Hyperbranched ethylene-based oils and greases

Abstract

A process to prepare a relatively inexpensive utility fluid comprises contacting together ethylene and a coordination-insertion catalyst and, optionally, an alpha-olefin, in a continuously-fed backmixed reactor zone under conditions such that a mixture of a hyperbranched oligomer and a branched oligomer is formed. The hyperbranched oligomer has an average of at least 1.5 methine carbons per oligomer molecule, and at least 40 methine carbons per one-thousand total carbons, and at least 40 percent of the methine carbons is derived from the ethylene, and the average number of carbons per molecule is from 25 to 100, and at least 25 percent of the hyperbranched oligomer molecules has a vinyl group and can be separated from the branched oligomer, which has an average number of carbons per molecule of up to 20. The coordination-insertion catalyst is characterized as having an ethylene/octene reactivity ratio up to 20 and a kinetic chain length up to 20 monomer units.

Claims

1. A process to prepare a utility fluid composition comprising: (1) contacting together ethylene and at least one coordination-insertion catalyst and, optionally, an alpha-olefin, wherein the coordination-insertion catalyst is a metal-ligand complex wherein the metal is selected from zirconium, hafnium and titanium, and has an ethylene/octene reactivity ratio up to 20, and a kinetic chain length up to 20 monomer units; in a continuously-fed backmixed reactor zone under conditions such that a mixture of at least two oligomer products is formed, the mixture including a hyperbranched oligomer having an average of at least 1.5 methine carbons per oligomer molecule, and having at least 40 methine carbons per one-thousand total carbons, and wherein at least 40 percent of the methine carbons is derived from the ethylene, and wherein the average number of carbons per molecule is from 25 to 100, and wherein at least 25 percent of the hyperbranched oligomer molecules has a vinyl group; and at least one branched oligomer having an average number of carbons per molecule that is less than 20; (2) separating the hyperbranched oligomer from the branched oligomer; and (3) recovering the hyperbranched oligomer, the branched oligomer, or both.

2. The process of claim 1 wherein the metal-ligand complex is a compound of the formula ##STR00014## wherein M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3, or +4; n is an integer of from 0 to 3, wherein when n is 0, X is absent; each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic, or two X are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; X and n are selected such that the metal-ligand complex of the formula is, overall, neutral; each Z is independently O, S, N(C.sub.1-C.sub.40)hydrocarbyl, or P(C.sub.1-C.sub.40)hydrocarbyl; L is (C.sub.1-C.sub.40)hydrocarbylene or (C.sub.1-C.sub.40)heterohydrocarbylene, wherein the (C.sub.1-C.sub.40)-hydrocarbylene has a portion that comprises a 2-carbon atom linker backbone linking the Z atoms in the formula and the (C.sub.1-C.sub.40)heterohydrocarbylene has a portion that comprises a 2-atom atom linker backbone linking the Z atoms in the formula, wherein each atom of the 2-atom linker of the (C.sub.1-C.sub.40)-heterohydrocarbylene independently is a carbon atom or a heteroatom, wherein each heteroatom independently is O, S, S(O), S(O).sub.2, Si(R.sup.C).sub.2, Ge(R.sup.C).sub.2, P(R.sup.P), or N(R.sup.N), wherein independently each R.sup.C is unsubstituted (C.sub.1-C.sub.18)hydrocarbyl or the two R.sup.C are taken together to form a (C.sub.2-C.sub.19)alkylene, each R.sup.P is unsubstituted (C.sub.1-C.sub.18)hydrocarbyl; and each R.sup.N is unsubstituted (C.sub.1-C.sub.18)hydrocarbyl, a hydrogen atom or absent; R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b independently is a hydrogen, (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)-heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO, or halogen atom, and each of the others of R.sup.1a, R.sup.2a, R.sup.1b, and R.sup.2b independently is a hydrogen, (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)-heterohydrocarbyl, N(R.sup.N).sub.2, NO.sub.2, OR.sup.C, SR.sup.C, Si(R.sup.C).sub.3, CN, CF.sub.3, F.sub.3CO or halogen atom; each of R.sup.3a, R.sup.4a, R.sup.3b, R.sup.4b, R.sup.6c, R.sup.7c, R.sup.8c, R.sup.6d, R.sup.7d, and R.sup.8d independently is a hydrogen atom, (C.sub.1-C.sub.40)hydrocarbyl, (C.sub.1-C.sub.40)-heterohydrocarbyl, Si(R.sup.C).sub.3, Ge(R.sup.C).sub.3, P(R.sup.P).sub.2, N(R.sup.N).sub.2, OR.sup.C, SR.sup.C, NO.sub.2, CN, CF.sub.3, RCS(O), RCS(O).sub.2, (RC).sub.2CN, RCC(O)O, RCOC(O), RCC(O)N(R), (RC)2NC(O) or halogen atom; each of R.sup.5c and R.sup.5d is independently a (C.sub.6-C.sub.40)aryl or (C.sub.1-C.sub.40)heteroaryl; each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and heterohydrocarbylene groups is independently unsubstituted or substituted with 1 to 5 more substituents R.sup.S; and each R.sup.S is independently a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C.sub.1-C.sub.18)alkyl, F.sub.3C, FCH.sub.2O, F.sub.2HCO, F.sub.3CO, R.sub.3Si, R.sub.3Ge, RO, RS, RS(O), RS(O).sub.2, R.sub.2P, R.sub.2N, R.sub.2CN, NC, RC(O)O, ROC(O), RC(O)N(R), or R.sub.2NC(O), or two of the R.sup.S are taken together to form an unsubstituted (C.sub.1-C.sub.18)alkylene, wherein each R independently is an unsubstituted (C.sub.1-C.sub.18)alkyl.

