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    • 专利摘要:
    HYPER-BRANCHED ETHYLENE-BASED OLIGOMERS. A process for preparing a fluid of relatively inexpensive utility comprises contacting ethylene and an insertion-coordination catalyst, and optionally an alpha-olefin, in a continuously fed back-mix reactor zone under conditions such that a mixture of a hyper-branched oligomer and a branched oligomer is formed. The hyper-branched oligomer has an average of at least 1.5 methine carbons per oligomer molecule, and at least 40 methine carbons per thousand total carbons, and at least 40 percent of the methine carbons are derived from ethylene, and the average number of carbon per molecule is 25 to 100, and at least 25% of the molecules of the hyper-branched oligomer have a vinyl group and can be separated from the branched oligomer, which has an average number of carbons per molecule of up to 20. insertion-coordination is characterized as having an ethylene/octene reactivity ratio of up to 20 and a kinetic chain length of up to 20 monomer units.
    公开号:BR112015031326B1
    申请号:R112015031326-4
    申请日:2014-06-24
    公开日:2021-05-25
    发明作者:Jerzy Klosin；Daniel J. Arriola；Brad C. Bailey；Zenon Lysenko；Gordon R. Roof；Austin J. Smith
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    [001] The invention relates to utility fluids and particularly to compositions and processes for preparing utility fluids by an olefin insert oligomerization using ethylene.
    [002] The polymerization of ethylene, propylene and alpha-olefins by transition metal coordination-insertion catalysts mainly leads to the formation of polymers with linear structures. However, polymers with linear structures do not always exhibit properties such as desirable rheology under certain conditions. Rheological behavior is often important in identifying oils or greases that are suitable for use as, for example, lubricants, dielectric fluids, and the like. In view of this, researchers in the art have been looking for branched materials in an effort to better control rheological behavior.
    [003] An example of this is found in US Patent 6,303,717, in which branch points are made in situ in a "chain walking" polymerization, so called because the catalyst center is believed to "walk" along the aliphatic chain to randomly create branch points or modify the length. By this mechanism virtually any carbon within a linear alpha-olefin can become a methine branch point (IUPAC: methylidene). In this patent, ethylene and olefin based oils, including a highly branched ethylene monopolymer, are prepared using a nickel(II) and palladium(II) complex class of alpha-diimine binders as catalysts. While these chain walking catalysts can induce polymerization at relatively low temperatures, they unfortunately tend to produce low yields, leaving significant levels of metals in the final product.
    [004] Another example is found in US Patent 4,855,526, which describes materials including at least 20 mole percent (mol%) of ethylene with alpha-olefin comonomers. These are prepared using an aluminum-titanium Ziegler-Natta coordination-insertion catalyst. In this patent, the branches are produced by incorporating alpha-olefin and the polymer structure is linear.
    [005] Additional examples of coordination-insert polymerization include US Patents 7,238,764 and 7,037,988, which disclose the use of an olefin comonomer other than ethylene. US Patent 7,238,764 demonstrates the use of a catalyst which has very low reactivity towards alpha-olefins as compared to its reactivity to ethylene.
    [006] US Patent 6,835,698 describes the production of ethylene-olefin based copolymers having a claimed range for the ethylene-olefin dyad level with ethylene levels in the product ranging from 23% mol to 49% mol. These materials are produced by a selection of catalyst packages that create an ethylene-olefin structure fitting the specified dyad level.
    [007] There is still a need in the technique for convenient, efficient and controllable processes to adjust the rheological behavior of a product for a specific end-use application.
    [008] In one aspect, the invention provides a process for preparing a fluid composition of utility comprising (1) contacting ethylene and at least one coordination-insertion catalyst and optionally an alpha-olefin, wherein the coordination catalyst -insertion is a metal-binder complex in which the metal is selected from zirconium, hafnium and titanium, having an ethylene/octene reactivity ratio of up to 20, and a kinetic chain length of up to 20 monomer units, in a zone of backmix reactor fed continuously under conditions 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 thousand total carbons, and where at least 40 percent of the methine carbons are derived from ethylene, and where the average number of carbons per molecule is 25 to 100, and where at least 25 percent d hyperbranched oligomer molecules have a vinyl group; and (b) a branched oligomer having an average number of carbons per molecule that is up to 20; (2) separate the hyper-branched oligomer and the branched oligomer; and (3) recovering the hyper-branched oligomer, the branched oligomer, or both.
    [009] In another aspect, the invention provides a composition prepared by the defined process.
    [010] The following formulas are described as follows.
    [011] Formulas (I) and (II) represent generalized metallocene catalysts useful in the invention.
    [012] Formula (III) represents a generalized bis-phenylfoxy catalyst useful in the invention.
    [013] Formula (IV) represents a coordination-insertion catalyst of the formula (L)ZrMe2 where (L) = 2',2'''- (ethane-1,2-diylbis(oxy))bis(3- (3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethyl-pentan-2-yl)-[1 ,1'-biphenyl]-2-ol).
    [014] Formula (V) represents a coordination-insertion catalyst of formula (L)ZrMe2 where (L) = 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-tri- methylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)ethoxy)-3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[ 1,1'-bi-phenyl]-2-ol.
    [015] Formula (VI) represents a coordination-insertion catalyst of formula (L)ZrMe2 where (L) = 3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-2' -(2-((3'-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3,5-difluoro-2'-hydroxy-5'-(2,4,4- trimethylpentan-2-yl)-[1,1'-biphenyl]-2-yl)oxy)ethoxy)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl) -[1,1'-biphenyl]-2-ol.
    [016] Formula (VII) represents a coordination-insertion catalyst of the formula (L)HfMe2 where (L) = 2',2'''- (ethane-1,2-diylbis(oxy))bis(3- (3,6-di-tert-butyl-9H-carbazol-9-yl)-3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'- biphenyl]-2-ol).
    [017] The Formula (VIII) represents a coordination-insertion catalyst of the formula (L)ZrMe2 where (L) = 2',2'''- (ethane-1,2-diylbis(oxy))bis(3- (3,6-di-tert-butyl-9H-carbazol-9-yl)-3',5'-difluoro-5-(2,4,4-trimethylpentan-2-yl)-[1,1'- biphenyl]-2-ol).
    [018] The inventive process offers advantages that it can be employed to produce a hyper-branched product having particularly desirable rheological properties, including unexpectedly low viscosity for a given molecular weight, for example, in some embodiments less than 60 centipoise (cP, 0 .06 pascal seconds, Pa*s) at room temperature. It may also have a low pour point, in some modalities less than -25 oC, and a high flash point, in some modalities above 200 oC. In particular, the process can be relatively inexpensive to carry out as it uses low cost and readily available raw materials, particularly ethylene, and is a continuous process employing a conventional back-mix reactor. In particular, it employs an insertion-coordination catalyst selected from a group of catalyst families, and the catalyst can operate efficiently and over a wide thermal operating range, in some non-limiting modes supporting temperatures in excess of 200 °C.
