiment, US 8,471,085 B2 29 30 a bulky silyl group is one wherein the silicon atom of the 2,4,6-tripheneyl group. In some embodiments, the Substituted bulky silyl group attached to the pyrrole ring carbon is phenyl group which may be utilized as a bulky substituent attached to four carbon atoms. may be a 2-methylphenyl group, a 2,4-dimethylphenyl group, In an embodiment, the bulky substituent may indepen a 2,6-dimethylphenyl group, a 3.5-dimethylphenyl group, or dently be an alkyl group, a Substituted alkyl group, a a 2.4.6-tripheneyl group. In other embodiments, the Substi cycloalkyl group, a Substituted cycloalkyl group, an aromatic tuted phenyl group which may be utilized as a bulky substitu group, a Substituted aromatic group, an aryl group, a Substi ent may be a 2-methylphenyl group; alternatively, a 3-meth tuted aryl group, anaralkyl group, a Substituted aralkyl group, ylphenyl group; alternatively, a 4-methylphenyl group; or a silyl group. Generally, the alkyl group, a Substituted alkyl alternatively, a 2,3-dimethylphenyl group; alternatively, a group, a cycloalkyl group, a Substituted cycloalkyl group, an 10 2,4-dimethylphenyl group; alternatively, a 2,5-dimethylphe aromatic group, a Substituted aromatic group, an aryl group, nyl group; alternatively, a 2,6-dimethylphenyl group; alterna a Substituted aryl group, an aralkyl group, a Substituted tively, a 3,4-dimethylphenyl group; alternatively, a 3.5-dim aralkyl group, and silyl group which may be utilized as the ethylphenyl group; or alternatively, a 2.4.6-tripheneyl group. bulky Substituent may have the same number of carbonatoms In another aspect, each bulky Substituent may indepen as the bulky organyl (or hydrocarbyl)pyrrole substituent dis 15 dently be a trimethylsilyl group, a triethylsilyl group, a tri closed herein. Alkyl groups, Substituted alkyl groups, isopropylsilyl group, a tri-t-butylsilyl group, or a triphenylsi cycloalkyl groups, Substituted cycloalkyl groups, aromatic lyl group; alternatively, a trimethylsilyl group, a triethylsilyl groups, Substituted aromatic groups, aryl groups, Substituted group, a triisopropylsilyl group, or a tri-t-butylsilyl group. In aryl groups, aralkyl groups, Substituted aralkyl groups, and an embodiment, each bulky substituent may be a trimethyl silyl groups are generally disclosed herein and those that meet silyl group; alternatively, a triethylsilyl group; alternatively, a the criteria for a bulky substituent may be utilized, without triisopropylsilyl group; alternatively, a tri-t-butylsilyl group; limitation to further describe the pyrrole compound which or alternatively, a triphenylsilyl group. may be utilized in some aspect and embodiments disclosed In an non-limiting example, the pyrrole compound may be herein. 2-methyl-4-isopropylpyrrole, 2-ethyl-4-isopropylpyrrole, In an embodiment, each bulky Substituent may indepen 25 2-methyl-4-sec-butylpyrrole, 2-ethyl-4-sec-butylpyrrole, dently be a propan-2-yl group, a butan-2-yl, a 2-methylpro 2-methyl-4-isobutylpyrrole, 2-ethyl-4-isobutylpyrrole, pan-1-yl group, a 2-methylpropan-2-yl group, a pentan-2-yl 2-methyl-4-t-butylpyrrole, 2-ethyl-4-t-butylpyrrole, 2-me group, a pentan-3-yl group, a 2-methylbutan-1-yl group, a thyl-4-neo-pentylpyrrole, or 2-ethyl-4-neopentylpyrrole. In 2-methylbutan-2-yl group, a 3-methylbutan-2-yl group, 2.2- Some non-limiting examples, the pyrrole compound may be dimethylpropan-1-yl group, a hexan-2-yl group, a hexan-3-yl 30 2-methyl-4-isopropylpyrrole, 2-ethyl-4-isopropylpyrrole, group, a 2-methylpentan-1-yl group, 2-ethylbutan-1-yl 2-methyl-4-t-butylpyrrole, 2-ethyl-4-t-butylpyrrole, 2-me group, a 2-methylpentan-2-yl group, a 2,3-dimethylbutan-1- thyl-4-neo-pentylpyrrole, or 2-ethyl-4-neopentylpyrrole. In yl group, a 2,3-dimethylbutan-2-yl group, a heptan-2-yl other non-limiting examples, the pyrrole compound may be group, a heptan-3-yl group, a heptan-4-yl group, a 2-methyl 2-methyl-4-isopropylpyrrole; alternatively, 2-ethyl-4-isopro hexan-1-yl group, a 2-ethylpentan-1-yl group, a 2-methyl 35 pylpyrrole; alternatively, 2-methyl-4-sec-butylpyrrole; alter hexan-2-yl group, a 2,3-dimethylpentan-1-yl group, a 2.3- natively, 2-ethyl-4-sec-butylpyrrole; alternatively, 2-methyl dimethylpentan-2-yl group, a 2,3,3-trimethylpentan-1-yl 4-isobutylpyrrole; alternatively, 2-ethyl-4-isobutylpyrrole; group, a 2.3,3-trimethylpentan-2-yl group, an octan-2-yl alternatively, 2-methyl-4-t-butylpyrrole; alternatively, group, an octan-3-yl group, an octan-4-yl group, a 2-methyl 2-ethyl-4-t-butylpyrrole; alternatively, 2-methyl-4-neo-pen heptan-1-yl group, a 2-ethylhexan-1-yl group, a 2-methyl 40 tylpyrrole; or alternatively, 2-ethyl-4-neopentylpyrrole. In heptan-2-yl group, a nonan-2-yl group, a nonan-3-yl group, a another non-limiting example, the pyrrole compound may be nonan-4-yl group, a nonan-5-yl group, a decan-2-yl group, a 3,4-diisopropylpyrrole, 3,4-di-sec-butylpyrrole, 3,4-diisobu decan-3-yl group, a decan-4-yl group, or a decan-5-yl group. tylpyrrole, 3,4-di-t-butylpyrrole, or 3,4-di-neo-pentylpropy In other embodiments, each bulky substituent may indepen lpyrrole. In yet another embodiment, the pyrrole compound dently be a propan-2-yl group, a butan-2-yl, a 2-methylpro 45 may be 3,4-diisopropylpyrrole: alternatively, 3,4-di-sec-bu pan-1-yl group, a 2-methylpropan-2-yl group, a pentan-2-yl tylpyrrole; alternatively, 3,4-diisobutylpyrrole; alternatively, group, a pentan-3-yl group, a 2-methylbutan-1-yl group, a 3,4-di-t-butylpyrrole; or alternatively, 3,4-di-neo-pentylpro 2-methylbutan-2-yl group, a 3-methylbutan-2-yl group, 2.2- pylpyrrole dimethylpropan-1-yl group; alternatively, propan-2-yl group, Metal Alkyl a 2-methylpropan-2-yl group, or a 2.2-dimethylpropan-1-yl 50 Generally, and according to one aspect of this disclosure, group. In other embodiments, each bulky Substituent may the metal alkyl may be any heteroleptic or homoleptic metal independently be a propan-2-yl group; alternatively, a butan alkyl compound. For example, the metal of the metal alkyl 2-yl; alternatively, a 2-methylpropan-1-yl group; alterna can comprise, consistessentially of, or consist of Group 1, 2, tively, a 2-methylpropan-2-yl group; alternatively, a pentan 11, 12, 13, or 14 metal; or alternatively, a Group 13 or 14 2-yl group; alternatively, a pentan-3-yl group; alternatively, a 55 metal; or alternatively, a Group 13 metal. In some embodi 2-methylbutan-1-yl group; alternatively, a 2-methylbutan-2- ments and aspects, the metal alkyl may comprise, consist yl group; alternatively, a 3-methylbutan-2-yl group; alterna essentially of, or consist of a lithium alkyl, Sodium alkyl, tively, 2,2-dimethylpropan-1-yl group. magnesium alkyl, boron alkyl, a Zinc alkyl, or an aluminum In an aspect, each bulky substituent may independently be alkyl. In this aspect, for example, Suitable metal alkyls a phenyl group or a Substituted phenyl group; alternatively, a 60 include, but are not limited to, n-butyl lithium, sec-butyl phenyl group; or alternatively, a Substituted phenyl group. In lithium, tert-butyl lithium, diethyl magnesium, or diethyl an embodiment, the Substituted phenyl group which may be Zinc. In an embodiment the metal alkyl may comprise, consist utilized as a bulky substituent may be a 2-methylphenyl essentially of, or consist of an aluminum alkyl. group, a 3-methylphenyl group, a 4-methylphenyl group, a According to a further aspect and in any embodiment of 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 65 this disclosure, the metal alkyl may comprise a metal alkyl 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a halide. Metal alkyl halides are described herein and may be 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, or a utilized as the metal alkyl component of the oligomerization US 8,471,085 B2 31 32 catalyst system. The halide portion of the metal alkyl halide any trialkylaluminum compound described herein. The alky may be chloride; alternatively bromide; or alternatively laluminum halide compound of the mixture may be any alky iodide. laluminum compound described herein. In some embodi In some aspects and embodiments according to this disclo ments, the mixture of the trialkylaluminum compound and Sure, the metal alkyl can be a non-hydrolyzed alkylaluminum the alkylaluminum halide may comprise, consist essentially compound. In an embodiment, the non-hydrolyzed alkyl alu of or consist of a mixture of triethylaluminum and diethyla minum compound may be a trialkyl aluminum compound, an luminum chloride, a mixture of triethylaluminum and ethy alkyl aluminum halide, or and alkyl aluminum alkoxide. laluminum dichloride, or a mixture of triethylaluminum and Generally, each alkyl group of any metal alkyl described ethylaluminum sesquichloride. In an embodiment, the metal herein (e.g. alkyl aluminum compound or alkylaluminum 10 alkyl component of the oligomerization catalyst system may halide, among others), if there is more than one, may inde comprise, consist essentially of or consist of a mixture of pendently be a C to Coalkyl group; alternatively, a C to Co triethylaluminum and diethylaluminum chloride. alkyl group; or alternatively, a C to C alkyl group. In an In another aspect and in any embodiments, specific embodiment, each alkyl group(s) may independently be a examples of metal alkyls that are useful in this disclosure may methyl group, an ethyl group, a propyl group, abutyl group, 15 comprise, consist essentially of, or consist of, but are not a pentyl group, a hexyl group, a heptyl group, or an octyl limited to, trimethylaluminum (TMA), triethylaluminum group; alternatively, a methyl group, a ethyl group, a butyl (TEA), ethylaluminum dichloride, tripropylaluminum, group, a hexyl group, or an octyl group. In some embodi diethylaluminum ethoxide, tributylaluminum, disobutylalu ments, each alkyl group of any metal alkyl described herein minum hydride, triisobutylaluminum, diethylaluminum may independently be a methyl group, an ethyl group, an chloride (DEAC), and combinations thereof. In other aspects, n-propyl group, an n-butyl group, an iso-butyl group, a and in any embodiments, specific examples of metal alkyls n-hexyl group, or an n-octyl group; alternatively, a methyl that are useful in this disclosure can comprise or can include, group, an ethyl group, a n-butyl group, or an iso-butyl group; but are not limited to triethylaluminum (TEA), diethylalumi alternatively, a methyl group; alternatively, an ethyl group; num chloride (DEAC), or any combination thereof. alternatively, an n-propyl group; alternatively, an n-butyl 25 group; alternatively, an iso-butyl group; alternatively, a In a non-limiting embodiment, useful aluminoxanes may n-hexyl group; or alternatively, an n-octyl group. have a repeating unit of Formula I: According to another aspect of this disclosure, the metal alkyl can comprise, consist essentially of, or consist of a Formula I trialkylaluminum compound, a dialkylaluminum halide com 30 pound, an alkylaluminum dihalide compound, a dialkylalu --or minum hydride compound, an alkylaluminum dihydride R compound, a dialkylaluminum hydrocarboxide compound, an alkylaluminum dihydrocarboxide compound, an alkyl alu wherein R' is a linear or branched alkyl. Alkyl groups for minum sesquihalide compound, an alkylaluminum sesquihy 35 metal alkyls have been independently described herein and drocarboxide compound, an aluminoxane, or any combina may be utilized without limitation to further describe the tion thereof. In some embodiments, the metal alkyl can aluminoxanes having Formula I. Generally, in of Formula I is comprise, consist essentially of, or consist of a trialkylalu greater than 1; or alternatively greater than 2. In an embodi minum compound, dialkylaluminum halide compound, an ment, n may be range from 2 to 15; or alternatively, range alkylaluminum dihalide compound, or any combination 40 from 3 to 10. thereof, alternatively, a trialkylaluminum compound; alterna In a non-limiting embodiment, useful aluminoxanes which tively, a dialkylaluminum halide compound; alternatively, an may be utilized in the catalyst system may comprise, consist alkylaluminum dihalide compound; alternatively, a