3. The process of claim 1 wherein the coordination-insertion catalyst is selected from the group consisting of ##STR00015## ##STR00016## and combinations thereof.

4. The process of claim 1 wherein the metal-ligand complex is a compound of the formula ##STR00017## wherein M is the metal center, and is a Group 4 metal selected from titanium, zirconium or hafnium; T is an optional bridging group which, if present, is selected from dialkylsilyl, diarylsilyl, dialkylmethyl, ethylenyl (CH.sub.2CH.sub.2) or hydrocarbylethylenyl wherein one, two, three or four of the hydrogen atoms in ethylenyl are substituted by hydrocarbyl, where hydrocarbyl can be independently C.sub.1 to C.sub.16 alkyl or phenyl, tolyl, or xylyl, and when T is present, the catalyst represented can be in a racemic or a meso form; L.sub.1 and L.sub.2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, optionally substituted, that are each bonded to M, or L.sub.1 and L.sub.2 are the some or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, the rings of which are optionally substituted with one or more R groups, with any two adjacent R groups being optionally joined to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic substituent; Z is nitrogen, oxygen or phosphorus; R is a cyclic linear or branched C.sub.1 to C.sub.40 alkyl or substituted alkyl group; and X.sub.1 and X.sub.2 are, independently, hydrogen, halogen, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, substituted silylcarbyl radicals, germylcarbyl radicals, or substituted germylcarbyl radicals; or both X are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms; or both together form an olefin, diolefin or aryne ligand.

5. The process of claim 1, further comprising (4) performing a hydrogenation, halogenation, etherification, hydroxylation, esterification, oxidation, or hydroformylation of the hyperbranched oligomer, the branched oligomer, or both.