    [019] The inventive process to prepare the hyperbranched products generally includes reaction of the starting monomers to form a mixture of these oligomers. As the term is used here, "oligomers" are molecules, formed by consecutive addition of monomer or comonomer units, that have an average molecular size of no more than 50 units. The average size is calculated as the total number of embodied comonomer units divided by the total number of oligomer molecules. Alternatively, another indication of molecular size is the average number of carbons per molecule, which is the total carbon count divided by the total number of molecules.
    [020] The starting monomer can be ethylene alone, or a proportion of an alpha-olefin comonomer can be included along with ethylene. If an alpha-olefin is included, it can be selected, in a non-limiting example, from linear alpha-olefins having 3 to 12 carbons, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene , 1-octene, 1-nonene, 1-decene, undecene, 1-dodecene, and combinations thereof. Smaller linear alpha-olefins having 3 to 7 carbons are preferred because they allow for a higher branching density of the final product oligomers. Branched alpha olefins may also be employed in the feed process, and may include in non-limiting embodiments single or multiple branched alpha olefin monomers having from 5 to 16 carbons, wherein the first substituted carbon is in the "3" position or position higher than vinyl, and combinations thereof. It is generally preferred that the first substitution be at position “4” or greater.
    [021] Note that the ethylene/alpha-olefin reactivity ratio is distinct from any catalyst and is expected to vary with the reaction temperature. For any given catalyst the olefin-ethylene reactivity ratio (r1) is determined by performing a low conversion co-oligomerization and observing the oligomer composition (F) resulting from a chosen monomer composition (f). Equation 1 below is the relationship between F, f and r1, which can be used to estimate r1 from a single oligomerization or obtain a statistically more reliable value for r1 from a series of oligomerizations: (1-F2)/F2 = r1 (1-f2)/f2 (equation 1) FTIR or 13C NMR measurements of oligomer composition (F) are commonly used to determine the reactivity ratio, with 13C NMR being preferred. Alpha-olefin monomer fractions (f2) ranging from 33-66% are generally used for determining the reactivity ratio, with a value of 50% being preferred. The preferred method for determining the ethylene-olefin reactivity ratio involves an equimolar level of olefin and ethylene dissolved in a compatible solvent, such as an alkane, as f1 = f2 = ^. After a co-oligomerization of this mixture to low conversion (<20%), the resulting oligomer compositions (F) are used in equation 1 to determine the reactivity ratio r1.
    [022] Regardless of whether an alpha-olefin is used, however, the catalyst selected for use in the invention has an ethylene/octene reactivity ratio that is up to 20, preferably from 1 to 20, more preferably from 1 to 12 and more preferably from 1 to 6. While ethylene/alpha-olefin reactivity ratios will, in general, normally vary with processing temperature, the set of maximum ratios here apply for any and all processing temperatures.
    [023] Where an alpha-olefin other than octene will be included, it is additionally necessary to determine the ethylene reactivity ratio for the specific selected alpha-olefin in order to determine how much of the selected alpha-olefin monomer will be needed to achieve a composition of target oligomer. A simple random copolymerization model refers to the mole fraction of alpha-olefin monomer (f2) to the mole fraction of alpha-olefin in the copolymer (F2), where r1 is the ratio of ethylene reactivity to alpha-olefin reactivity , based on equation 1 above, where r1 = ethylene reactivity/alpha-olefin reactivity; F2 = mole fraction of alpha-olefin in product oligomer; and f2 = mole fraction of alpha-olefin monomer. Thus, for a given catalyst and with minimal experimentation, those skilled in the art will be able to easily determine the fraction of alpha-olefin monomer (F2) needed to achieve the desired alpha-olefin polymer content (F2). For example, using the random incorporation model, if r1 = 5, and 10 mol% alpha-olefin is desired in the target hyper-branched oligomer (F2 = 0.10), then 3 mol% alpha-olefin ( f2 = 0.36) would be expected to be required in the free monomer in the vicinity of the catalyst. On the other hand, an ethylene/alpha-olefin reactivity ratio of r1=15 would result in 63% alpha-olefin monomer (f2 = 0.63) needed to guarantee the same 10% mol content of alpha-olefin in the target hyperbranched oligomer. Because of the in situ generation and consumption of alpha-olefins, the added alpha-olefin content can be determined by conventional mass balance calculations, taking into account that they both process feed streams and effluents.
    [024] Notwithstanding the above, it is preferred that only a small amount of alpha-olefin is included, if any. This amount preferably ranges from 0 to 30% by mol; more preferably from 0 to 25% by mol; even more preferably from 0 to 20% by mol; even more preferably from 0 to 10% by mol; and most preferably from 0 to 5% by mol. The amount of added alpha-olefin is most commonly preferred to be 0 mol% because added alpha-olefins tend to be more expensive than the spectrum of alpha-olefins that are created in situ. While ethylene feed streams often have a small fraction (less than 1% by mol) of alpha-olefin monomer impurities such as propylene, it is expected that this would have no significant detrimental effect on process operation or oligomer properties.
    [025] In the inventive process, the selected starting monomer or monomers are in contact with a suitable insertion-coordination catalyst. As the term is used here, "insertion-coordination" means that the catalysts are capable of consecutively inserting unsaturated monomers, with the result that previously unsaturated carbons in the monomers and the oligomer become the backbone of a new oligomer. This catalyst can be selected, in one embodiment, from a wide variety of metal-binder complexes. Those skilled in the art will be aware that catalyst performance varies with process temperature and may also vary with conversion and composition of the reaction mixture. Preferred catalysts are those having an activity level of 100,000 grams of oligomer per gram of catalyst metal (g/g cat). Also preferred are catalysts capable of producing a chain termination rate that results in a product oligomer of a desired molecular weight and having a high fraction, preferably at least 25%, more preferably at least 50%, and most preferably at least 75 % of vinyl groups.