dialkyla essentially of, or consist of methylaluminoxane (MAO), luminum hydride compound; alternatively, an alkylalumi ethylaluminoxane, modified methylaluminoxane (MMAO), num dihydride compound; alternatively, a dialkylaluminum 45 n-propylaluminoxane, iso-propyl-aluminoxane, n-butylalu hydrocarboxide compound; alternatively, an alkylaluminum minoxane, sec-butylaluminoxane, iso-butylaluminoxane, dihydrocarboxide compound; alternatively, an alkylalumi t-butylaluminoxane, 1-pentylaluminoxane, 2-pentylalumi num sesquihalide compound; alternatively, an alkylalumi noxane, 3-pentylaluminoxane, iso-pentylaluminoxane, neo num sesquihydrocarboxide compound; or alternatively, an pentylaluminoxane, or mixtures thereof. In some non-limit aluminoxane. Applicable alkyl groups and halides for the 50 ing embodiments, aluminoxanes may comprise, consist metal alkyl, metal alkylhalides, and/or metal alkyl hydrocar essentially of, or consist of methylaluminoxane (MAO), boxides are described herein and may be utilized to further modified methylaluminoxane (MMAO), isobutyl aluminox describe the suitable metal alkyls. ane, t-butylaluminoxane, or mixtures thereof. In other non Exemplary trialkyl aluminum compounds include but are limiting embodiments, useful aluminoxanes may be methy not limited to, trimethylaluminum (TMA), triethylaluminum 55 laluminoxane (MAO); alternatively, ethylaluminoxane: (TEA), tripropylaluminum, tri-n-butylaluminum, or tri alternatively, modified methylaluminoxane (MMAO); alter isobutylaluminum, or mixtures thereof. Exemplary alkylalu natively, n-propylaluminoxane; alternatively, iso-propylalu minum halide compounds may include, but are not limited to, minoxane; alternatively, n-butylaluminoxane; alternatively, diethylaluminum chloride (DEAC), diethylaluminum bro sec-butylaluminoxane; alternatively, iso-butylaluminoxane: mide, ethylaluminum dichloride, ethylaluminum sesquichlo 60 alternatively, t-butylaluminoxane; alternatively, 1-pentylalu ride, and mixtures thereof. In various embodiments, the tri minoxane; alternatively, 2-pentylaluminoxane; alternatively, alkylaluminum compound may be triethylaluminum. 3-pentyl-aluminoxane; alternatively, iso-pentylaluminoxane: According to a further aspect, the metal alkyl compound or alternatively, neopentylaluminoxane. may comprise, consist essentially of, or consist of a mixture Halogen Containing Compound of a trialkylaluminum compound and an alkylaluminum 65 While not intending to be bound by theory, it is thought that halide. Generally, the trialkylaluminum compound of the a halogen containing compound can improve product purity mixture may comprise, consist essentially of, or consist of and/or selectivity of the oligomerization process. In some US 8,471,085 B2 33 34 aspects and embodiments, the halogen containing compound According to a further aspect and in any embodiment, the may be a chloride containing compound, a bromide contain halogen containing compound can comprise a C to Cs ing compound, or an iodide containing compound. In an organic halide; alternatively, a C to Co organic halide; or embodiment, the halogen containing compound may be a alternatively, a C to Cs organic halide. By way of example, chloride containing compound. according to this aspect, the halogen containing compound In an aspect, the halogen containing compound, regardless can comprise, consist essentially of, or consist of carbon of whether it is a chloride, bromide, or iodide containing tetrachloride, carbon tetrabromide, chloroform, bromoform, compound, may be a metal halide, alkyl metal halide, or an dichloromethane, dibromoethane, diiodomethane, chlo organic halide. In various embodiments and aspect, the halo romethane, bromomethane, iodomethane, dichloroethane, gen containing compound may be a metal chloride; alterna 10 tetrachloroethane, trichloroacetone, hexachloroacetone, tively, a metal bromide; or alternatively, a metal iodide. In an hexachlorocyclohexane, 1,3,5-trichlorobenzene, hexachlo embodiment, the halogen containing compound may be a robenzene, trityl chloride, benzyl chloride, benzyl bromide, metal alkyl chloride; alternatively, a metal alkyl bromide; or benzyl iodide, chlorobenzene, bromobenzene, iodobenzene, alternatively, a metal iodide. In an embodiment, the halogen hexafluorobenzene, or any combination thereof. containing compound may be an organic chloride; alterna 15 In an aspect, the catalyst system may have a molar ratio of tively, an organic bromide; or alternatively, an organic iodide. metal in the transition metal compound to metal in the metal Moreover, and in another aspect, the halogen containing alkyl ranging from 1:1 to 1:150; alternatively, 1:1 to 1:100; or compound comprises a group 3 metal halide, a group 4 metal alternatively, 1:9 to 1:21. In an embodiment, when the tran halide, a group 5 metal halide, a group 13 metal halide, a sition metal compound is a chromium compound (e.g. a chro group 14 metal halide, a group 15 metal halide, or any com mium(III) carboxylate composition) and the metal alkyl is an bination thereof. By way of example, the halogen containing alkylaluminum compound (e.g. triethylaluminum, diethyla compound can be or the halogen containing compound can luminum chloride, or a mixture thereof), the catalyst system comprise Scandium chloride, yttrium chloride, lanthanum may have a molar ratio of chromium to aluminum ranging chloride, titanium tetrachloride, zirconium tetrachloride, from 1:1 to 1:150; alternatively, 1:1 to 1:100; or alternatively, hafnium tetrachloride, borontrichloride, aluminum chloride, 25 1:9 to 1:21. gallium chloride, silicon tetrachloride, trimethyl chlorosi In an aspect, the catalyst system may have a molar ratio of lane, germanium tetrachloride, tin tetrachloride, phosphorus nitrogen of the pyrrole compound to metal of the transition trichloride, antimony trichloride, antimony pentachloride, metal compound ranging from 1.0:1 to 4.0:1, alternatively bismuth trichloride, borontribromide, aluminum tribromide, from 1.5:1 to 3.7:1; alternatively from 1.5:1 to 2.5:1, alterna silicon tetrachloride, silicon tetrabromide, aluminum fluo 30 tively from 2.0:1 to 3.7:1; alternatively from 2.5:1 to 3.5:1; or ride, molybdenum pentachloride, tungsten hexachloride, tri alternatively from 2.9:1 to 3.1:1. In an embodiment when the tylhexachloroantimonate, or any combination thereof. transition metal compound is a chromium compound (e.g. a In accordance with another aspect, the halogen containing chromium(III) carboxylate composition) the molar ratio of compound may comprise, consistessentially of, or consist of chromium to pyrrole may range from 1.0:1 to 4.0:1, alterna a Group 1, 2, 12, or 13 alkyl metal halide; alternatively, a 35 tively from 1.5:1 to 3.7:1; alternatively from 1.5:1 to 2.5:1; Group 12 or 13 alkyl metal halide; or alternatively, an alky alternatively from 2.0:1 to 3.7:1; alternatively from 2.5:1 to laluminum halide oran alkyltinhalide. According to a further 3.5:1; or alternatively from 2.9:1 to 3.1:1. aspect, the halogen containing compound may comprise, Oligomerization Process consistessentially of, or consist of an alkylaluminum halide. The oligomerization catalyst system described herein may In some embodiment, the alkylaluminum halide may be an 40 be utilized within an oligomerization process or a process to alkylaluminum chloride; alternatively, an alkylaluminum prepare an oligomerization product. Generally, the oligomer bromide; or alternatively, and alkylaluminum iodide. In other ization process or process to prepare an oligomerization prod embodiments, the alkyltinhalide may be an alkyltin chloride: uct comprises oligomerizing a feedstock olefin with the oli alternatively, an alkyltin bromide; or alternatively, an alkyltin gomerization catalyst as described herein. iodide. In an embodiment, the alkyl metal halide may be an 45 In various embodiments and in accordance with one alkylaluminum halide. In another embodiment, the alky aspect, the feedstock olefin may comprise, consistessentially metal halide may be an alkyltin halide. of or consist of an alpha olefin and the oligomerization In various embodiments and according to another aspect, process may be an oligomerization process for preparing an the halogen containing compound can comprise, consist alpha olefin oligomerization product; alternatively, the feed essentially of, or consist of a dialkylaluminum halide, an 50 stock olefin may comprise, consist essentially of, or consist alkylaluminum dihalide, or an alkylaluminum sesquihalide, of a linear alpha olefin and the oligomerization process may or any combination thereof, alternatively, a dialkylaluminum be an oligomerization process for preparing an linear alpha halide; alternatively, an alkylaluminum dihalide; or alterna olefin oligomerization product; or alternatively, the feedstock tively, an alkylaluminum sesquihalide. In this aspect, the olefin may comprise, consist essentially of consist of a nor alkyl group of the alkylaluminum halide, the alkyltin halide, 55 mal alpha olefin and the oligomerization process may be an the dialkylaluminum halide, the alkylaluminum dihalide, or oligomerization process for preparing a normal alpha olefin the alkylaluminum sesquihalide may be a C to Cs alkyl oligomerization product. group. Moreover and in this aspect, the halogen containing In one aspect, the oligomerization process for preparing an compound can comprise, consist essentially of or consist of olefin oligomerization product may be an olefin trimerization diethylaluminum chloride, ethylaluminum sesquichloride, 60 process for preparing an olefin trimer product. In an embodi ethylaluminum dichloride, tributyltin chloride, dibutyltin ment, the trimerization feedstock olefin may comprise, con dichloride, or any combination thereof; alternatively, diethy sist essentially of consist of an alpha olefin and the oligo laluminum chloride, ethylaluminum sesquichloride, ethyla merization process can be an trimerization process for luminum dichloride, or any combination thereof, or alterna preparing an alpha olefintrimerization product; alternatively, tively, diethylaluminum chloride; alternatively, 65 the trimerization feedstock olefin may comprise, consist ethylaluminum sesquichloride; or alternatively, ethylalumi essentially of, or consist of a linear alpha olefin and the num dichloride. oligomerization process may bean trimerization process for US 8,471,085 B2 35 36 preparing an linear alpha olefin trimerization product; or components which do not adversely affect and can enhance alternatively, the trimerization feedstock olefin may com the resultant catalyst system, such as, for example, transitions prise, consist essentially of or consist of a normal alpha metals and/or halides. olefin and the oligomerization process may be an trimeriza The amount of aromatic compound that may be used in the tion process for preparing an normal alpha olefin trimeriza preparation of the oligomerization catalyst system may be in tion product. a range up to 15 weight percent, based on the amount of Generally, the feedstock olefin(s), alpha olefin(s), linear solvent in the reactor, range from 0.001 to 10 weight percent, alpha olefin(s), or normal alpha olefin(s) may be C to Co., C. or range from 0.01 to 5 weight percent. Excess aromatic to C, or C to Co olefin(s), alpha olefin(s), linear alpha compound may inhibit catalyst system activity and insuffi 10 cient aromatic compound may not stabilize the catalyst sys olefin(s), or normal alpha olefin(s). In an embodiment, the tem. Generally, the moles of aromatic compound per mole of olefin may comprise, consist essentially of, or consist of metal in the transition metal compound (e.g. chromium com ethylene. When the feedstock olefin comprises, consists pound) in the catalyst system may be in a range up to 6,000, essentially of, or consist of ethylene, the oligomerization range from 10 to 3,000, or range from 20 to 1,000 moles of process may be an ethylene trimerization process, the trimer 15 aromatic compound per mole of metal (e.g. chromium com product may be 1-hexene, and the trimerization product com pound) in the catalyst