6. The process of claim 1, wherein at least 55 percent of the methine carbons is derived from the ethylene.

7. The process of claim 6, wherein at least 70 percent of the methine carbons is derived from the ethylene.

8. The process of claim 1 wherein at least 50 percent of the hyperbranched oligomer molecules has a vinyl group.

9. The process of claim 8 where at least 75 percent of the hyperbranched oligomer molecules has a vinyl group.

10. A utility fluid composition prepared by the process of claim 1.

Description

EXAMPLES 1-7 AND COMPARATIVE EXAMPLE A

Steady-State Continuous Stir Tank Reactor (CSTR) Oligomerizations

(1) Small scale continuous flow solution oligomerizations are carried out in a computer controlled Autoclave Engineers reactor equipped with an internal stirrer and a single, stationary baffle operating at about a 9.5 minute (min) average residence time. Purified mixed alkanes solvent (Isopar E, available from ExxonMobil, Inc. consisting of C7-C9 isoalkanes) and ethylene are supplied at 1.00 gram per minute (g/min) to a 0.10 liter (L) reactor equipped with a jacket for temperature control, internal cooling coils, and thermocouple. For the various examples the reactor temperature set points range from 60 C. to 132 C. and are maintained by circulating heated oil through the jacket and cooling water through the internal cooling coils. A mass flow controller is used to deliver ethylene to the reactor.

(2) The examples use various coordination-insertion catalysts which are activated with bis (octadecyl)methylammonium tetrakis(pentafluorophenyl) borate ([HNMe(C.sub.18H.sub.37).sub.2][B(C.sub.6F.sub.5).sub.4], abbreviated as BOMATBP). Modified methy aluminoxane (MMAO) is used as a scavenger, which moderates the effects of polar impurities on catalyst performance. The catalysts are delivered to the reactor as a 0.0001 mole/L solution in toluene; the catalyst activator, BOMATPB, is delivered to the reactor as a 0.00012 mole/L solution in Isopar E; and the MMAO scavenger is delivered as a 0.01 mole/L solution in Isopar E.

(3) The Isopar solvent and solutions of catalyst, activator, and scavenger are fed into the reactor with syringe pumps, with a 1.2 molar ratio of BOMATPB and a 20:1 molar ratio of MMAO per catalyst metal such as Hf or Zr. The feed streams are introduced into the bottom of the reactor via two eductor tubes. The reactor is run liquid-full at 300 to 400 pounds per square inch gauge (psig, 2.1 to 2.7 megapascals, MPa) with vigorous stirring, while the products are removed through an exit line at the top of the reactor. The reactor effluent is electrically heat traced and insulated as it passes through an optical spectrophotometer cell that monitors the ethylene concentration (in grams per deciliter, g/dL). Oligomerization is stopped by the addition of a small amount of water and 2-propanol into the exit line along with a 2:1 mixture of Irgafos 168 and Irganox 1010 stabilizers, which are added at total level of 2000 parts per million (ppm) based on the mass of ethylene feed. This means that 0.2 g stabilizer is added for every 100 g of ethylene feed. The product is devolatilized to remove light olefins, i.e., the branched oligomer having average carbon numbers of 20 or less, and a hyperbranched oligomer, which is an oligomeric oil, is then collected under an inert nitrogen atmosphere and dried in a temperature ramped vacuum oven for approximately 10 hours (h), with a final high temperature set point of 140 C.

(4) Several catalysts are tested in the continuous flow reactor as shown in Tables 1 through 8. For each designated reaction temperature the catalyst feed rate is varied until a targeted steady-state ethylene conversion (i.e., oligomer production rate) is attained. A steady-state condition is defined as having been achieved when six (6) residence times have elapsed under constant feed with negligible change in ethylene conversion or pressure. The catalyst feed rate is reported in ppm, which is a ratio of catalyst metal weight per weight of total reactor contents. Quantities Cn and Bn are calculated from the .sup.13C NMR spectra of the recovered oils, where Cn is the ratio of total carbons per unsaturation and Bn is the ratio of methine carbons per unsaturation. Because there are no added chain transfer agents such as hydrogen or metal alkyls, it is assumed that each oil molecule has a single unsaturation and therefore Cn is assumed to be the average number of carbons per molecule and Bn is assumed to be the average number of methine branch points per molecule. The quantity Pv is the percent of unsaturated groups that are vinyls and is also expected to be the vinyl endgroup percentage, because each oil molecule is assumed to have a single unsaturated endgroup.