    [026] The kinetic chain length is also important in identifying particularly suitable catalysts for the present invention. Kinetic chain length is defined as the average number of monomeric repeating units incorporated by a catalyst prior to a chain transfer or chain growth termination reaction. For linear insertion-coordination oligomers, the kinetic chain length is equal to the number average degree of polymerization (DPn), or the number average molecular weight Mn) divided by the weight average repeating unit formula. For branched ethylene-based oligomers, the kinetic chain length is more difficult to estimate because it depends on knowledge of the branching level. For an ethylene oligomerization, the kinetic chain length can be determined from measurements of molecular weight and methine carbon level (branching), as follows: a) The number-average degree of polymerization (DPn) is calculated from the numerical average molecular weight (Mn), divided by repeating unit weight (28.1 g/mol) or 13C NMR measurement of Cn, as described by equations 2-4 below, where DPn=Cn/2. b) The average number of branches per oligomer molecule (Bn) is calculated from 13C NMR data as described by equation 6 below. c) Kinetic chain length is derived from the knowledge of DPn and Bn, and the fact that an ethylene oligomer molecule with b branch points is composed of b+1 kinetic chains, where kinetic chain length = DPn / (1+Bn).
    [027] For a given catalyst, the kinetic chain length may vary with the monomer concentration and temperature, but in the present invention, the kinetic chain length incorporated with the catalyst is desirably no more than 20 monomer units. Kinetic chain length is easier to measure when linear oligomers are intentionally prepared and Bn is zero.
    [028] Examples of suitable insertion-coordination catalysts may generally include, in certain non-limiting embodiments, metal-binder complexes including any of the metals zirconium, hafnium, or titanium, and preferably zirconium or hafnium. Among such catalysts may be certain metallocene catalysts, including certain geometry constrained catalysts, bis-phenylphenoxy catalysts, provided the catalyst selected meets the ethylene/octene reactivity ratio and kinetic chain length requirements as defined above.
    [029] The metallocene compounds useful here are cyclopentadienyl titanium derivatives, zirconium and hafnium. These metallocenes (eg titanocenes, zirconocenes and hafnocenes) can be represented by one of the following formulas:
    Formula I Formula II wherein M is the metal center, and is a Group 4 metal, preferably titanium, zirconium or hafnium; T is an optional bridging group which, if present, in preferred embodiments is selected from dialkylsilyl, diarylsilyl, dialkylmethyl, ethylenyl (-CH2-CH2-) or hydrocarbylethylenyl wherein one, two, three or four of the hydrogen atoms in ethylenyl are substituted by hydrocarbyl, where hydrocarbyl may independently be C1 to C16 alkyl or phenyl, tolyl, xylyl and the like, and when T is present, the catalyst depicted may be in a racemic or meso form; L1 and L2 are the same or different, optionally substituted cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, which are each attached to M, or L1 and L2 are the same or different cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl rings, the rings of which are optionally substituted with one or more R groups, with any two adjacent R groups being joined to form a substituted or unsubstituted, saturated, partially unsaturated, or cyclic or polycyclic aromatic substituent; Z is nitrogen, oxygen or phosphorus; R' is a linear or branched cyclic C1 to C40 alkyl or substituted alkyl group; and X1 and X2 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 bonded to the metal atom to form a metallacycle ring containing from about 3 to about 20 carbon atoms; or the two together form an olefin, diolefin or amine binder.
    [030] Among the metallocene compounds that can be used in this invention are stereorigid, chiral or asymmetric metallocenes, bridged or unbridged, or so-called "restricted geometry". See, for non-limiting example purposes only and for further discussion of methods of preparation, US Patent 4,892,851; US Patent 5,017,714; US Patent 5,132,281; US Patent 5,155,080; US Patent 5,296,434; US Patent 5,278,264; US Patent 5,318,935; US Patent 5,969,070; US Patent 6,376,409; US Patent 6,380,120; US Patent 6,376,412; WO-A- (PCT/US92/10066); WO 99/07788; WO-A-93/19103; WO 01/48034; EP-A2-0 577 581; EP-A1-0 578 838; WO 99/29743 and also from the academic literature, for example, “The Influence of Aromatic Substituents on the Polymerization Behavior of Bridged Zirconocene Catalysts,” Spaleck, W., et al., Organometallics 1994, Vol. 954-963; “Ansa-Zirconocene Polymerization Catalysts with Annelated Ring Ligands—Effects on Catalytic Activity and Polymer Chain Lengths,” Brintzinger, H., et al., Organometallics 1994, Vol. 964-970; “Constrained geometry complexes—Synthesis and applications,” Braunschweig, H., et al., Coordination Chemistry Reviews 2006, 250, 2691–2720; and documents referred to therein, all of which are incorporated herein by reference in their entirety.
    [031] In certain particular embodiments, the catalyst selected may be a compound of Formula (III)
    where M is titanium, zirconium, or hafnium, each independently being in a formal oxidation state of +2, +3 or +4; n is an integer from 0 to 3, where when n is 0, X is absent; each X independently is a monodentate ligand that is neutral, monoanionic, or dianionic, or two Xs are taken together to form a bidentate ligand that is neutral, monoanionic, or dianionic; X and en are selected such that the metal-ligand complex of Formula (III) is generally neutral; each Z is independently O, S, N(C1-C40)hydrocarbyl, or P(C1-C40)hydrocarbyl; L is (C1-C40)hydrocarbylene or (C1-C40)heterohydrocarbylene, wherein the (C1-C40)hydrocarbylene has a moiety comprising a linker structure of 2 to 5 carbon atoms linking the Z moieties in Formula (III) , wherein each atom of the 2 to 5 atom (C1-C40)heterohydrocarbylene linker has a part comprising a 2 to 5 carbon atom linker structure linking the Z moieties in Formula (III), wherein each atom of such The 2 to 5 atom linker of the (C1-C40)heterohydrocarbylene independently is a carbon atom or a heteroatom, wherein each heteroatom independently is O, S, S(O), S(O)2, Si(RC)2, Ge(RC)2, P(RP), or N(RN); wherein each RC independently is unsubstituted (C1-C18)hydrocarbyl or the two RC are taken together to form a (C2-C19)alkylene, each RP is unsubstituted (C1-C18)hydrocarbyl; and each RN is unsubstituted (C1-C18)hydrocarbyl, a hydrogen atom, or absent; R1a, R2a, R1b, and R2b are independently a hydrogen, (C1-C40)hydrocarbyl; (C1-C40)heterohydrocarbyl, N(RN)2, NO2, ORC, SRC, Si(RC)3, Ge(RC)3, CN, CF3, F3CO, or halogen atom, and each of the others of R1a, R2a, R1b, and R2b are independently a hydrogen, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, N(RN)2, NO2, ORC, SRC, Si(RC)3, CN, CF3, F3CO or atom of halogen, each of R3a, R4a, R3b, R4b, R6c, R7c, R8c, R6d, R7d, and R8d is independently a hydrogen atom, (C1-C40)hydrocarbyl, (C1-C40)heterohydrocarbyl, Si(RC )3, Ge(RC)3, P(RP)2, N(RN)2, ORC, SRC, NO2, CN, CF3, RCS(O)- , RCS(O)2-, (RC)2C=N -, RCC(O)O-, RCOC(O)-, RCC(O)N(R)-, (RC)2NC(O)-, or halogen atom; each of R5c and R5d is independently a (C6-C40)aryl or (C1-C40)heteroaryl; and each of the aforementioned aryl, heteroaryl, hydrocarbyl, heterohydrocarbyl, hydrocarbylene, and heterohydrocarbylene groups are independently substituted or unsubstituted with 1 to 5 more RS substituents; and each independent RS is a halogen atom, polyfluoro substitution, perfluoro substitution, unsubstituted (C1-C18)alkyl, F3C-, FCH2O-, F2HCO-, F3CO-, R3Si-, R3Ge-, RO-, RS-, RS (O)-, RS(O)2-, R2P-, R2N-, R2C=N-, NC-, RC(O)O-, ROC(O)-, RC(O)N(R)-, or R2NC(O)-, or two of the RS are taken to form an unsubstituted (C1-C18)alkylene, where each independent R is an unsubstituted (C1-C18)alkyl.