system. prises 1-hexene. Contacting of the aromatic compound and catalyst system One composite catalyst system which may be used in the may occur under any conditions sufficient to stabilize the invention is the combination of chromium (III) ethylhex catalyst system in the presence of heat. Generally, the tem anoate, 2,5-diethylpyrrole, triethylaluminum, and diethylalu peratures for contacting may range from -50° C. to 70° C. minum chloride. This composite catalyst system can be used, range from -10°C. to 70° C., or range from 5° C. to 30° C. for example, to trimerize ethylene to form 1-hexene. Other Generally, contacting times may be less than 5 hours, range catalyst applicable catalyst systems may be readily discerned from 0.01 seconds to 4 hours, or range from 0.1 seconds to 3 from the present disclosure. hours. Longer contact times may not improve catalyst system In one aspect, contacting and/or reacting the chromium 25 stability, and shorter contact times may be insufficient to compound, pyrrole compound, and metal alkyl is carried out allow complete contacting of the aromatic compound and in the presence of an unsaturated hydrocarbon. The unsatur catalyst system and, therefore, may not be sufficient to stabi ated hydrocarbon can be any aromatic or aliphatic hydrocar lize the catalyst System. Any pressure which allows thorough bon, in a gas, liquid or Solid state. In some embodiments, the contacting of the aromatic compound and catalyst system 30 may be used. Generally, any pressure which can maintain the unsaturated compound may be an aromatic hydrocarbon; aromatic compound and catalyst system in liquid form may alternatively, an unsaturated aliphatic compound. To effect be used. The catalyst system preparation is generally per thorough contacting of the chromium compound, the pyrrole formed under an inert atmosphere. Such as nitrogen or argon, compound, and metal alkyl, the unsaturated hydrocarbon to decrease the amount of water vapor and oxygen present. may be in a liquid state. It will be understood, however, that 35 Nitrogen is often used due to cost and availability. In addition Some embodiments may be used in connection with appro to the discussion herein, other applicable examples of transi priate catalyst systems, irrespective of the method of produc tion metal compounds and oligomerization catalyst systems, ing the catalyst system. In one aspect, the unsaturated hydro and their exemplary preparation, are provided in U.S. Pat. No. carbon can be 1-hexene. Alternatively, the contacting and/or 6,133,495 and U.S. Pat. No. 7,384,886, which are hereby reacting the chromium compound, pyrrole compound, and 40 incorporated by reference in their entireties for all purposes. metal alkyl can be carried out in the absence of 1-hexene. The oligomerization reaction products, e.g., olefin trimers, The unsaturated hydrocarbon can have any number of car can be prepared from the catalyst system of this invention by bon atoms per molecule. Usually, the unsaturated hydrocar Solution, slurry, and/or gas phase reaction techniques using bon will comprise less than 70 carbonatoms per molecule, or conventional equipment and contacting processes. Contact less than 20 carbon atoms per molecule. Exemplary unsatur 45 ing of the monomer or monomers with a catalyst system can ated, aliphatic unsaturated hydrocarbon compounds include, be effected by any manner known in the art. One convenient but are not limited to, ethylene, 1-hexene, 1,3-butadiene, and method is to suspend the catalyst system in an organic mixtures thereof. In one aspect of the invention, the unsatur medium and to agitate the mixture to maintain the catalyst ated aliphatic hydrocarbon compound is 1-hexene. If 1-hex system in Solution throughout the trimerization process. ene is the target oligomer to be formed, this may decrease the 50 Other known contacting methods can also be employed. need for Subsequent purification steps. Aromatic hydrocar For example, a continuous-feed autoclave reactor with a bons that may be used as the unsaturated hydrocarbon in the fluid jacket or internal heat transfer coil and any suitable preparation of the catalyst system may include, but are not stiffing mechanism, such as, for example, mechanical stirring limited to, C to Cso aromatic compounds; alternatively, C to or the sparging with an inert gas, typically nitrogen, may be Co aromatic compounds; alternatively, C to Cs aromatic 55 used. In another embodiment, a loop reactor with mechanical compounds; or alternatively, C to Co aromatic compounds. stirring, such as, for example, a circulating pump, can be Exemplary aromatic hydrocarbons include, but are not lim used. Alternatively, tubular reactions for carrying out the ited to, benzene, toluene, ethylbenzene, Xylene, mesitylene, oligomerization may also be used in connection with the hexamethylbenzene, and mixtures thereof. In an embodi invention. ment, the aromatic compound may be toluene; alternatively 60 The oligomerization or trimerization process can be car ethylbenzene, or alternatively, xylene. Without being limited ried out in solvent which is used as the process medium. If by theory, it is believed that that use of an unsaturated hydro employed, any number of hydrocarbon solvent may be used carbon during the preparation of the catalyst system improved as the process medium for the oligomerization or trimeriza catalyst system stability. tion reaction. In embodiment, the solvent that may be utilized It should be recognized, that the reaction mixture compris 65 as the process medium may be hydrocarbon or halogenated ing a chromium compound, the pyrrole compound, metal hydrocarbon; alternatively, a hydrocarbon; or alternatively a alkyl and unsaturated hydrocarbon can contain additional halogenated hydrocarbon. Hydrocarbons and halogenated US 8,471,085 B2 37 38 hydrocarbon can include, for example, aliphatic hydrocar bons; or alternatively, C to Cs halogenated aliphatic hydro bons, aromatic hydrocarbons, petroleum distillates, haloge carbons. The halogenated aliphatic hydrocarbons may be nated aliphatic hydrocarbons, halogenated aromatic hydro cyclic or acyclic and/or may be linear or branched, unless carbons, or combinations thereof, alternatively aliphatic otherwise specified. Non-limiting examples of suitable halo hydrocarbons, aromatic hydrocarbons, halogenated aliphatic genated aliphatic hydrocarbons which may be utilized hydrocarbons, halogenated aromatic hydrocarbons, and com include methylene chloride, chloroform, carbon tetrachlo binations thereof; alternatively, aliphatic hydrocarbons; alter ride, dichloroethane, trichloroethane, and combinations natively, aromatic hydrocarbons; alternatively, halogenated thereof; alternatively, methylene chloride, chloroform, aliphatic hydrocarbons; or alternatively, halogenated aro dichloroethane, trichloroethane, and combinations thereof; matic hydrocarbons. Aliphatic hydrocarbons which may be 10 alternatively, methylene chloride; alternatively, chloroform: useful as a solvent include C to Coaliphatic hydrocarbons; alternatively, carbon tetrachloride; alternatively, dichloroet alternatively C to Caliphatic hydrocarbons; or alterna hane; or alternatively, trichloroethane. Halogenated aromatic tively, Cs to Coaliphatic hydrocarbons. The aliphatic hydro hydrocarbons which may be useful as a solvent include C to carbons may be cyclic or acyclic and/or may be linear or Co halogenated aromatic hydrocarbons; or alternatively, C branched, unless otherwise specified. Non-limiting examples 15 to Co halogenated aromatic hydrocarbons. Non-limiting of suitable acyclicaliphatic hydrocarbon solvents that may be examples of Suitable halogenated aromatic hydrocarbons utilized singly or in any combination include propane, iso include chlorobenzene, dichlorobenzene, and combinations butane, n-butane, butane (n-butane or a mixture of linear and thereof; alternatively chlorobenzene and dichlorobenzene. branched Cacyclic aliphatic hydrocarbons), pentane (n-pen The choice of the oligomerization solvent may be made on tane or a mixture of linear and branched Cs acyclic aliphatic the basis of convenience in processing. For example, isobu hydrocarbons), hexane (n-hexane or mixture of linear and tane may be chosen to be compatible with diluents used for branched Cacyclic aliphatic hydrocarbons), heptane (n-hep the formation of polyolefins in a Subsequent processing step. tane or mixture of linear and branched C, acyclic aliphatic In some embodiments, a reaction product or reaction feed hydrocarbons), octane (n-octane or a mixture of linear and stock olefin may be utilized as the solvent/process medium. branched Cs acyclic aliphatic hydrocarbons), and combina 25 For example, since 1-hexene may be the reaction product of tions thereof, alternatively, iso-butane, n-butane, butane an ethylene trimerization process, it may be chosen as the (n-butane or a mixture of linear and branched C acyclic oligomerization solvent to decrease the need for separation. aliphatic hydrocarbons), pentane (n-pentane or a mixture of In accordance with another embodiment of this invention, linear and branched Cs acyclic aliphatic hydrocarbons), hex a slurry process can be carried out in a diluent (medium), ane (n-hexane or mixture of linear and branched Cacyclic 30 which is a product of the olefin oligomerization process. aliphatic hydrocarbons), heptane (n-heptane or mixture of Therefore, the choice of reactor diluent, or medium, may be linear and branched C, acyclic aliphatic hydrocarbons), based on the selection of the initial olefin reactant and/or the octane (n-octane or a mixture of linear and branched Cs oligomerization product. For example, if the oligomerization acyclic aliphatic hydrocarbons), and combinations thereof. catalyst is used to trimerize ethylene to 1-hexene, the solvent alternatively, iso-butane, n-butane, butane (n-butane or a mix 35 for the oligomerization reaction could be 1-hexene. If ethyl ture of linear and branched C acyclic aliphatic hydrocar ene and hexene are trimerized, the oligomerization reaction bons), pentane (n-pentane or a mixture of linear and branched solvent could be 1-hexene, and/or a trimerization product. If Cs acyclic aliphatic hydrocarbons), heptane (n-heptane or 1,3-butadiene was trimerized to 1,5-cyclooctadiene, the tri mixture of linear and branched C, acyclic aliphatic hydrocar merization reactor solvent could be 1,3-butadiene or 1.5- bons), octane (n-octane or a mixture of linear and branched 40 cyclooctadiene. Cs acyclic aliphatic hydrocarbons), and combinations Reaction temperatures and pressures can be any tempera thereof, alternatively, propane; alternatively, iso-butane; ture and pressure which are suitable to trimerize the olefin alternatively, n-butane; alternatively, butane (n-butane or a reactants using the catalyst system. Generally, reaction tem mixture of linear and branched Cacyclic aliphatic hydrocar peratures are within a range of -20°C. to 250° C. In another bons); alternatively, pentane (n-pentane or a mixture of linear 45 aspect of the invention, reaction temperatures are within a and branched Cs acyclic aliphatic hydrocarbons); alterna range of 60° C. to 200° C. In yet another aspect, reaction tively, hexane (n-hexane or mixture of linear and branched C. temperatures are within a range of 80° C. to 150° C. Gener acyclic aliphatic hydrocarbons); alternatively, heptane ally, reaction pressures are within a range of atmospheric to (n-heptane or mixture of linear and branched C, acyclic ali 2500 psig. In another aspect of the invention, reaction pres phatic hydrocarbons); or alternatively, octane (n-octane or a 50 Sures may be within a range of atmospheric to 2500 psig; or mixture of linear and branched Cs acyclic aliphatic hydrocar alternatively, within a range of atmospheric to 1600 psig. In bons). Non-limiting examples of Suitable cyclic aliphatic yet another aspect of the invention, the reaction pressure hydrocarbon solvents include cyclohexane, methylcyclohex ranges between 300 psig and 900 psig. When the olefinic ane; alternatively cyclohexane, or alternatively, methylcyclo compound is ethylene, the reaction may be performed