Example 1

(5) The coordination-insertion catalyst shown in Formula (I) is used at the temperatures shown in Table 1 and at an overall reactor feed rate of 7.43 g/min. Results are shown in Table 1, and oligomer in g/min in that table refers to production rate for the hyperbranched oligomer.

(6) TABLE-US-00001 TABLE 1 13CNMR Data 13CNMR Temp Catalyst Oligomer Ethylene Ethylene per 1000 carbons Visc Flash calculations ( C.) (ppm) (g/min) (g/dL) (% conv) methines vinyl vinylene vinylidene (Pa * s) Pt ( C.) Cn Bn Pv 132 0.26 0.61 0.20 97.7 41.28 20.58 3.18 1.94 .160 199 38.9 1.61 80.1 80 0.28 0.68 ~0 >99 65.53 15.43 3.97 2.84 .090 227 45.0 2.95 69.4 82 0.12 0.51 0.54 94.1 53.24 24.15 2.42 1.85 .039 195 35.2 1.87 85.0 82 0.09 0.46 0.69 92.5 50.35 25.42 2.28 1.71 .055 201 34.0 1.71 86.4

Example 2

(7) The Formula (I) coordination-insertion catalyst is used at 70 C. with an overall reactor feed rate of 7.43 g/min and all other conditions employed in Example 1. The first two steady-state conditions (first two rows) have an ethylene concentration below the detection limit. Results are shown in Table 2.

(8) TABLE-US-00002 TABLE 2 13CNMR Data 13CNMR Temp Catalyst Oligomer Ethylene Ethylene per 1000 carbons Visc Flash calculations ( C.) (ppm) (g/min) (g/dL) (% conv) methines vinyl vinylene vinylidene (Pa * s) Pt ( C.) Cn Bn Pv 70 0.37 0.80 ~0 >99 79.2 8.54 5.99 3.90 .167 218 54.3 4.30 46.3 70 0.74 0.85 ~0 >99 81.79 7.24 6.20 4.15 .191 228 56.9 4.65 41.2 70 0.10 0.63 0.09 99.0 69.53 16.83 3.81 2.70 .077 220 42.8 2.98 72.1 70 0.08 0.50 0.39 95.9 62.92 20.39 2.83 2.37 .057 231 39.1 2.46 79.7

Example 3

(9) The same catalyst as in previous examples is used at 60 C. with an overall reactor feed rate of 7.43 g/min. The last four steady-states have an ethylene concentration below the detection limit. Results are shown in Table 3.

(10) TABLE-US-00003 TABLE 3 13CNMR Data 13CNMR Temp Catalyst Oligomer Ethylene Ethylene per 1000 carbons Visc Flash calculations ( C.) (ppm) (g/min) (g/dL) (% conv) methines vinyl vinylene vinylidene (Pa * s) Pt ( C.) Cn Bn Pv 60 0.09 0.53 0.42 95.6 67.71 22.03 3.06 2.37 .047 211 36.4 2.47 80.2 60 0.11 0.68 0.06 99.4 75.95 16.15 4.05 2.96 .074 215 43.2 3.28 69.7 60 0.07 0.38 1.03 89.1 60.74 25.82 2.35 1.95 .035 213 33.2 2.02 85.7 60 1.10 0.88 ~0 >99 83.59 6.10 6.58 4.48 .209 220 58.3 4.87 35.5 60 0.15 0.81 ~0 >99 80.4 11.99 5.16 3.66 .119 206 48.1 3.86 57.6 60 0.12 0.78 ~0 >99 77.86 14.54 4.81 3.56 .093 202 43.6 3.40 63.5 60 0.15 0.77 ~0 >99 80.06 11.95 4.83 3.38 .119 228 49.6 3.97 59.3

Example 4

(11) The Formula (II) coordination-insertion catalyst is used at 60 C. with an overall reactor feed rate of 7.43 g/min. The last three steady-states have an ethylene concentration below the detection limit. Results are shown in Table 4.