    [032] In more particular embodiments, the catalyst may be selected from compounds represented by formulas (IV) to (VIII).


    [033] The preparation of these bis-phenylphenoxy compounds can be by any means known or envisioned by those skilled in the art, but in general involve means and methods as are disclosed, for example, in US Serial Number PCT/US2012/0667700, filed on November 28, 2012, claiming Priority for Provisional Application US 61/581,418, filed December 29, 2011 (Attorney Registry No. 71731) and US Serial Number 13/105018, filed May 11, 2011 , Publication Number 20110282018, claiming priority to US Provisional Application 61/487,627, filed March 25, 2011 (Attorney Registry No. 69,428). This is illustrated in a non-limiting embodiment, in Example 10 herein, but those skilled in the art will recognize that similar and analogous processes can be used to prepare other bis-phenylphenoxy compounds useful within the given definition.
    [034] The reaction sequence taking place in the process of the invention can be defined according to the following reaction sequences: 1. The metal catalyst center (M) of the coordination-insertion catalyst mediates the co-oligomerization of ethylene with alpha -linear and/or branched olefins. It should be noted that, even in the presence of added alpha-olefin comonomers, there will be a substantial amount of ethylene homopolymerization to prepare short linear alpha-olefin species. When the ethylene homopolymer is formed in the presence of alpha-olefins, only the minor oligomer products are anticipated to be linear, because the metal catalyst center M is preferably selected to have a high reactivity to alpha-olefins. The co-oligomerization is preferably done in the absence of any chain transfer agent that would reduce the vinyl content of the oligomer. Unwanted chain transfer agents include, for example, hydrogen (H2) and metal alkyl groups such as AlR and ZnR, where Al is aluminum, Zn is zinc, and R is independently selected from the group consisting of linear alkyl, branched alkyl and its alkoxy analogues.
    [035] The events included within this first step of the reaction sequence, therefore, may include: 1(a) homopolymerization of ethylene
    transfer or chain termination for linear alpha-olefins
    2. Co-oligomerization of ethylene and linear alpha-olefins results in branched products, some of which are branched alpha-olefin species that can further react to form hyper-branched oligomer. This random co-oligomerization of ethylene and alpha-olefins implies that the larger oligomer molecules will have more branch points than the smaller oligomer molecules, and that there will be a substantial presence of linear alpha-olefin species among the smaller oligomer products. Events included within this second step, therefore, include: 2(a) co-oligomerization of ethylene with linear alpha-olefins
    2(b) transfer or chain termination to form branched alpha-olefins
    (reaction sequence 4) 3. Finally, hyper-branching occurs when branched alpha-olefins are incorporated into an oligomer molecule, consequently:
    (reaction sequence 5)
    [036] In carrying out the process of the invention, it is desirable that the contact between the monomers and the coordination-insertion catalyst occurs in a reactor zone with backmix fed continuously. As the term is used here, “backmix reactor zone” refers to an environment where a reaction product is mixed with unconverted reactor feeds. A continuous stirred tank reactor is preferred for this purpose, while it should be noted that piston flow reactors are specifically designed to prevent back-mixing. However, a loop reactor can perform a variable degree of back-mixing by recycling a portion of the reactor effluent to a piston flow zone feed, with the recycling rate moderating the degree of back-mixing. Thus, piston flow reactors are not preferred, while a loop reactor with a piston flow zone is preferred. In the inventive process, backmixing guarantees the reaction of oligomers already produced with new raw material, for example, ethylene. It is this continuous contact that allows the oligomers to become branched through repeated olefin insertion.
    [037] The conditions under which contact occurs in the continuously fed, back-mixed reactor zone may include a temperature desirably ranging from 0 °C to 250 °C, more desirably from 25 °C to 200 °C, and more desirably from 50 °C to 180 °C; an ethylene partial pressure desirably ranging from 15 psi (pounds per square inch, 103 kilopascal, kPa) to 500 psi (3450 kPa), more desirably from 30 psi (207 kPa) to 300 psi (2070 kPa), and most desirably from 50 psi (345 kPa) to 200 psi (1380 kPa); and a residence time desirably ranging from 1 minute (min) to 120 min, more desirably from 5 min to 60 min, and more desirably from 10 min to 30 min. A reactor system can be composed of many shorter residence time reaction zones or a few longer residence time reaction zones. However, those skilled in the art will readily understand that changing parameters can be employed for reasons of convenience, change in yield, avoidance of undesirable side products or degradation, and the like.
    [038] The result of the process is the production of at least two products, called a hyper-branched product and a branched product. For the sake of understanding, the term "hyper-branched oligomer" refers to the desired or target "hyper-branched" oil or grease, regardless of its production order or relative proportion. These materials are collectively referred to herein as "utility fluids." "Hyper-branched" means that oligomer molecules comprise a random distribution of straight-chain segments joined through methine carbons and have an average of at least 1.5 methine carbons per molecule. "Linear chain segments" are defined as the portion of a polymer or oligomer consisting of consecutive methylene carbons having a molecular formula of [CH2]n where the mean n is preferably from 3 to 13. Hyperbranching is present when the carbons methine are randomly located in the molecule and are not isolated to the main polymer structure as with a standard ethylene-olefin copolymer. The 13C NMR measurement of methine carbons can be used to determine the level of global branching. It should be noted that, due to the nature of insertion-coordination, continuous contact of the raw material and back-mixed product with the catalyst would be expected to eventually result in true, complete polymerization, or an excessive level of branching, thus forming a material which may contain a predominant amount of a non-hyperbranched product. Thus, the reaction conditions, namely, time, temperature and pressure, are desirably controlled in order to produce the desired hyper-branched oligomer. The final hyper-branched oligomer can be further characterized in that at least 40 percent of the methine carbons are derived from ethylene; the average number of carbons per molecule is from 25 to 100; and at least 25 percent of the hyperbranched oligomer molecules have a vinyl group. In particular modalities, the “hyper-branched” product has at least 55 methine carbons per thousand total carbons, and in more preferred modalities, it has at least 70 methine carbons per thousand total carbons. This level of branching is affected by the incorporation of added alpha-olefins and the incorporation of in situ generated olefins.