at an hexane. Aromatic hydrocarbons which may be useful as a 55 ethylene partial pressure ranging from 20 psi to 2500 psi; solvent include C to Cao aromatic hydrocarbons; or alterna alternatively, from 100psi to 2000; alternatively, from 200 psi tively, C to Co aromatic hydrocarbons. Non-limiting to 1500 psi; or alternatively, from 300 psi to 1000 psi. examples of suitable aromatic hydrocarbons that may be uti If the reaction temperature is too low can produce too much lized singly or in any combination include benzene, toluene, undesirable insoluble product, Such as, for example, polymer, Xylene (including ortho-Xylene, meta-xylene, para-Xylene, or 60 and if the reaction temperature is too high it can cause deac mixtures thereof), and ethylbenzene, or combinations tivation of the catalyst system and isomerization of the reac thereof; alternatively, benzene: alternatively, toluene; alterna tion products. A reaction pressure that is too low can result in tively, Xylene (including ortho-Xylene, meta-xylene, para low catalyst system activity. xylene or mixtures thereof); or alternatively, ethylbenzene. Optionally, hydrogen may be added to the reactor to accel Halogenated aliphatic hydrocarbons which may be useful as 65 erate the reaction and/or increase catalyst system activity. If a solvent include C to Cs halogenated aliphatic hydrocar desired, hydrogen also may be added to the reactor to Sup bons; alternatively, C to Cohalogenated aliphatic hydrocar press polymer production. When hydrogen is utilized, the US 8,471,085 B2 39 40 hydrogen partial pressure may range from 2 psi to 100 psi; After the catalyst system has been deactivated, the oligo alternatively, 5 psi to 75 psi; or alternatively, 10 psi to 50 psi. merization product(s). Such as, for example, 1-hexene, can be The contents of the reactor may be agitated or stirred by an removed. Any removal process can be used, including for inert gas (e.g. nitrogen) purge, by introducing the reactant, example, distillation. hydrogen, fluid medium, or catalyst or exhausting the effluent In an aspect, the oligomerization process or the process to in a manner causing agitation, by mechanical or magnetic prepare an oligomerization product comprising contacting stirring, or in any other Suitable manner. the feedstock olefin with the oligomerization catalyst system The reaction usually is run continuously by steadily charg using a pyrrole compound having Substituent attached at the ing lower 1-olefin reactant(s), catalyst system, and process 2- and 5-positions and wherein at least one the carbon atoms 10 of the groups attached to 2- and 5-position of the pyrrole ring medium and removing the liquid contents of the reactor. For is a secondary carbon atom (or alternatively, both of the example, a continuous stirred tank reactor system can be carbon atoms of the groups attached to 2- and 5-position of employed that includes feed systems for catalyst system, the pyrrole ring is a secondary carbonatom) described herein reactant and medium and a discharge system for the effluent. produces less polymer than the process using an oligomer Alternatively, a batch process can also be employed. 15 ization catalyst system using 2,5-dimethylpyrrole as the pyr The trimerization reaction is an exothermic process, so the role compound. In an aspect wherein the oligomerization is reaction temperature usually can be regulated by circulating an ethylene trimerization process, the catalyst System using a cooling water through a jacket or heat transfer coil, thus pyrrole compound having Substituent attached at the 2- and transferring heat out of the reactor. Efficient heat transfer out 5-positions and wherein at least one the carbon atoms of the of the reactor enables effective maintenance of the desired groups attached to 2- and 5-position of the pyrrole ring is a reaction temperature. Another advantage of more effective secondary carbon atom (or alternatively, both of the carbon heat transfer is that the trimerization reaction can be run at a atoms of the groups attached to 2- and 5-position of the higher throughput for a given temperature, which can pyrrole ring is a secondary carbon atom) produces an oligo improve production efficiency. merization product having a greater selectivity to 1-hexene In an aspect, the reactor effluent is treated to deactivate the 25 than an oligomerization catalyst system using 2,5-dimeth active catalyst system, and may further be treated to separate ylpyrrole as the pyrrole compound. In another aspect wherein products, recycle the residual reactants, medium, and other the oligomerization is an ethylene trimerization process, the components suitable for recycling, and dispose of any com catalyst system using a pyrrole compound having Substituent ponents that are not recycled. attached at the 2- and 5-positions and wherein at least one the When the oligomerization or trimerization process is 30 carbon atoms of the groups attached to 2- and 5-position of deemed to be complete, the reactor effluent stream compris the pyrrole ring is a secondary carbon atom (or alternatively, ing solvent, olefin product(s), catalyst system, and some poly both of the carbon atoms of the groups attached to 2- and mer and/or oligomer, may be contacted with an alcohol to 5-position of the pyrrole ring is a secondary carbon atom) deactivate the active catalyst system. Any alcohol which is produces a 1-hexene product having a greater purity than an soluble in the reactor effluent stream can be used. As used 35 oligomerization catalyst system using 2,5-dimethylpyrrole as herein, the term “alcohol includes monoalcohols, diols, and the pyrrole compound. In an embodiment, the catalyst system polyols. The alcohol may be selected by boiling point, using a pyrrole compound having Substituent attached at the molecular weight, or such that the alcohol will not azeotrope 2- and 5-positions and wherein at least one the carbon atoms with the olefin monomer product. In some embodiments, the of the groups attached to 2- and 5-position of the pyrrole ring alcohol has a boiling point different from the olefin product in 40 is a secondary carbon atom (or alternatively, both of the the reactor effluent stream. In an exemplary process, wherein carbon atoms of the groups attached to 2- and 5-position of the catalyst system is used to trimerize ethylene to 1-hexene, the pyrrole ring is a secondary carbon atom) produces an an alcohol with six or more carbon atoms per molecule may oligomerization selectivity to C products at least 0.5%, be used. In an embodiment the alcohol may be a C to Co, Ca 1.0%, 1.5%, or 2.0% (absolute) greater than the oligomeriza to Co., or C to C2 alcohol. In some embodiments, the alco 45 tion selectivity to C products produced by an oligomeriza hol is selected to be easily removable from the oligomeriza tion catalyst system using 2,5-dimethylpyrrole as the pyrrole tion product (e.g. the trimerization product 1-hexene). Exem compound. plary alcohols include, but are not limited to, 1-hexanol, In another aspect, an ethylene trimerization process or the 2-hexanol, 3-hexanol, 2-ethyl-hexanol, 1-heptanol, 2-hep process to prepare an ethylene trimerization product compris tanol, 3-heptanol, 4-heptanol, 2-methyl-3-heptanol, 1-oc 50 ing contacting the feedstock olefin with the oligomerization tanol, 2-octanol, 3-octanol, 4-octanol, 7-methyl-2-decanol, catalyst system using a pyrrole compound having a hydrogen 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, atom located on at least one pyrrole ring carbonatom adjacent 2-ethyl-1-decanol, and mixtures thereof. In an embodiment to the nitrogen atom of the pyrrole ring and a bulky group the alcohol may be 2-ethyl-1-hexanol. located on a pyrrole ring carbon atom adjacent to any pyrrole Alternatively, a low molecular weight diol or polyol, for 55 carbonatom bearing the hydrogenatom adjacent to the nitro example ethylene glycol, can be used as a catalyst deactiva gen atom of the pyrrole ring (or alternatively, has a hydrogen tion agent. Diols and polyols commonly have much higher atom located on each pyrrole ring carbonatom adjacent to the boiling points than monoalcohols of comparable molecular nitrogenatom of the pyrrole ring and a bulky group located on weight, and thus may be easily separated from Some oligo the pyrrole ring carbon atoms adjacent to the pyrrole ring merization products (e.g. the trimerization product 1-hex 60 carbonatom bearing the hydrogenatom adjacent to the nitro ene). gen atom of the pyrrole ring) may have a higher productivity The alcohol is added to the reactor effluent stream in an (g Ce/g transition metal—e.g. Cr) than the process using amount Sufficient to quench and/or kill the catalyst system to 2,4-dimethylpyrrole as the pyrrole compound, provides a inhibit, or halt: (1) production of undesirable solids, i.e., higher selectivity to C products than the process using 2,4- polymer; and/or (2) oligomerization (or alternatively, trimer 65 dimethylpyrrole as the pyrrole compound, and/or provides a ization) product purity degradation due to isomerization, in higher purity 1-hexene product than the process using 2,4- the product separation process. dimethylpyrrole as the pyrrole compound; alternatively, has a US 8,471,085 B2 41 42 higher productivity (g C/g transition metal—e.g. Cr) than the product than the process using 2,4-dimethylpyrrole as the process using 2,4-dimethylpyrrole as the pyrrole compound; pyrrole compound; alternatively, has a higher productivity (g alternatively, provides a higher selectivity to C products than C/g transition metal—e.g. Cr) than the process using 2,4- the process using 2,4-dimethylpyrrole as the pyrrole com dimethylpyrrole as the pyrrole compound; alternatively, pro pound; or alternatively, provides a higher purity 1-hexene vides a higher selectivity to C products than the process product than the process using 2,4-dimethylpyrrole as the using 2,4-dimethylpyrrole as the pyrrole compound; or alter pyrrole compound. In an embodiment, the productivity (g natively, provides a higher purity 1-hexene product than the C/g transition metal—e.g. Cr) of the catalyst system using process using 2,4-dimethylpyrrole as the pyrrole compound. any herein described pyrrole compound having a hydrogen In an embodiment, the productivity (gC/g transition metal— atom located on at least one pyrrole ring carbonatom adjacent 10 e.g. Cr) of the catalyst system utilizing the catalyst system to the nitrogen atom of the pyrrole ring and a bulky group using any herein described pyrrole compound having For located on a pyrrole ring carbon atom adjacent to any pyrrole mula P2, Formula P3, or Formula P4 wherein R'P and R' carbonatom bearing the hydrogenatom adjacent to the nitro of Formula P2 and R’ of Formula P3 may be any pyrrole gen atom of the pyrrole ring (or alternatively, has a hydrogen substituent group disclosed herein while R'' of Formula P2, atom located on each pyrrole ring carbonatom adjacent to the 15 RP of Formula P3, and R. and RP of Formula P4 may be nitrogenatom of the pyrrole ring and a bulky group located on any herein described bulky pyrrole substituent may be 50%, the pyrrole ring carbon atoms adjacent to the pyrrole ring 75%, or 100% (relative) greater than the productivity of the carbonatom bearing the hydrogenatom adjacent to the nitro process using 2,4-dimethylpyrrole as the pyrrole compound. gen atom of the pyrrole ring) may be 50%, 75%, or 100% In some embodiments, the trimerization selectivity of a trim (relative) greater than the productivity of the process using erization process utilizing the catalyst system using any 2,4-dimethylpyrrole as the pyrrole compound. In some herein described pyrrole compound having Formula P2. For embodiments, the trimerization selectivity of a trimerization mula P3, or Formula P4 wherein R'' and R' of Formula P2 process utilizing the catalyst system using any herein and R’’ of Formula P3 may be any pyrrole substituent group described pyrrole compound having a hydrogenatom located disclosed herein while R'' of Formula P2, R of Formula on at least one pyrrole ring carbon atom adjacent to the 25 P3, and R and R of