(12) TABLE-US-00004 TABLE 4 13CNMR Data 13CNMR Temp Catalyst Oligomer Ethylene Ethylene per 1000 carbons Visc Flash calculations ( C.) (ppm) (g/min) (g/dL) (% conv) methines vinyl vinylene vinylidene (Pa * s) Pt ( C.) Cn Bn Pv 60 0.25 0.56 0.29 96.8 75.55 13.23 1.45 11.78 .048 206.5 37.8 2.86 50.0 60 0.61 0.65 ~0 >99 79.33 9.75 1.68 13.28 .056 202.5 40.5 3.21 39.5 60 1.23 0.67 ~0 >99 78.93 8.53 2.01 14.34 .054 200.6 40.2 3.17 34.3 60 2.45 0.67 ~0 >99 79.18 7.04 1.78 16.28 .049 206.6 39.8 3.15 28.0

Example 5

(13) The Formula (III) coordination-insertion catalyst is used at 60 C. with an overall reactor feed rate of 7.35 g/min. Three of the steady-states have an ethylene concentration below the detection limit. Results are shown in Table 5.

(14) TABLE-US-00005 TABLE 5 13CNMR Data 13CNMR Temp Catalyst Oligomer Ethylene Ethylene per 1000 carbons Visc Flash calculations ( C.) (ppm) (g/min) (g/dL) (% conv) methines vinyl vinylene vinylidene (Pa * s) Pt ( C.) Cn Bn Pv 60 0.25 0.39 0.21 97.9 87.25 20.60 3.74 5.97 .033 210 33.0 2.88 68.0 60 0.62 0.48 ~0 >99 90.93 17.32 4.25 6.54 .039 214 35.6 3.23 61.6 60 1.24 0.53 ~0 >99 94.78 15.49 4.47 6.85 .047 216 37.3 3.54 57.8 60 2.48 0.58 ~0 >99 96.83 13.86 4.75 7.41 .048 208 38.4 3.72 53.3 60 0.19 0.45 0.37 96.2 86.78 24.56 3.83 5.93 .018 29.1 2.53 71.6 60 0.12 0.37 0.56 94.1 83.94 25.42 3.56 5.43 .019 29.1 2.44 73.9 60 0.07 0.27 1.06 88.9 78.83 28.02 2.77 4.81 .016 28.1 2.21 78.7

Example 6

(15) The Formula (V) coordination-insertion catalyst is used at 60 C. with an overall reactor feed rate of 7.35 g/min. Results are shown in Table 6.

(16) TABLE-US-00006 TABLE 6 13CNMR Data 13CNMR Temp Catalyst Oligomer Ethylene Ethylene per 1000 carbons Visc Flash calculations ( C.) (ppm) (g/min) (g/dL) (% conv) methines vinyl vinylene vinylidene (Pa * s) Pt ( C.) Cn Bn Pv 60 0.25 0.20 0.26 97.3 76.76 12.44 3.08 19.46 .016 28.6 2.19 35.6 60 0.12 0.17 0.40 95.9 74.8 13.97 2.89 18.64 .014 28.2 2.11 39.4 60 0.07 0.11 0.59 94.0 71.57 15.57 2.61 17.91 .015 27.7 1.98 43.1 60 0.62 0.22 0.14 98.5 74.39 10.87 3.33 20.01 .017 29.2 2.17 31.8

Example 7 and Comparative Example A

(17) The Formula (IV) coordination-insertion catalyst is used at 60 C. and 70 C. with an overall reactor feed rate of 7.35 g/min. The first steady-state has an ethylene concentration below the detection limit. Results are shown in Table 7. Notably, Comparative Example A shows less than 40 methines per 1000 carbons and insufficient methine branch carbons per molecule to qualify as a hyperbranched product. This low level of branching can be explained by the low ethylene conversion (90.3%) resulting in a higher free ethylene concentration (0.96 g/dl). This condition creates a less favorable environment for the re-incorporation of alpha-olefin product and results in less branching.