    [039] Additional desired characteristics of the hyper-branched products produced include modalities in which it is an oligomer oil having a pour point of less than 0°C, and modalities in which the oligomer oil has a pour point of less than -20 °C or even less than -25 °C.
    [040] The "branched" product, which can be a single product or group of products, can in many respects correspond to the "hyper-branched" product except that it will have an average number of carbons per molecule that is 20 or less. These "branched" products are therefore referred to as "light olefins." Because the process of the invention is designed to allow the production of particularly hyper-branched products, it is desirable to devolatilize the product mixture to separate the hyper-branched and branched products from one another and thus recover the hyper-branched product .
    [041] A feature of the invention is that the hyperbranched product may also contain a desirable level of unsaturation, i.e. at least 25 percent vinyl end groups, preferably at least 50 percent, and more preferably at least 90% , as discussed above. This efficient functionalization allows for subsequent processing as desired. For example, hydrogenation can be performed in order to optimize the fluid composition of utility for lubricant applications. Other types of subsequent processing, including but not limited to halogenations, etherification, hydroxylation, esterification, oxidation, hydroformylation, and combinations thereof, may also be carried out as desired.
    [042] It is important to note that the mechanism occurring in the present invention is coordination-insertion, where monomers add to a growing molecule through an organometallic center so that a molecular structure is formed from carbons that originated from unsaturated carbons in the units of monomer. Thus, an insertion-coordination oligomerization with ethylene alone will produce branches with almost exclusively an even number of carbons, and insertion-coordination co-oligomerization involving ethylene and an olefin with an odd number of carbons (N) will result in branches with an odd number. odd carbons (N-2). This is different from “chain walking,” which produces branches with a random distribution of odd and even numbers of carbons. Thus, those skilled in the art will understand without further guidance how to distinguish these by 13C NMR.
    [043] Furthermore, it is suggested here that the relatively high weight percentage of the product having methine branch carbons resulting from the coordination-insertion mechanism serves to ensure that most molecules are morphologically smaller and still have the same molecular weight , which results in reduced viscosity, while at the same time the absence of crystallinity with respect to molecular interaction offers excellent useful fluid behavior at cooler temperatures. Finally, the relatively high level of unsaturation offers greater opportunity for further functionalization or product recycling. These advantages offer utility fluids, in the form of oils and greases, that are suitable for a wide variety of applications, such as for lubricants, hydraulic fluids, and dielectric fluids.
    [044] The determination of the characterization properties listed above can be performed as follows:
    [045] For measurement of 13C NMR, product samples are dissolved in 10 millimeter (mm) nuclear magnetic resonance (NMR) tubes in chloroform-d1 (deuterated chloroform), for which 0.02 molar (M) acetylacetonate chromium, Cr(AcAc)3, is added. The typical concentration is 0.50 grams per 2.4 milliliters (g/ml). The tubes are then heated in a heating block set to 50 °C. Sample tubes are repeatedly shaken and heated to achieve a smooth flowing fluid. For samples with visible wax present, tetrachloroethane-d2 (deuterated tetrachloroethane) is used as the solvent instead of chloroform-d1, and the sample preparation temperature is 90 °C. 13C NMR spectra are taken on a Bruker Avance 400 megaherz (MHz) Spectrophotometer equipped with a 10 mm cryoprobe. The following acquisition parameters are used: 5 second relaxation delay, 13.1 millisecond 90 degree pulse, 256 scans. Spectra are centered at 80 parts per million (ppm) with a spectral width of 250 ppm. All measurements are taken without sample rotation at 50 °C (for chloroform-d1 solutions) or 90 °C (for tetrachloroethane-d2 solutions). 13 C NMR spectra are referenced to 77.3 ppm for chloroform-d1 or 74.5 ppm for tetrachloroethane-d2.
    [046] As is well known to those skilled in the art, 13C NMR spectra can be analyzed to determine the following amounts: Number of methine carbons per thousand total carbons Number of methyl carbons per thousand total carbons Number of vinyl groups per thousand total carbons Number of vinylidene groups per thousand total carbons Number of vinylene groups per thousand total carbons
    [047] Based on the results obtained in the analysis of 13C NMR spectra, the average number of carbons per molecule (Cn) will be determined using the following equation, which is based on the observation that each methine carbon, vinylidene group and additional vinylene group result in an additional methyl carbon chain end: 1000/Cn = methyl carbons - methine carbons - vinylidene groups - vinylene groups (equation 2)
    [048] Alternatively, the average number of carbons per molecule (Cn) can be determined for cases where each oligomer molecule has a unique unsaturation that occurs after the end of the chain. Exclusive terminal unsaturation is common when oligomerizations and polymerizations occur without the presence of added chain transfer agents such as hydrogen or metal alkyl. 1000 / Cn = vinyl group + vinylidene group + vinylene group (equation 3)
    [049] An alternative determination of the average number of carbons per molecule (Cn) can be performed by simply calculating the average of the two previous methods. The advantage of this method is that it no longer uses vinylidene and vinylene group levels and gives the correct Cn even when no vinyls are present. 1000 / Cn = (methyl carbons - methine carbons + vinyl group)/2 (equation 4)
    [050] The determination of the mean level of branching, in terms of number of branches per thousand (1000) carbon atoms (Bc), is equal to the methine carbon count per thousand total carbons. Bc = methine carbons (equation 5)
    [051] The average degree of branch number, in terms of number of branches per oligomer molecule (Bn), can be determined by multiplying Bc and Cn and solving the base of thousand carbons Bn = Bc * Cn /1000 (equation 6)
    [052] Determination of the mole fraction of oligomers having a vinyl group (Fv) is done as follows: Fv = (vinyl group) * Cn / 1000 (equation 7)
    [053] For the case where each molecule has a unique unsaturation, Fv becomes: Fv = (vinyl group)/(vinyl group + vinylidene group + vinylene group) (equation 8)