Formula P4 may be any herein nitrogenatom of the pyrrole ring and a bulky group located on described bulky pyrrole substituent may be 1.0%, 1.5%, a pyrrole ring carbon atom adjacent to any pyrrole carbon 2.0%, or 2.5% (absolute) greater than the oligomerization atom bearing the hydrogen atom adjacent to the nitrogen selectivity to C products produced by an oligomerization atom of the pyrrole ring (or alternatively, has a hydrogenatom catalyst system using 2,5-dimethylpyrrole as the pyrrole located on each pyrrole ring carbon atom adjacent to the 30 compound. In other embodiments, the purity of the 1-hexene nitrogenatom of the pyrrole ring and a bulky group located on produced by the trimerization process utilizing the catalyst the pyrrole ring carbon atoms adjacent to the pyrrole ring system using any herein described pyrrole compound having carbonatom bearing the hydrogenatom adjacent to the nitro Formula P2, Formula P3, or Formula P4 wherein R'? and gen atom of the pyrrole ring) may be 1.0%, 1.5%, 2.0%, or R" of Formula P2 and R’’ of Formula P3 may be any 2.5% (absolute) greater than the oligomerization selectivity 35 pyrrole substituent group disclosed herein while R'' of For to C products produced by an oligomerization catalyst sys mula P2, R of Formula P3, and RP and RP of Formula tem using 2,5-dimethylpyrrole as the pyrrole compound. In P4 may be any herein described bulky pyrrole substituent other embodiments, the purity of the 1-hexene produced by may be 0.5%, 1.0%, 1.5%, or 2.0 (absolute) greater than the the trimerization process utilizing the catalyst system using oligomerization purity of the 1-hexene product produced by any herein described pyrrole compound having a hydrogen 40 an oligomerization catalyst system using 2,5-dimethylpyr atom located on at least one pyrrole ring carbonatom adjacent role as the pyrrole compound. to the nitrogen atom of the pyrrole ring and a bulky group Articles Prepared in Accordance with this Disclosure located on a pyrrole ring carbon atom adjacent to any pyrrole According to yet a further aspect of this disclosure and in carbonatom bearing the hydrogenatom adjacent to the nitro the various embodiments, this disclosure encompasses vari gen atom of the pyrrole ring (or alternatively, has a hydrogen 45 ous articles prepared from the olefin oligomers made by the atom located on each pyrrole ring carbonatom adjacent to the disclosed process. For example and not as a limitation, this nitrogenatom of the pyrrole ring and a bulky group located on disclosure encompasses an article prepared from the oligo the pyrrole ring carbon atoms adjacent to the pyrrole ring merization product produced from the process as described carbonatom bearing the hydrogenatom adjacent to the nitro herein. For example, the article can be produced using the genatom of the pyrrole ring) may be 0.5%, 1.0%, 1.5%, or 2.0 50 oligomerization product in which the oligomerization prod (absolute) greater than the oligomerization purity of the uct is a copolymer. Also by way of example, the article can be 1-hexene product produced by an oligomerization catalyst produced using the oligomerization product in which the system using 2,5-dimethylpyrrole as the pyrrole compound. oligomerization product is a polyethylene copolymer and the In yet another aspect, an ethylene trimerization process or oligomerization product is 1-hexene. the process to prepare an ethylene trimerization product com 55 In a further aspect, and also by way of example, the article prising contacting the feedstock olefin with the oligomeriza can be produced using the oligomerization product in which tion catalyst system using any herein described pyrrole com the oligomerization product is a high density polyethylene, a pound having Formula P2. Formula P3, or Formula P4 low density polyethylene, a medium density polyethylene, a wherein R P and RF of Formula P2 and RP of Formula P3 linear low density polyethylene. In these aspects, the oligo may be any pyrrole Substituent group disclosed herein while 60 merization product can be subjecting to blending, heating, RP of Formula P2, RP of Formula P3, and R.P and RP of melting, compounding, extruding, injection molding, preci Formula P4 may be any bulky pyrrole substituent disclosed sion molding, blow molding, forming a film, forming a coat herein may have a higher productivity (g C/g transition ing, or any combination thereof, in forming the article. metal—e.g. Cr) than the process using 2,4-dimethylpyrrole as Comparative Results the pyrrole compound, provides a higher selectivity to C 65 Referring to FIGS. 1 and 2 and Tables 1 and 2, the oligo products than the process using 2,4-dimethylpyrrole as the merization studies were carried out to compare the catalytic pyrrole compound, and/or provides a higher purity 1-hexene behavior of different pyrroles understandard selective 1-hex US 8,471,085 B2 43 44 ene oligomerization reaction conditions to identify pyrrole the productivity of 2,5-dibenzylpyrrole (productivity -23, compounds that provide active ethylene trimerization catalyst 400 g C6/g Cr) as compared to that of 2,5-diethylpyrrole systems, determine their relative levels of oligomerization (productivity -75,800 g C6/g Cr), although increased steric activity, determine the catalyst system's productivity, deter effects may play a significant role. mine the catalyst system's selectivity to C products, and/or 5 General Disclosure Information determine the purity of the C fraction (i.e. the weight % of All publications and patents mentioned in this disclosure 1-hexene found in the C products produced in the oligomer are incorporated herein by reference in their entireties, for the ization. purpose of describing and disclosing the constructs and meth FIG. 1 illustrates a plot of the C productivities (g C6/g Cr) odologies described in those publications, which might be as a function oftemperature (C.), for chromium-based cata 10 lyst systems prepared using the following pyrroles: 2,5-dim used in connection with the methods of this disclosure. Any ethylpyrrole (2,5-DMP); 2,5-dibenzylpyrrole (2,5-DBP); publications and patents discussed above and throughout the 2,4-dimethylpyrrole (2,4-DMP); 2-methyl-4-isopropypyr text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be con role (2-M-4-IPP; and 2,5-diethylpyrrole (2,5-DEP) over the Strued as an admission that the inventors are not entitled to tested temperatures. As can be seen in FIG. 1, each pyrrole has 15 a unique temperature profile in the oligomerization catalyst antedate such disclosure by virtue of prior invention. system and can optimized optimum or desirable operating Unless indicated otherwise, when a range of any type is conditions for the catalyst system using a particular pyrrole disclosed or claimed, for example a range of the number of compound. From FIG.1, it can be seen that the productivity of carbon atoms, molar ratios, temperatures, and the like, it is the catalyst systems using 2,5-disubstituted pyrrole and 2,4- intended to disclose or claim individually each possible num disubstituted having a bulky Substituent in the 4-position on ber that such a range could reasonably encompass, including the pyrrole ring were more acutely affected by variations in any Sub-ranges encompassed therein. For example, when temperature than other catalyst systems. The data illustrated describing a range of the number of carbon atoms, each in FIG. 1 are provided in detail in Table 1. possible individual integral number and ranges between inte Table 2 data provide the 1-hexene purity (%. 1-hexene of C. 25 gral numbers of atoms that the range includes are encom product produced in the oligomerization), shown as in FIG.2, passed therein. Thus, by disclosing a C to Co alkyl group or and the C selectivity, shown as in FIG. 2, for the indicate an alkyl group having from 1 to 10 carbonatoms or “up to 10 pyrrole compounds. These data are reported at the tempera carbon atoms, Applicants intent is to recite that the alkyl ture (C.) of the highest observed productivity (g C6/g Cr), group can have 1,2,3,4,5,6,7,8,9, or 10 carbonatoms, and which is provided in Table 2, using the catalyst prepared 30 these methods of describing Such a group are interchange according to the Examples. Among other things, these data able. When describing a range of measurements such as illustrate that 2,5-disubstituted pyrroles provide catalyst sys molar ratios, every possible number that such a range could tems with higher productivity that those that contain non-2, reasonably encompass can, for example, refer to values 5-disubstituted pyrroles. Additionally, these data show that within the range with one significant digit more than is 2.4-substitued pyrroles having a bulky substituent in the 4-po 35 present in the end points of a range. In this example, a molar sition of the pyrrole ring provide catalyst systems that have ratio between 1.03:1 and 1.12:1 includes individually molar increased C productivities, increased C selectivities, and/or ratios of 1.03:1, 1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, produce a C product having a higher 1-hexene purity than 1.10:1, 1.11:1, and 1.12:1. Applicants intent is that these two catalyst system using a 2.4-substitued pyrrole that does not methods of describing the range are interchangeable. More have a bulky substituent in the 4-position of the pyrrole ring 40 over, when a range of values is disclosed or claimed, Appli (e.g. 2,4-dimethylpyrrole. Generally, the catalytic productiv cants intend to reflect individually each possible number that ity was observed to increase on moving from the non-Substi Such a range could reasonably encompass, Applicants also tuted pyrrole, to the 2,4-disubstitued pyrrole, to 2- or 5-sub intend for the disclosure of a range to reflect, and be inter stituted pyrrole, to the prototypical 2,5-dimethylpyrrole. changeable with, disclosing any and all Sub-ranges and com The FIG. 2 and Table 2 data further illustrates the highest 45 binations of Sub-ranges encompassed therein. In this aspect, 1-hexene purities and C6 selectivities generally are obtained Applicants disclosure of a C to Co alkyl group is intended with the 2,5-disubstituted pyrrole compound or 2,4-disubsti to literally encompass a C to C alkyl, a C to Cs alkyl, a C tuted compounds having a bulky Substituent in the 4-position to C, alkyl, a combination of a C to C and a Cs to C, alkyl, of the pyrrole ring have at their highest measured catalyst and so forth. When describing a range in which the end points productivity temperatures. As indicated in FIG. 2, the 2.5- 50 of the range have different numbers of significant digits, for DMP, 2,5-DEP, 2,5-DIP, 2,5-DBP 2-M-4-IPP, as well as oth example, a molar ratio from 1:1 to 1.2:1, every possible ers such as 2-MeInd., would appear to offer a good combina number that Such a range could reasonably encompass can, tion of selectivity and purity. for example, refer to values within the range with one signifi In other comparisons, 2-methyl-3-ethyl-5-methylpyrrole cant digit more than is present in the end point of a range (productivity -21,700 g C6/g Cr) and 2-methylindole (pro 55 having the greatest number of significant digits, in this case ductivity -3.500 g C6/g Cr)—two compounds characterized 1.2:1. In this example, a molar ratio from 1:1 to 1.2:1 includes by a similar Substitution pattern and similar steric conges individually molar ratios of 1.01, 1.02, 1.03, 1.04, 1.05, 1.06, tion provide very different productivities. While not intend 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14, 1.15, 1.16, 1.17, ing to be bound by theory, it is possible that the electron 1.18, 1.19, and 1.20, all relative to 1, and any and all sub withdrawing phenyl group fused to the pyrrole ring in 60 ranges and combinations of sub-ranges encompassed therein. 