(18) TABLE-US-00007 TABLE 7 Ex or Temp Catalyst Oligomer C.sub.2H.sub.4 C.sub.2H.sub.4 .sup.13C NMR Data per 1000 carbons .sup.13C NMR calculations CEx ( C.) (ppm) (g/min)* (g/dL) (% conv) Methines Vinyl Vinylene Vinylidene Cn Bn Pv CEx A 60 0.13 0.52 0.96 90.3 37.32 22.74 0.43 4.60 36.0 1.34 81.9 Ex 7 70 1.21 0.82 ~0 >99 53.27 10.71 1.04 6.97 53.4 2.85 57.2

Examples 8-9 and Comparative Examples B-D

Semi-Batch Oligomerizations

(19) Semi-batch oligomerizations are conducted in a 2 L Parr batch reactor. The reactor is heated by an electrical heating mantle, and is cooled by an internal serpentine cooling coil containing cooling water. Both the reactor and the heating/cooling system are controlled and monitored by a Camile TG process computer. The bottom of the reactor is fitted with a dump valve, which empties the reactor contents into a stainless steel dump pot, which is prefilled with a catalyst kill solution (typically 5 mL of an Irgafos/Irganox/toluene mixture).

(20) The dump pot is vented to a 30 gallon blowdown tank, with both the pot and the tank N.sub.2 purged. All chemicals used for oligomerization or catalyst makeup are run through purification columns to remove any impurities that may affect oligomerization. Liquid feeds such as alpha-olefin and solvents are passed through two columns, the first containing Al.sub.2O.sub.3 alumina, the second containing Q5, which is a copper reactant to scrub oxygen. Ethylene feed is passed through two columns, the first containing Al.sub.2O.sub.3 alumina and 4 Angstroms () average pore size molecular sieves to remove water, the second containing Q5 reactant. The N.sub.2, used for transfers, is passed through a single column containing Al.sub.2O.sub.3 alumina, 4 average pore size molecular sieves, and Q5 reactant.

(21) The reactor is loaded first from the shot tank containing alpha-olefin, depending on desired reactor load. The shot tank is filled to the load set points by use of a lab scale to which the shot tank is mounted. Toluene or Isopar E solvent is added in the same manner as alpha-olefin. After liquid feed addition, the reactor is heated up to the polymerization temperature set point. Ethylene is added to the reactor when at reaction temperature to maintain reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flow meter and integrated to give overall ethylene uptake after catalyst injection.

(22) The catalyst and BOMATPB activator are mixed with the appropriate amount of purified toluene to achieve a desired molarity solution. The catalyst and activator are handled in an inert glove box, drawn into a syringe and pressure transferred into the catalyst shot tank. This is followed by three rinses of toluene, 5 mL each. Immediately after catalyst addition the run timer begins. Ethylene is then added continuously by the Camile to maintain reaction pressure set point in the reactor. If the ethylene uptake rate is low, then the headspace is purged, more catalyst and activator are added, and the ethylene pressure is re-established. After a designated time or ethylene uptake the agitator is stopped and the bottom dump valve opened to empty reactor contents to the dump pot. The dump pot contents are poured into trays placed in a lab hood where the solvent is evaporated off overnight. The trays containing the remaining polymer are then transferred to a vacuum oven, where they are heated up to 140 C. under vacuum to remove any remaining volatile species. After the trays cool to ambient temperature, the product is weighed for yield/efficiencies, and submitted for testing.