    [054] To determine the molar fraction of methine carbons that is derived from ethylene feed instead of added alpha-olefin monomer derivatives, mass balance calculations can be performed. Those skilled in the art will be able to do this easily in the appropriate context with process variables taken into account. However, for some cases of added alpha-olefin monomer, it is alternatively possible to conservatively measure or estimate this amount. For example: a. Added propylene monomer will result in methyl branches when incorporated into the oligomer structure. One skilled in the art can use 13C NMR spectral data to calculate the level of methyl branching per thousand carbons. Each methyl branch must be accompanied by a methine carbon that is not derived from ethylene. Therefore, the calculation of the fraction of ethylene-derived methine carbons is given below: b. Fraction of methine derived from ethylene = (methine carbons - methyl branches)/(methine carbons) (equation 9) c. Added hexene monomer will result in n-butyl branches when incorporated into the oligomer structure. One skilled in the art can use 13C NMR spectral data to calculate the level of n-butyl branching per thousand carbons. However, some n-butyl branches should occur in the absence of added hexene as chain ends and ethylene-based branches. Nevertheless, assigning all n-butyl branches to added hexene incorporation results is a conservative estimate of ethylene-derived methine carbons as follows: Ethylene-derived methine carbon fraction = (methine carbons - n-butyl branches) /(methine carbons) (equation 10)
    [055] The most definitive determination of the ethylene-derived methine fraction is made using the mass balance data surrounding the oligomerization process. The mass balance data will indicate the net molar consumption of added monomer which can be a cumulative value for a semi-batch process or a rate value for a fully continuous process. The mass balance will also indicate the total moles of carbon as oligomers, which can be a cumulative value for a semi-batch process or a rate value for a fully continuous process. Liquid monomer added per thousand carbons = 1000 * (moles of added monomer liquid)/(total moles of carbon as oligomers) (equation 11)
    [056] The fraction of methine derived from ethylene is then calculated in the same way as the methods using only 13C NMR data: Fraction of methine derived from ethylene = (methine carbons - net monomer added per thousand carbons)/(methine carbons) ( equation 12)
    [057] Numerical average molecular weight (Mn) of the hyperbranched oligomer produced by the desirable ranges of the inventive process ranges from 350 Daltons (Da) to 1,400 Da, more desirably from 350 to 1,000 Da, and more desirably from 350 Da to 700 Da This can be determined using standard methods known to those skilled in the art, including gel permeation chromatography and gas chromatography. Furthermore, the determination of Mn from oligomers using 13C NMR techniques is possible, taking into account the fact that Mn is about 14 times the average number of carbons per molecule (Cn). The exact method used to relate 13C NMR data to Mn is affected by the choice of monomer as the feed for branched monomers and/or unsaturated multiples. However, those skilled in the art will easily understand how recipe changes may require changing this 13C NMR method to measure Mn.
    [058] Viscosity measurements can be performed on, for example, a Brookfield CAP 2000+ Viscometer with a 01 axis. Approximately 70 microliters (μL) of the sample is added via a micropipette to the center of the plate which is maintained at 25 °C. The shaft is dropped onto the sample and rotates at 1000 revolutions per minute (rpm) for 40 seconds until the viscosity measurement stabilizes. The instrument is calibrated to a Cannon Instruments viscosity standard of 203 cP (0.203 Pa*s) at 25°C. For high viscosity samples, the rotation rate is reduced to 300 rpm or until the torque percentage drops to between 50% and 75%.
    [059] Flash point measurements can be performed on, for example, an ERAFLASH instrument from ERA analytics with a high temperature accessory. An amount of sample, 2 mL, is added to the stainless steel sample cup via a micropipette and a stir bar is added. The sample cup and holder are placed in the sample chamber and the door is closed. Execution parameters for ERAFLASH include: agitation rate = 100 revolutions per minute (rpm), heat rate = 10 °C/min, with ignition every 2 °C, temperature range = 70 °C, ignition time = 2 milliseconds, air volume = 10 mL between 150 °C and 300 °C. After each sample, the chamber is cleaned and the electrodes are cleaned with a wire brush normally supplied by the manufacturer. EXAMPLES 1-7 and COMPARATIVE EXAMPLE A: Steady State Continuous Stirring Tank Reactor (CSTR) Oligomerizations
    [060] Small scale continuous flow solution oligomerizations are performed in a computer-controlled Autoclave EngineersTM reactor equipped with an internal agitator and a single, stationary deflector, operating at an average residence time of about 9.5 minutes (min ). Purified mixed alkanes solvent (Isopar™ E, available from ExxonMobil, Inc., consisting of C7-C9 isoalkanes) and ethylene are supplied at 1.00 grams per minute (g/min) to a 0.10 liter (L) reactor ) equipped with a temperature control jacket, internal cooling coils and thermocouple. For the various examples, temperature setpoints range from 60 °C to 132 °C and are maintained by circulating heated oil through the jacket and cooling water through internal cooling coils. A mass flow controller is used to release ethylene into the reactor.
    [061] The examples use various insertion-coordination catalysts that are activated with bis(octadecyl)methyl ammonium tetrakis(pentafluorophenyl) borate ([HNMe(C18H37)2][B(C6F5)4], abbreviated as BOMATBP). Modified Methyl Aluminoxane (MMAO) is used as a scavenger, which moderates the effects of polar impurities on catalyst performance. The catalysts are released into the reactor as a 0.0001 mol/L solution in toluene; the catalyst activator, BOMATPB, is released into the reactor as a 0.00012 mol/L solution in IsoparTM E; and the MMAO cleaner is released as a 0.01 mol/L solution in IsoparTM E.
    [062] Isopar™ solvent and catalyst, activator, and scavenger solutions 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 . Food streams are introduced into the bottom of the reactor through two eductors. The reactor is run complete with liquid at 300 to 400 pounds per square inch of gauge (psig, 2.1 to 2.7 megapascal, MPa), with vigorous agitation, while products are removed through an outlet line at the top. of the reactor. Reactor effluent is traced electrically heated and isolated as it passes through an optical spectrophotometer cell that monitors the ethylene concentration (in grams per deciliter, g/dL). Oligomerization is stopped by adding a small amount of water and 2-propanol to the outlet line along with a 2:1 mixture of IrgafosTM 168 and IrganoxTM 1010 stabilizers, which are added at total levels of 2000 parts per million (ppm) with based on the mass of the ethylene feed. This means that 0.2g of stabilizer is added for every 100g of ethylene feed. The product is devolatilized to remove "light olefins," that is, the "branched oligomer" having average carbon numbers of 20 or less, and a hyper-branched oligomer, which is an oligomeric oil, is then collected under an inert atmosphere of nitrogen and dried in a vacuum oven at a rising temperature for approximately 10 hours (h), with a high final temperature setpoint of 140 °C.