2-methyl indole produces a catalyst with low activity. As a Accordingly, Applicants reserve the right to proviso out or further illustration, indole (productivity -800 g C6/g Cr), exclude any individual members of any such group, including which also has an electron-withdrawing group fused to the any Sub-ranges or combinations of Sub-ranges within the pyrrole ring, produces a catalyst with almost an order of group, if for any reason Applicants choose to claim less than magnitude lower productivity than the pyrrole catalyst (pro 65 the full measure of the disclosure, for example, to account for ductivity -6.400 g C6/g Cr). Again, while not intending to be a reference that Applicants are unaware of at the time of the theory-bound, it is possible that electronic effects may reduce filing of the application. US 8,471,085 B2 45 46 In any application before the United States Patent and DEP); 2,5-dibenzylpyrrole (2,5-DBP or DBP); 2,5-diisopro Trademark Office, the Abstract of this application is provided pylpyrrole (2,5-DIP or DIP); indole (Ind); 2-methylindole for the purpose of satisfying the requirements of 37 C.F.R. (2-MeInd); and pyrrole (Pyr). S1.72 and the purpose stated in 37 C.F.R.S1.72(b) “to enable The pyrrole compounds 2,4-dimethylpyrrole (2,4-DMP), the United States Patent and Trademark Office and the public indole, and 2-methylindole were purchased from Aldrich. generally to determine quickly from a cursory inspection the Both indole (RP>99%) and 2-methylindole (RP 98%) were nature and gist of the technical disclosure.” Therefore, the dried under vacuum at 110° C. for several hours without Abstract of this application is not intended to be used to further purification (RP is the reported purity in wt %; MP is construe the scope of the claims or to limit the scope of the the measured purity in wt %). The 2,4-dimethylpyrrole (2,4- 10 DMP, RP 97%) was purified by distillation under nitrogen subject matter that is disclosed herein. Moreover, any head (bp=165-167° C.) producing a colorless liquid (MP 99.5%). ings that may be employed herein are also not intended to be Other pyrrole ligands, such as 2,5-diethylpyrrole used to construe the scope of the claims or to limit the scope (2,5-DEP), 2,5-dibenzylpyrrole (2,5-DBP), 2,5-diisopropy of the subject matter that is disclosed herein. Any use of the lpyrrole (2,5-DIP), and 2-methyl-4-isopropypyrrole (2-M-4- past tense to describe an example otherwise indicated as 15 IPP) were obtained from Chemstep (Carbon-Blanc, France). constructive or prophetic is not intended to reflect that the The 2,5-DIP(RP>95%) was received as a colorless liquid constructive or prophetic example has actually been carried (MP 96.8%) and was used without further purification. 2.5- Out. DEP (RP>97%) was distilled (MP 98.5%) prior to use. The For any particular compound disclosed herein, the general 2.5-DBP (RP82%) was received as an orange waxy material structure or name presented is also intended to encompass all (MP 82.2%) and was used without further purification. 2-M- structural isomers, conformational isomers, and stereoiso 4-IPP was distilled (MP98.1%) prior to use. The identity of mers that may arise from a particular set of Substituents, these four pyrroles was confirmed by GC-MS. unless indicated otherwise. Thus, a general reference to a B. Catalyst Preparation. compound includes all structural isomers unless explicitly A catalyst Solution was prepared using the standard proce indicated otherwise; e.g. a general reference to butane include 25 dure described here, in which the molar ratios of TEA (tri n-pentane, 2-methyl-butane, and 2,2-dimethylpropane. Addi ethylaluminum) to DEAC (diethylaluminum chloride) to pyr tionally, the reference to a general structure or name encom role compound to Cr were standardized to TEA:DEAC: passes all enantiomers, diastereomers, and other optical iso pyrrole:Cr-11:8:3:1. Anhydrous, degassed ethylbenzene was mers whether in enantiomeric or racemic forms, as well as added to a dry vial in a drybox. To this vial was added neat mixtures of stereoisomers, as the context permits or requires. 30 triethylaluminum (TEA) and neat diethylaluminum chloride For any particular formula or name that is presented, any (DEAC). The contents were mixed and allowed to stand for general formula or name presented also encompasses all con 15 minutes. The selected pyrrole was then slowly added, as gas evolution was observed in most cases. Chromium(III) formational isomers, regioisomers, and stereoisomers that 2-ethylhexanoate (7.25 wt % Cr in ethylbenzene) was used as may arise from a particular set of Substituents. 35 the transition metal compound and was added slowly to the The present disclosure is further illustrated by the follow alkylaluminum/pyrrole Solution with stirring. The catalyst ing examples, which are not to be construed in any way as solution was diluted to a concentration of 5.6 mg Cr/mL by imposing limitations upon the scope thereof. On the contrary, adding an appropriate amount of ethylbenzene to constitute it is to be clearly understood that resort may be had to various the active catalyst what was used as prepared. Orange colored other aspects, embodiments, modifications, and equivalents 40 solutions were observed for 2,4-DMP, 2-methylindole, and thereof which, after reading the description herein, may be 2.5-DEP based catalyst, which are typical. 2,5-DBP initially Suggested to one of ordinary skill in the art without departing produced an orange Solution, but gradually precipitated a from the spirit of the present invention or the scope of the noticeable amount of grey solid over the course of 24 h. Both appended claims. indole and pyrrole produced an orange solution with a white, In the following examples, unless otherwise specified, the 45 fluffy solid which was removed by filtration. 2,5-DIP pro syntheses and preparations described therein were carried out duced copious amounts of black precipitate Suggesting that under an inert atmosphere such as nitrogen and/or argon. the catalyst solution was fairly unstable Solvents were purchased from commercial sources and were typically dried prior to use. Unless otherwise specified, Example 1 reagents were obtained from commercial sources. 50 Oligomerization Reactions EXAMPLES Oligomerization reaction studies comparing the catalytic General Experimental Procedures and Starting behavior of different pyrroles understandard selective 1-hex Materials 55 ene oligomerization reaction conditions, were performed as follows. The standard reactor was a 1 L batch reactor, and Unless specified otherwise, all reactions were performed oligomerization reactions were carried out at the indicated under an inert atmosphere. All glassware was dried in an oven temperature under 50 psig H, and under 850 psig ethylene at 100° C. for 4 hours and brought into an inert atmosphere with ethylene uptake on demand, over a 30 minute run time, glovebox (dry box) while warm. All solvents were purchased 60 using 2.5 mg Cr, in 450 mL of cyclohexane. This methodol from Aldrich as anhydrous grade and were stored over freshly ogy was useful for identifying various Substituted pyrroles activated 5 A molecular sieves. that provided reactive catalysts. A. Pyrroles. Catalyst System Productivity as a Function of Temperature The following abbreviations are used for the pyrrole and The activity of selected pyrroles and their catalyst systems indole ligands used herein: 2,4-dimethylpyrrole (2,4-DMP); 65 was investigated. Particularly, catalyst systems that employed 2-methyl-4-isopropylpyrrole (2-M-4-IPP); 2.5-dimethylpyr 2,5-dimethylpyrrole (2,5-DMP), 2,5-dibenzylpyrrole role (2,5-DMP or DMP); 2,5-diethylpyrrole (2,5-DEP or (2,5-DBP), 2,4-dimethylpyrrole (2,4-DMP), pyrrole, 2,5-di US 8,471,085 B2 47 48 ethylpyrrole (2,5-DEP), and 2-methyl-4-isopropylpyrrole TABLE 1-continued (2-M-4-IPP) were investigated for their catalytic temperature profile, in which their activity and productivity were exam Productivity (g C/g Cr) versus temperature for a variety of pyrrole ined as a function of temperature. FIG. 1 illustrates a plot of compounds. These data are illustrated in FIG. 1. productivity (g C/g Cr) as a function of temperature (C.). 5 for chromium-based catalyst systems prepared using the fol Temperature Productivity lowing pyrroles: 2,5-dimethylpyrrole (2,5-DMP); 2,5-diben Pyrrole Compound (° C.) (g C6 g Cr) Zylpyrrole (2,5-DBP); 2,4-dimethylpyrrole (2,4-DMP); pyr role; 2,5-diethylpyrrole (2,5-DEP), and 2-methyl-4- 10 100 11,882 isopropylpyrrole (2-M-4-IPP). The FIG. 1 productivity 115 14,278 Versus temperature data are listed in Table 1. Among other W \ 130 13,523 things, these studies indicated that each pyrrole typically is 145 13.404 N characterized by its own unique temperature profile, which H can be readily ascertained, and which can be used to establish 15 optimum or desirable operating conditions. 2,4-DMP As illustrated in FIG. 1 and the data in Table 1, one conse 100 30,300 quence of comparing the productivities of various catalyst 115 43,900 systems at a single standard temperature is that an incomplete comparative picture may result. For example, at higher tem peratures (130-135° C.) the 2,5-DMP and 2,5-DEP catalyst systems provide somewhat comparable results (25.900 g N C6/g Crand 22.828 g C6/g Cr, respectively), but when com H pared at their respective highest productivities at about 2-methy4-isopropyl pyrrole 92-95°C., this difference in productivity was exaggerated. At 25 these lower temperatures, the 2,5-DMP (99.460 g C6/g Cr, W \ 11590 6,1386.427 95°C.) is about 31% more productive than the corresponding 125 2,977 2,5-DEP catalyst system (75,757 g C6/g Cr, 92° C.). N H Catalyst System Productivity as a Function of Pyrrole Sub 30 pyrrole stitution The data the oligomerizations, data provided in Table 1 and FIG. 1, illustrate that 2,5-disubstituted pyrroles provide cata 1-Hexene Purity and Selectivity as a Function of Pyrrole lysts with generally higher productivity that those that contain 35 Substitution non-2,5-disubstituted pyrroles. Generally, the catalytic pro Table 2 and FIG. 2 provide a comparison of the C selec ductivity was observed to increase on moving from the non tivities (% C of total oligomerized product) and % 1-hexene substituted pyrrole to 2,4-dimethylpyrrole, to 2,4-disubsti (by weight) in the C product (1-hexene purity) for catalyst tuted pyrroles having a bulky Substituent in the 4-position, to systems using the indicated pyrroles at the catalyst systems the 2,5-disubstituted pyrroles (2,5-dimethylpyrrole being the 40 highest observed productivity. FIG. 2 and Table 2 data illus prototypical 2,5-disubstituted pyrrole). trate the highest 1-hexene purities and C selectivities gener ally are obtained with the 2,5-disubstituted pyrrole com TABLE 1. pounds and 2,4-disubstituted pyrroles having a bulky Productivity (g C/g Cr) versus temperature for a variety of pyrrole Substituent in the 4-position at their highest measured catalyst compounds. These data are illustrated in FIG. 1. 45 productivity temperatures. As indicated in FIG. 2, the 2.5- Temperature Productivity DMP, 2,5-DEP, 2,5-DIP, and 2,5-DBP 2-M-4-IPP, as well as Pyrrole Compound (° C.) (g C6 g Cr) others such as 2-MeInd, would appear to offer a good com bination of C selectivity and 1-hexene purity. 92 75,757 / \ 98 74.478 50 1-Hexene Productivity as a Function of Pyrrole-Based or 105 66.443 Indole-Based Catalyst Systems N 115 39,233 130 22,828 Additional experiments were conducted to evaluate the DEP potential effect of using fused-ring compounds such as indole or Substituted indole as the nitrogen-containing compound in 55 W \ 10595 99.46087,300 the catalysts systems. 2-Methyl-3-ethyl-5-methylpyrrole (21. 115 60,660 700 g C/g Cr) and 2-methylindole (3,500 g C/g Cr) have a N 125 43,000 similar Substitution pattern, with similar steric congestion. 135 25,900 However, the productivities of the catalyst systems produced 2,5-DMP 60 using these tow compound differed by over 600%. Moreover, indole (800 g C/g Cr) produced a catalyst with almost an 45 2,792 order of magnitude lower productivity than the pyrrole cata O W \ O 7085 23,41115,021 lyst (6,400 g C/g Cr). These data can be compared to the 115 9,325 N productivity of 2,5-dibenzylpyrrole (23.400 g C/g Cr) as H 65 compared to that of 2,5-diethylpyrrole (75.800 g C/g Cr), DBP although increased steric effects may play a role in this observed productivity. US 8,471,085 B2 49 50 TABLE 2