Examples 8-10 and Comparative Examples B AND C

(23) A series of semi-batch oligomerizations are performed with a Formula (I) coordination-insertion catalyst at 80 C. and at several different pressures using 300 g toluene as a reaction solvent. The semibatch nature of the reaction is due to the continuous feeding of ethylene gas to maintain a constant pressure, and excess butene is purged out to allow the continued consumption of ethylene. No alpha-olefin comonomers are added to the reaction. The average number of carbons per product oligomers is calculated assuming all molecules have a single unsaturation group. Results are shown in Table 8. Comparative Examples B and C show insufficient branching to qualify as producing a hyperbranched product. This is because the reaction was stopped at a low yield. As the yield grows over time, there is an ever-increasing opportunity for branching and the branch creation is cumulative. The yield necessary for hyperbranching is dependent on the ethylene pressure, since branching is a result of the re-insertion of alpha-olefin product, which competes with ethylene insertion.

(24) TABLE-US-00008 TABLE 8 13C NMR Data per 1000 carbons 13C NMR Ex or Pressure Catalyst BOMATPB Ethylene Ethylene Yield n- Calculations CEx (KPa) (moles) (moles) (g initial) (g added) (g) methines vinyl vinylene vinylidene butyl Cn Bn Pv Ex 8 31.9 1.8 2.16 35.4 500.7 256.4 54.03 28.60 2.23 3.00 17.20 29.6 1.60 84.5 Ex 9 8.8 0.7 0.84 7.2 52 41.1 64.36 19.12 3.75 4.47 24.22 36.6 2.35 69.9 Ex 10 8.8 2 2.4 8 126.5 108.6 72.94 13.23 4.67 5.10 28.63 43.5 3.17 57.5 CEx B 31.9 0.1 0.12 37 10.4 6.8 24.21 33.08 0.76 0.91 5.60 28.8 0.70 95.2 CEx C 16.8 0.1 0.12 18.9 32.1 11.2 40.43 32.48 0.81 1.46 9.62 28.8 1.16 93.5

Comparative Example D

(25) A semi-batch oligomerization is performed with the Formula (I) catalyst at 80 C. with ethylene and 1-hexene as comonomers and no other added solvent except that used to deliver the catalyst. The semi-batch nature of the reaction is due to the continuous feeding of ethylene gas to maintain a constant pressure. However, the consumption is 1-hexene is low enough to have negligible impact on the ethylene to hexene ratio in the reaction mixture. The average number of carbons per product oligomers is calculated assuming all molecules have a single unsaturation group. The fraction of methines derived from ethylene is conservatively estimated from the .sup.13C NMR data using the relation below, which indicates at least 14% of the methine carbons is derived from ethylene, where 14%=(10893)/108. While the oligomer made in this comparative Example D has significant branching, those branches are largely due to incorporation of added 1-hexene rather than derived from ethylene.

(26) The in situ alpha olefin creation by the catalyst is not significant when compared to the 1-hexene added to the reactor. Therefore only a small minority of the branched are expected to result from in situ olefin creation.
Fraction of methines derived from ethylene=(methine carbonsn-butyl branches)/(methine carbons)(equation 10)

(27) TABLE-US-00009 TABLE 9 Pres- Ethyl- 13C NMR Data per 1000 carbons 13C NMR Temp sure Hexene Catalyst BOMATPB ene (g Ethylene Yield n- Calculations ( C.) (KPa) (g) (moles) (moles) initial) (g added) (g) methines vinyl vinylene vinylidene butyl Cn Bn Pv 80 7.3 236 6.1 7.34 5.5 21.6 108.11 9.74 14.73 2.67 93.01 36.9 3.98 35.9

Example 11

(28) A coordination-insertion catalyst suitable for use in the present invention is prepared as following steps. Confirmation of each product is obtained via .sup.1H NMR and .sup.19F NMR.