    [063] Various catalysts are tested in the continuous flow reactor as shown in Tables 1 to 8. For each designated reaction temperature, the catalyst feed rate is varied to a target steady-state ethylene conversion (ie, rate of oligomer production) be achieved. A steady state condition is defined as being reached when six (6) times the residence time has elapsed under constant feed with negligible change in ethylene conversion or pressure. Catalyst feed rate is reported in ppm, which is a ratio of catalyst metal weight to total reactor content weight. Cn and Bn amounts are calculated from the 13C NMR spectra of the recovered oils, where Cn is the ratio of total carbons to unsaturation and Bn is the ratio of methine carbons to unsaturation. Due to the fact that there are no chain transfer agents such as hydrogen or alkyl of metals, it is assumed that each oil molecule has a unique unsaturation and therefore Cn will be considered the average number of carbons per molecule and Bn is assumed to be the average number of methine branch points per molecule. The amount Pv is the percentage of unsaturated groups that are vinyl and should also be the percentage of vinyl end-group, because each oil molecule is assumed to have a single unsaturated end-group. Example 1
    [064] The insertion-coordination catalyst shown in Formula (I) is used at the temperatures shown in Table 1 and at a general reactor feed rate of 7.43 g/min. The results are shown in Table 1, and “oligomer” in g/min in this table refers to the production rate for the hyper-branched oligomer. Example 2
    [065] 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 conditions of " steady state” (first two rows) have an ethylene concentration below the detection limit. The results are seen in Table 2. Example 3
    [066] The same catalyst as the previous examples is used at 60 °C with a total reactor feed rate of 7.43 g/min. The last four steady states have an ethylene concentration below the detection limit. The results are seen in Table 3. Table 1
    Example 4
    [067] Insertion-coordination Formula (II) catalyst is used at 60 °C with a total reactor feed rate of 7.43 g/min. The last three steady states have an ethylene concentration below the detection limit. The results are seen in Table 4. Example 5
    [068] Insertion-coordination Formula (III) catalyst is used at 60 °C with a total reactor feed rate of 7.35 g/min. Three of the steady states have an ethylene concentration below the detection limit. The results are seen in Table 5. Example 6
    [069] Insertion-coordination Formula (V) catalyst is used at 60°C with a total reactor feed rate of 7.35 g/min. The results are shown in Table 6.

    Example 7 and Comparative Example A:
    [070] The insertion-coordination Formula (IV) catalyst is used at 60°C and 70°C with a total reactor feed rate of 7.35 g/min. The first steady state has an ethylene concentration below the detection limit. The results are seen in Table 7. Notably, Comparative Example A shows less than 40 methine per 1000 carbons and insufficient branching methine carbons per molecule to qualify as a hyper-branched product. This low level of branching can be explained by the low ethylene conversion (90.3%), resulting in a higher concentration of free ethylene (0.96 g/dl). This condition creates a less favorable environment for re-incorporating the alpha-olefin product and results in less branching.
    EXAMPLES 8-9 and COMPARATIVE EXAMPLES BD: Semi-batch Oligomerizations
    [071] Semi-batch oligomerizations are performed in a 2 L Parr™ batch reactor. The reactor is heated by an electrical heating mantle, and is cooled by an internal coil cooling coil containing the 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 equipped with a discharge valve, which empties the reactor contents into a stainless steel discharge pot, which is filled with a Catalyst Kill solution (typically 5 mL of an IrgafosTM/IrganoxTM/ mixture/ toluene).
    [072] The dump pot is vented to a 30 gallon purge tank, with the pot and tank purged with N2. All chemicals used for oligomerization or catalyst composition are run through purification columns to remove any impurities that might affect oligomerization. Liquid feeds such as alpha-olefin and solvents are passed through two columns, the first containing Al2O3 alumina, the second containing Q5, which is a copper reagent for entraining oxygen. The ethylene feed is passed through two columns, the first containing Al2O3 alumina and 4 Angstroms ( médio) average pore size molecular sieves to remove water, the second containing reagent Q5. The N2, used for transfers, is passed through a single column containing Al2O3 alumina, 4 Â average pore size molecular sieves, and Q5 reagent.
    [073] The reactor is loaded before the alpha-olefin-containing dose tank, depending on the desired reactor load. The dose tank is filled to the defined charging points by use of a laboratory scale to which the dose tank is mounted. Toluene or IsoparTM solvent is added in the same way as alpha-olefin. After addition of liquid feed, the reactor is heated to the set point of polymerization temperature. Ethylene is added to the reactor when at reaction temperature to maintain the reaction pressure set point. Ethylene addition amounts are monitored by a micro-motion flowmeter and integrated to give full ethylene absorption after catalyst injection.
    [074] The BOMATPB catalyst and activator are mixed with the appropriate amount of purified toluene to achieve a solution of desired molarity. Catalyst and activator are treated in an inert glove box, withdrawn into a syringe and transferred under pressure to the catalyst dose tank. This is followed by three toluene washes, 5 ml each. Immediately after adding the catalyst, the run timer will start. Ethylene is then continuously added by the CamileTM to maintain the set point of reaction pressure in the reactor. If the ethylene absorption rate is low, then the part 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 discharge valve is opened to empty the reactor contents from the discharge pot. The contents of the discharge pot are poured into trays placed in a laboratory cover where the solvent is evaporated overnight. The trays containing the remaining polymer are then transferred to a vacuum oven, where they are heated to 140°C under vacuum to remove any remaining volatile species. After the trays cool to room temperature, the product is weighed for yield/efficiency, and submitted for testing. Examples 8-10 and Comparative Examples B and C
    [075] A series of semi-batch oligomerizations is carried out with a coordination-insertion catalyst of Formula (I) at 80°C and at several different pressures using 300g toluene as a reaction solvent. The semi-batch nature of the reaction is due to the continuous supply of ethylene gas to maintain a constant pressure, and excess butene is purged out to allow for continued ethylene consumption. No alpha-olefin comonomer is added to the reaction. The average number of carbons per product oligomers is calculated assuming all molecules have a unique unsaturation group. The results are seen in Table 8. Comparative Examples B and C show insufficient branching to qualify as producing a hyper-branched product. This is because the reaction was stopped at a low yield. As income grows over time, there is increasing opportunity for branching and branching is cumulative. The yield required for hyperbranching is dependent on ethylene pressure, since branching is a result of reinsertion of the alpha-olefin product, which competes with ethylene insertion.