1-Hexene purity (% of total C product) and C selectivity (% of total oligomerized product) for a variety of pyrrole compounds, reported at the temperature (C.) of the highest observed productivity (g C/g Cr), using the catalyst prepared according to the Examples.

Productivity Temperature 1-Hexene C6 Pyrrole Compound (gCs/g Cr) (° C.) Purity Selectivity

789 115 95.21 93.1 W

indole

3,508 115 98.48 94.93

N H 2-methylindole

/ \ 3,631 115 98.89 94.57

N H 2,5-DIP f \ 6.427 90 96.54 95.39

N H pyrrole

14,284 115 96.46 92.89

2,4-DMP d 43,900 100 98.90 95.95

N H 2-methy4-isopropyl pyrrole Outy C 23,411 85 99.38 96.13

N H DBP

W \ 99.456 95 99.02 91.72

N H 2,5-DMP US 8,471,085 B2 51 52 TABLE 2-continued 1-Hexene purity (% of total C product) and C selectivity (% of total oligomerized product) for a variety of pyrrole compounds, reported at the temperature (C.) of the highest observed productivity (g Calg Cr), using the catalyst prepared according to the Examples. Productivity Temperature 1-Hexene C6 Pyrrole Compound (gCs/g Cr) (° C.) Purity Selectivity S->- 75,757 92 99.20 94.21