(a) Step 1: Preparation of 2-(2-bromoethoxy)-1,5-difluoro-3-iodobenzene

(29) ##STR00010##

(30) A mixture of 2-iodo-4,6-difluorophenol (10.00 g, 38.28 mmol) [prepared according to WO/2012/027448], 1,2-dibromoethane (144 g, 765 mmol), potassium carbonate (10.582 g, 76.566 mmol), and acetone (250 mL) is heated to reflux for 1 hour. The mixture is allowed to cool to room temperature and concentrated. The residue is partitioned in a 50/50 methylene chloride/water mixture and extracted with methylene chloride. The combined organic phases are washed with 2 N NaOH (300 mL), brine (300 mL), water (300 mL), dried over MgSO.sub.4, filtered through a pad of silica gel and concentrated. The resulting oil is purified via column chromatography using a hexanes:ethyl acetate gradient to afford 12.5 g (86.8%) of the product as a slightly yellow oil.

(b) Step 2: Preparation of 1,5-difluoro-2-(2-(4-fluoro-2-iodophenoxy)ethoxy)-3-iodobenzene

(31) ##STR00011##

(32) A mixture of 2-(2-bromoethoxy)-1,5-difluoro-3-iodobenzene (3.85 g, 10.6 mmol), 2-iodo-4-fluorophenol (2.525 g, 10.61 mmol) [prepared according to WO/2012/027448], potassium carbonate (3.094 g, 22.39 mmol), and acetone (80 mL) is heated to reflux and allowed to stir overnight. The mixture is cooled to room temperature and filtered. The cake is washed with acetone. The filtrate is concentrated to afford the crude as dark brown oil which as purified by column chromatography using 5% ethyl acetate in hexanes to afford 3.69 g (65.1%) of the product as a colorless oil.

(c) Step 3: Preparation of 3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2-(2-((3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-fluoro-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)-[1,1-biphenyl]-2-yl)oxy)ethoxy)-3,5-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1-biphenyl]-2-ol

(33) ##STR00012##

(34) A mixture of 1,2-dimethoxyethane (69 mL), 3,6-di-tert-butyl-9-(2-((tetrahydro-2H-pyran-2-yl)oxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl)-9H-carbazole (4.00 g, 5.71 mmol) [prepared according to US2011/0282018], 1,5-difluoro-2-(2-(4-fluoro-2-iodophenoxy)ethoxy)-3-iodobenzene (1.41 g, 2.711 mmol), a solution of NaOH (0.6849 g, 17.12 mmol) in water (16 mL) and THF (40 mL) is purged with N.sub.2 for 15 minutes, then Pd(PPh.sub.3).sub.4 (0.1318 g, 0.1142 mmol) is added and heated to 85 C. overnight. The mixture is allowed to cool to room temperature and concentrated. The residue is taken up in methylene chloride (200 mL), washed with brine (200 mL), dried over anhydrous MgSO.sub.4, filtered through a pad of silica gel, and concentrated to afford the crude protected ligand. To the crude is added tetrahydrofuran (50 mL), methanol (50 mL) and approximately 100 mg of p-toluenesulfonic acid monohydrate. The solution is heated to 60 C. overnight, then cooled and concentrated. To the crude ligand is added methylene chloride (200 mL), washed with brine (200 mL), dried over anhydrous MgSO.sub.4, filtered through a pad of silica gel and concentrated to afford a brown crystalline powder. The solid is purified by column chromatography using a gradient of methylene chloride:hexanes to afford 1.77 g (52.4%) of the product as a white solid.

(d) Step 4: Formation of Metal-ligand Complex

(35) ##STR00013##

(36) To a mixture of ZrCl.sub.4 (0.086 g, 0.37 mmol) and ligand (0.456 g, 0.37 mmol) suspended in toluene (4 mL) was added 3M MeMgBr (0.52 mL, 1.56 mmol) in diethyl ether. After stirring for 1 hr at room temperature, hexane (10 mL) was added and the suspension was filtered giving colorless solution. Solvent was removed under reduced pressure to give 0.386 g (77.4%) of product metal-ligand complex.