JP5613416B2 - High viscosity fluid production process - Google Patents

Description

The present invention relates to a process for producing polyalphaolefins (PAO) in the presence of a non-coordinating anionic activator and a metallocene catalyst comprising hydrogen.

Efforts to improve the performance of natural mineral oil based lubricants through the synthesis of oligomeric hydrocarbon fluids have been an important research and development challenge in the oil industry for at least 50 years. These efforts have relatively recently brought many synthetic lubricants to the market. For improved lubricant properties, industrial research efforts on synthetic lubricants have been directed to useful viscosities over a wide temperature range, i.e., fluids exhibiting improved fluid viscosity index (VI). On the other hand, it has also been directed to fluids that exhibit values equal to or better than mineral oils for lubricity, thermal stability, oxidation stability and pour point.

The relationship between the viscosity and temperature of the lubricating oil is considered to be one of the main criteria for selection when the lubricant is specifically used. Mineral oils commonly used as the base for single and multi-grade lubricants vary in viscosity with changes in temperature. Fluids that exhibit relatively large changes in clay with temperature are said to have a low viscosity index (VI). VI is an empirical value that indicates the rate at which the viscosity of the oil changes within a given temperature range. An oil with a high VI will, for example, fade more slowly at a higher temperature than a low VI oil. Higher VI oils usually have a higher viscosity at higher temperatures, which will have better lubricity and better protect the contact parts of the machine, preferably at high temperatures and / or over a wide range of temperatures Because it is more desirable. VI is calculated according to ASTM D 2270.

If the lubricant is expected to provide lubricity in a low temperature environment, it is also important that the lubricant has good properties at low temperatures. These low temperature properties are such as the pour point of pure fluid according to ASTM D 97, the low temperature Brookfield viscosity of pure or blended fluid according to ASTM D 2983, or the Cold Cranking Simulator (CCS) viscosity. It can be measured by any other suitable method.

As newer equipment or engines are often operated at harsher conditions, it is becoming more important that the lubricant has good shear stability. The shear stability of pure fluids or lubricant blends is measured by a number of methods, such as the sonic shear test according to ASTM D 2603 or the tapered roller bearing (TRB) shear test according to the CEC L-45-T A to D method. Is possible.

PAO contains hydrocarbons produced by catalytic oligomerization (polymerization to low molecular weight products) of linear alpha-olefin (LAO) monomers. These include copolymers of ethylene and higher olefins described in US Pat. No. 4,956,122 and the patents cited therein, although lower olefin oligomerized copolymers such as ethylene and propylene can also be used, Usually including the range of 1-octene to 1-dodecene, 1-decene is the preferred material.

PAO products are important in the lubricant market. There are two classes of synthetic hydrocarbon fluids (SHF), usually produced from linear alpha-olefins, these are PAO and HVI-PAO (high viscosity index PAO). Different viscosity grades of PAO are usually produced using promoted BF ₃ or AICI ₃ catalysts.

In particular, PAO may be produced by polymerization of olefin raw materials in the presence of a catalyst such as AlCl ₃ , BF ₃ , or promoted AlCl ₃ , BF ₃ catalyst. PAO production methods are disclosed, for example, in the following patents: US Pat. Nos. 3,149,178; 3,382,291; 3,742,082; 3,769,363; 3,780,128; 4,172,855 and 4,956,122. Is incorporated herein by reference. PAO is also described in Will, JG “Lubrication Fundamentals”, Marcel Dekker: New York, 1980. Following polymerization, products in the PAO lubricant range are typically hydrogenated to reduce residual unsaturation and are typically at a level of hydrogenation above 90%. High viscosity PAOs can also be conveniently produced by polymerizing alpha-olefins in the presence of a polymerization catalyst such as Friedel-Crafts catalyst. This includes, for example, boron trichloride, aluminum trifluoride or boron trifluoride promoted with each of the following: water; alcohols such as ethanol, propanol, or butanol; carboxylic acids; ethyl acetate or ethyl Esters such as propionic acid; ethers such as diethyl ether, diisopropyl ether and the like (see, for example, the methods disclosed in US Pat. Nos. 4,149,178 or 3,382,291).