    Comparative Example D
    [076] A semi-batch oligomerization is performed with the catalyst of Formula (I) at 80 °C with ethylene and 1-hexene as comonomers and no other solvent added except that used to release the catalyst. The semi-batch nature of the reaction is due to the continuous supply of ethylene gas to maintain a constant pressure. However, the consumption of 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 unique unsaturation group. The fraction of methine derived from ethylene is conservatively estimated from 13 3C NMR data using the ratio below, which indicates that at least 14% of the methine carbons are derived from ethylene, where 14% = (108-93)/108. While the oligomer prepared in this Comparative Example D has significant branching, these branches are largely due to the incorporation of added 1-hexene rather than the ethylene derivative. The creation of alpha olefin in situ by the catalyst is not significant when compared to 1-hexene added to the reactor. Therefore, only a small minority of branching is expected to result from in situ olefin creation. Fraction of methine derived from ethylene = (methine carbons - n-butyl branches)/(methine carbons) (equation 10)
    Example 11
    [077] An insertion-coordination catalyst suitable for use in the present invention is prepared as in the following steps. Confirmation of each product is obtained by 1H NMR and 19F NMR. (a) Step 1: Preparation of 2-(2-bromoethoxy)-1,5-difluoro-3-iodobenzene

    [078] A mixture of 2-iodo-4,6-difluorophenol (10.00 g, 38.28 mmol) [repared 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 cools to room temperature and is concentrated. The residue is partitioned into a 50/50 methylene chloride/water mixture and extracted with methylene chloride. The combined organic phases are washed with 2N NaOH (300ml), brine (300ml), water (300ml), dried over MgSO4, filtered through a silica gel pad and concentrated. The resulting oil is purified via column chromatography using a hexanes:ethyl acetate gradient to give 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

    [079] 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) ) [repared according to WO/2012/027448], potassium carbonate (3.094 g, 22.39 mmol), and acetone (80 mL) is heated to reflux and stirred overnight. The mixture is cooled to room temperature and filtered. The cake is washed with acetone. The filtrate is concentrated to give the crude as a dark brown oil which is purified by column chromatography using 5% ethyl acetate in hexanes to give 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

    [080] 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-carbazol (4.00 g , 5.71 mmol) [repared 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 (THF) (40 mL) is purged with N2 for 15 minutes, then Pd(PPh3)4 (0.1318 g, 0.1142 mmol) is added and heated to 85 °C overnight. The mixture cools to room temperature and is concentrated. The residue is taken up in methylene chloride (200 ml), washed with brine (200 ml), dried over anhydrous MgSO4, filtered through a silica gel pad and concentrated to give the crude protected binder. For the crude, tetrahydrofuran (50 mL), methanol (50 mL) and approximately 100 mg of p-toluenesulfonic acid monohydrate are added. The solution is heated to 60 °C overnight then cooled and concentrated. The crude binder is added methylene chloride (200 mL), washed with brine (200 mL), dried over anhydrous MgSO4, filtered through a silica gel pad, and concentrated to give brown crystalline powder. The solid is purified by column chromatography using a methylene chloride:hexanes gradient to give 1.77 g (52.4%) of the product as a white solid. d) Step 4: Metal-Binder Complex Formation
    (reaction sequence 9)
    [081] To a mixture of ZrCl4 (0.086 g, 0.37 mmol) and binder (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. The solvent is removed under reduced pressure to generate 0.386 g (77.4%) of the product metal-binder complex.
    权利要求:
    Claims (9)
    [0001]
    1. A process for preparing a utility fluid composition, characterized in that it comprises: (1) Contacting together ethylene and at least one insertion-coordination catalyst and, optionally, an alpha-olefin, the insertion-coordination catalyst being it is a metal-binder complex in which the metal is selected from zirconium, hafnium and titanium, and has an ethylene/octene reactivity ratio of up to 20, and a kinetic chain length of up to 20 monomer units; in a continuously fed back-mix reactor zone, under conditions where a mixture of at least two oligomer products is formed, the mixture including: - a hyper-branched oligomer having an average of at least 1.5 methine carbons per molecule of oligomer, and having at least 40 methine carbons per thousand total carbons, and wherein at least 40 percent of the methine carbons is derived from ethylene, and wherein the average number of carbons per molecule is from 25 to 100, and wherein at least 25 percent of hyperbranched oligomer molecules have a vinyl group; and at least one branched oligomer having an average number of carbons per molecule that is less than 20; (2) separate the hyper-branched oligomer from the branched oligomer; and (3) recovering the hyper-branched oligomer, the branched oligomer, or both.
    [0002]
    2. Process according to claim 1, characterized in that the metal-ligand complex is a compound of formula:
    [0003]
    3. Process according to claim 1, characterized in that the insertion-coordination catalyst is selected from the group consisting of:
    [0004]
    4. Process according to claim 1, characterized in that the metal-ligand complex is a compound of formula
    [0005]
    5. Process according to claim 1, characterized in that it further comprises: (4) performing a hydrogenation, halogenation, etherification, hydroxylation, esterification, oxidation or hydroformylation of the hyper-branched oligomer, the branched oligomer, or both.
    [0006]
    6. Process according to claim 1, characterized in that at least 55 percent of the methine carbons are derived from ethylene.
    [0007]
    7. Process according to claim 1, characterized in that at least 70 percent of the methine carbons are derived from ethylene.
    [0008]
    8. Process according to claim 1, characterized in that at least 50 percent of the hyper-branched oligomer molecules have a vinyl group.
    [0009]
    9. Process according to claim 1, characterized in that at least 75 percent of the hyper-branched oligomer molecules have a vinyl group.
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    同族专利:
    公开号 | 公开日
    CA2915067C|2021-08-03|
    BR112015031326A2|2017-07-25|
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    KR102173912B1|2020-11-05|
    KR20160040527A|2016-04-14|
    MX2015016913A|2016-04-04|
    EP3013776B1|2018-09-19|
    CA2915067A1|2014-12-31|
    WO2014209927A1|2014-12-31|
    CN105339327B|2020-01-21|
    TWI667068B|2019-08-01|
    TW201521869A|2015-06-16|
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    法律状态:
    2018-11-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-11-12| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-06| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|
    2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-25| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/06/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361840622P| true| 2013-06-28|2013-06-28|
    US61/840,622|2013-06-28|
    PCT/US2014/043754|WO2014209927A1|2013-06-28|2014-06-24|Hyperbranched ethylene-based oligomers|
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