15 What is claimed is: 4. The catalyst system according to claim 2, wherein R' 1. A catalyst system comprising: in Formula P2, R in Formula P3, and RP and R in a) a transition metal compound; Formula P4 independently are a propan-2-yl group, a butan b) a pyrrole compound having Formula P2, P3, or P4: 2-yl, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl P2 group, a pentan-2-yl group, a pentan-3-yl group, a 2-meth R12p ylbutan-1-yl group, a 2-methylbutan-2-yl group, a 3-meth R13p ylbutan-2-yl group, 2,2-dimethylpropan-1-yl group, a hexan e 2-yl group, a hexan-3-yl group, a 2-methylpentan-1-yl group, N-H 2-ethylbutan-1-yl group, a 2-methylpentan-2-yl group, a 2.3- S. 25 dimethylbutan-1-yl group, a 2,3-dimethylbutan-2-yl group, a R 14p heptan-2-yl group, a heptan-3-yl group, a heptan-4-yl group, H P3 a 2-methylhexan-1-yl group, a 2-ethylpentan-1-yl group, a R22p 2-methylhexan-2-yl group, a 2,3-dimethylpentan-1-yl group, H a 2,3-dimethylpentan-2-yl group, a 2,3,3-trimethylpentan-1- e 30 yl group, a 2.3,3-trimethylpentan-2-yl group, an octan-2-yl N-H group, an octan-3-yl group, an octan-4-yl group, a 2-methyl S. heptan-1-yl group, a 2-ethylhexan-1-yl group, a 2-methyl R24p heptan-2-yl group, a nonan-2-yl group, a nonan-3-yl group, a H P4 nonan-4-yl group, a nonan-5-yl group, a decan-2-yl group, a H 35 decan-3-yl group, a decan-4-yl group, or a decan-5-yl group. R33p 5. The catalyst system according to claim 2, wherein the e pyrrole compound is 2-methyl-4-isopropylpyrrole, 2-ethyl N-H 4-isopropylpyrrole, 2-methyl-4-t-butylpyrrole, or 2-ethyl-4- S. R34p t-butylpyrrole. 40 6. The catalyst system according to claim 2, wherein the H chromium compound comprises a chromium(II) or chro wherein mium(III) halide, 1,3-diketonate, or carboxylate. i) R'? and RP of Formula P2 and RPP of Formula P3 7. The catalyst system according to claim 2, wherein the independently area Cs hydrocarbyl grip: and chromium compound comprises a chromium(II) or chro ii) R' in Formula P2, RP in Formula P3, and RP and R in Formula P4 independently are a bulky Cs to 45 mium(III) carboxylate wherein each carboxylate is a C to Cs hydrocarbyl group or a bulky Cs to Cas silyl C. carboxylate. group; and 8. The catalyst system according to claim 2, wherein the c) a metal alkyl. chromium compound is chromium(III) 2-ethylhexanoate, 2. The catalyst system of claim 1, wherein chromium(III) octanoate, chromium(III) 2.2.6.6.-tetrameth a) the transition metal compound comprises a chromium 50 ylheptanedionate, chromium(III) naphthenate, chromium compound; and (III) acetate, chromium(III) propionate, chromium(III) b) the metal alkyl comprises an alkylaluminum compound. butyrate, chromium(III) neopentanoate, chromium(III) lau 3. The catalyst system of claim 2, wherein the R'' group in rate, chromium(III) Stearate, chromium(III) oxalate, chro Formula P2, RP group in Formula P3, and RP and R' mium(II) bis(2-ethylhexanoate), chromium(II) acetate, chro group in Formula P4 are attached such that mium(II) propionate, chromium(II) butyrate, chromium(II) i) the carbonatomattached to the pyrrole ring is attached to 55 neopentanoate, chromium(II) laurate, chromium(II) Stearate, three or four carbon atoms, chromium(II) oxalate, or any combination thereof. ii) the carbonatom adjacent to the carbon atom attached to 9. The catalyst system according to claim 2, wherein the pyrrole ring is attached to three or four carbon atoms, or transition metal compound comprises a chromium(II) or iii) the C to Cassilyl group has Formula Sil chromium(III) carboxylate wherein each carboxylate is a Ca 60 to Cocarboxylate and the metal alkyl comprises a mixture of S1 triethylaluminum and diethylaluminum chloride. Rls 10. The catalyst system according to claim 1, wherein the : metal alkyl comprises a group 1, 2, 11, 12, 13, or 14 of the Periodic Table metal alkyl compound. 65 11. The catalyst system according to claim 1, further com wherein R', R, and R independently area C, to Cs prising a halogen containing compound selected from a metal hydrocarbyl group. halide, an alkyl metal halide, or an organic halide. US 8,471,085 B2 53 54 12. The catalyst system of claim 1, wherein: 2-ethylbutan-1-yl group, a 2-methylpentan-2-yl group, a 2.3- a) the transition metal compound is chromium(III) 2-eth dimethylbutan-1-yl group, a 2,3-dimethylbutan-2-yl group, a ylhexanoate, chromium(III) octanoate, chromium(III) heptan-2-yl group, a heptan-3-yl group, a heptan-4-yl group, 2.2.6.6.-tetramethylheptanedionate, chromium(III) a 2-methylhexan-1-yl group, a 2-ethylpentan-1-yl group, a naphthenate, chromium(III) acetate, chromium(III) pro 5 2-methylhexan-2-yl group, a 2,3-dimethylpentan-1-yl group, pionate, chromium(III) butyrate, chromium(III) neo a 2,3-dimethylpentan-2-yl group, a 2,3,3-trimethylpentan-1- pentanoate, chromium(III) laurate, chromium(III) Stear yl group, a 2.3,3-trimethylpentan-2-yl group, an octan-2-yl ate, chromium(III) oxalate, chromium(II) bis(2- group, an octan-3-yl group, an octan-4-yl group, a 2-methyl ethylhexanoate), chromium(II) acetate, chromium(II) heptan-1-yl group, a 2-ethylhexan-1-yl group, a 2-methyl propionate, chromium(II) butyrate, chromium(II) neo 10 heptan-2-yl group, a nonan-2-yl group, a nonan-3-yl group, a pentanoate, chromium(II) laurate, chromium(II) Stear nonan-4-yl group, a nonan-5-yl group, a decan-2-yl group, a ate, chromium(II) oxalate, or a combination thereof; decan-3-yl group, a decan-4-yl group, or a decan-5-yl group. b) the pyrrole compound is 2-methyl-4-isopropylpyrrole, 2-ethyl-4-isopropylpyrrole, 2-methyl-4-t-butylpyrrole, 20. The oligomerization process of claim 13, wherein: 2-ethyl-4-t-butylpyrrole, or a combination thereof; and 15 a) the transition metal compound is chromium(III) 2-eth c) the metal alkyl is a trialkylaluminum compound, an ylhexanoate, chromium(III) octanoate, chromium(III) alkylaluminum halide compound, or a combination 2.2.6.6.-tetramethylheptanedionate, chromium(III) thereof. naphthenate, chromium(III) acetate, chromium(III) pro 13. An oligomerization process comprising: pionate, chromium(III) butyrate, chromium(III) neo pentanoate, chromium(III) laurate, chromium(III) Stear a) contacting a feedstock olefin with the catalyst system of ate, chromium(III) oxalate, chromium(II) bis(2- claim 1; and ethylhexanoate), chromium(II) acetate, chromium(II) b) oligomerizing the olefin under oligomerization condi propionate, chromium(II) butyrate, chromium(II) neo tions to form an oligomerization product. pentanoate, chromium(II) laurate, chromium(II) Stear 14. The oligomerization process of claim 13, wherein ate, chromium(II) oxalate, or a combination thereof; a) the feedstock olefin comprises ethylene and the oligo 25 b) the pyrrole compound is 2-methyl-4-isopropylpyrrole, merization product comprises 1-hexene, 2-ethyl-4-isopropylpyrrole, 2-methyl-4-t-butylpyrrole, b) the transition metal compound comprises a chromium (II) or chromium(III) carboxylate wherein each car 2-ethyl-4-t-butylpyrrole, or a combination thereof; and boxylate is a C to C carboxylate; and c) the metal alkyl is a trialkylaluminum compound, an c) the metal alkyl comprises a mixture of triethylaluminum 30 alkylaluminum halide compound, or a combination and diethylaluminum chloride. thereof. 15. The oligomerization process of claim 14, wherein the 21. A process for preparing a catalyst System, comprising process provides a higher selectivity to C products than a contacting: process using 2,4-dimethylpyrrole as the pyrrole compound. a) a transition metal compound; 16. The oligomerization process of claim 14, wherein the 35 b) a pyrrole compound having Formula P2, P3, or P4: process provides a higher purity 1-hexene product than a process using 2,4-dimethylpyrrole as the pyrrole compound. P2 17. The oligomerization process of claim 13, wherein the R12p pyrrole compound is 2-methyl-4-isopropylpyrrole, 2-ethyl R13p 4-isopropylpyrrole, 2-methyl-4-t-butylpyrrole, or 2-ethyl-4- 40 e t-butylpyrrole. N-H S. 18. The oligomerization process of claim 14, wherein the R 14p R" group in Formula P2, RP group in Formula P3, and H Rand R group in Formula P4 are attached such that P3 i) the carbonatomattached to the pyrrole ring is attached to 45 R22p three or four carbon atoms, H ii) the carbonatom adjacent to the carbon atom attached to e pyrrole ring is attached to three or four carbon atoms, or N-H S. iii) the C to Cassilyl group has Formula Sil R24p 50 H P4 S1 H Rls V R33p : e Re-si 55 N-H S. R34p wherein R', R, and R independently area C, to Cs H hydrocarbyl group. 19. The oligomerization process of claim 14, wherein R' 60 wherein in Formula P2, RP in Formula P3, and Re and RP in i) R'? and RP of Formula P2 and RPP of Formula P3 Formula P4 independently are a propan-2-yl group, a butan independently area C to Cs hydrocarbyl group; and 2-yl, a 2-methylpropan-1-yl group, a 2-methylpropan-2-yl ii) R' in Formula P2, RP in Formula P3, and RF and group, a pentan-2-yl group, a pentan-3-yl group, a 2-meth R” in Formula P4 independently are a bulky Cs to ylbutan-1-yl group, a 2-methylbutan-2-yl group, a 3-meth 65 Cs hydrocarbyl group or a bulky Cs to Cas silyl ylbutan-2-yl group, 2,2-dimethylpropan-1-yl group, a hexan group; and 2-yl group, a hexan-3-yl group, a 2-methylpentan-1-yl group, c) a metal alkyl. US 8,471,085 B2 55 56 22. The process of claim 21, wherein 27. The process of claim 22, wherein the R'' group in a) the transition metal compound comprises a chromium Formula P2, RP group in Formula P3, and RP and RP (II) or chromium(III) carboxylate wherein each car group in Formula P4 are attached such that boxylate is a C to Co. carboxylate; and i) the carbonatom attached to the pyrrole ring is attached to b) the metal alkyl comprises a mixture of triethylaluminum three or four carbon atoms, and diethylaluminum chloride. ii) the carbon atom adjacent to the carbon atom attached to 23. The process of claim 22, wherein the transition metal pyrrole ring is attached to three or four carbon atoms, or compound, the pyrrole compound, and the metal alkyl are iii) the C to Cassilyl group has Formula Sil contacted in the presence of an unsaturated compound to stabilize the catalyst system, wherein the unsaturated com 10 pound comprises a C to Cls aromatic compound. S1 24. The process of claim 23, wherein the aromatic com pound comprises benzene, toluene, ethylbenzene, xylene, mesitylene, hexamethylbenzene, or mixtures thereof. 25. The process of claim 22, wherein R'' in Formula P2, 15 R’ in Formula P3, and RP and RP in Formula P4 inde pendently are a propan-2-yl group, a butan-2-yl, a 2-methyl wherein R', R, and R independently area C, to Cs propan-1-yl group, a 2-methylpropan-2-yl group, a pentan hydrocarbyl group. 2-yl group, a pentan-3-yl group, a 2-methylbutan-1-yl group, 28. The process of claim 21, wherein: a 2-methylbutan-2-yl group, a 3-methylbutan-2-yl group, a) the transition metal compound is chromium(III) 2-eth 2,2-dimethylpropan-1-yl group, a hexan-2-yl group, a hexan ylhexanoate, chromium(III) octanoate, chromium(III) 3-yl group, a 2-methylpentan-1-yl group, 2-ethylbutan-1-yl 2.2.6.6,-tetramethylheptanedionate, chromium(III) group, a 2-methylpentan-2-yl group, a 2.3-dimethylbutan-1- naphthenate, chromium(III) acetate, chromium(III) pro yl group, a 2.3-dimethylbutan-2-yl group, a heptan-2-yl pionate, chromium(III) butyrate, chromium(III) neo group, a heptan-3-yl group, a heptan-4-yl group, a 2-methyl 25 pentanoate, chromium(III) laurate, chromium(III) stear hexan-1-yl group, a 2-ethylpentan-1-yl group, a 2-methyl ate, chromium(III) oxalate, chromium(II) bis(2- hexan-2-yl group, a 2.3-dimethylpentan-1-yl group, a 2.3- ethylhexanoate), chromium(II) acetate, chromium(II) dimethylpentan-2-yl group, a 2.3,3-trimethylpentan-1-yl propionate, chromium(II) butyrate, chromium(II) neo group, a 2.3,3-trimethylpentan-2-yl group, an octan-2-yl pentanoate, chromium(II) laurate, chromium(II) stear group, an octan-3-yl group, an octan-4-yl group, a 2-methyl 30 ate, chromium(II) oxalate, or a combination thereof; heptan-1-yl group, a 2-ethylhexan-1-yl group, a 2-methyl b) the pyrrole compound is 2-methyl-4-isopropylpyrrole, heptan-2-yl group, a nonan-2-yl group, a nonan-3-yl group, a 2-ethyl-4-isopropylpyrrole, 2-methyl-4-t-butylpyrrole, nonan-4-yl group, a nonan-5-yl group, a decan-2-yl group, a 2-ethyl-4-t-butylpyrrole, or a combination thereof; and decan-3-yl group, a decan-4-yl group, or a decan-5-yl group. c) the metal alkyl is a trialkylaluminum compound, an 26. The process of claim 22, wherein the pyrrole compound 35 alkylaluminum halide compound, or a combination is 2-methyl-4-isopropylpyrrole, 2-ethyl-4-isopropylpyrrole. thereof. 2-methyl-4-t-butylpyrrole, or 2-ethyl-4-t-butylpyrrole. ck ck ck ci: C