Other PAO syntheses can be found in the following US patents: 3,742,082 (Brennan); 3,769,363 (Brennan); 3,876,720 (Heilman); 4,239,930 (Allphin); 4,367,352 (Watts); 4,413,156 (Watts); 4,434,408 (Larkin); 4,910,355 (Shubkin); 4,956,122 (Watts); and 5,068,487 (Theriot).

Other types of HVI-PAO may be produced by the action of a reduced chromium catalyst supported with alpha-olefin monomers. Such PAOs are described in US Pat. Nos. 4,827,073 (Wu); 4,827,064 (Wu); 4,967,032 (Ho et al.); 4,926,004 (Pelrin et al.); And 4,914,254 (Pelrine). Commercially available PAOs include SpectraSyn® 2, 4, 5, 6, 8, 10, 40, 100 and SpectraSyn Ultra® 150, SpectraSyn-Ultra® 300, SpectraSyn Ultra (registered) Trademark) 1000 etc. (ExxonMobil Chemical Company, Houston, Texas).

Synthetic PAO is widely accepted and has a commercial advantage in the lubricant field compared to mineral-based lubricants. For improved lubricant properties, industrial research efforts in synthetic lubricants show useful viscosities over a wide temperature range, i.e. improved viscosity index, while also being equal to or better than mineral oil. The resulting PAO exhibits lubricity, thermal stability, oxidation stability and pour point.

These new synthetic lubricants reduce mechanical friction, improve mechanical efficiency over the full range of mechanical loads, and achieve these conditions over wider operating conditions than mineral oil lubricants.

The demands on the function of lubricants are becoming increasingly strict. Improved, such as high viscosity index (VI), low pour point, reduced volatility, high shear stability, improved anti-wear performance, good thermal stability, oxidation stability, and / or wide viscosity range New PAOs with properties are sought as a response to the demand for new functions of lubricants. There is also a need for new ways to provide new PAOs with such improved properties.

Efforts have been made to produce various PAOs using metallocene catalyst systems. Examples include U.S. Patent No. 6,706,828 (corresponding to U.S. Patent Application No. 2004/0147693), where PAO is a class of metallocene in the meso form using methylalumoxane as an activator under high hydrogen pressure. It is described that it is produced by a catalyst.

However, the comparative example of US Pat. No. 6,706,828 is rac-dimethylsilyl bis (2-methyl-indenyl) zirconium dichloride in combination with methylalumoxane (MAO) at 100 ° C. in the presence of hydrogen to produce polydecene. (Rac-dimethylsilylbis (2-methyl-indenyl) zirconium dichloride) is used. Similarly, WO 02/14384 is an isotactic polydecene said to have a Tg of −73.8 ° C., a KV _{100 of} 702 cSt, and a VI of 296 in Examples J and K; or a Tg of −66 ° C. MAO (hydrogen at 200 psi or 1 molar hydrogen) at 40 ° C. to produce an isotactic polydecene, said to have a kinematic viscosity at 100 ° C. (KV ₁₀₀ ) of 1624 cSt, and VI of 341 In combination,
rac-ethyl-bis (indenyl) zirconium dichloride or rac-dimethylsilyl-bis (2-methyl-indenyl) zirconium dichloride The use of zirconium dichloride) is disclosed. In addition, WO 99/67347 is an example of ethylidene bis (tetrahydroindenyl) in combination with MAO at 50 ° C. to produce polydecene in Example 1 where M _n is said to have 11,400 and 94% vinylidene double bond content. The use of ethylidene bis (tetrahydroindenyl) zirconium dichloride is disclosed.

Others are not particularly known to produce polymers or oligomers with any particular stereoregularity, but various metallocene catalysts are used to produce various PAOs such as polydecene. Examples include WO 96/23751, EP 0 613 873, U.S. Patent Nos. 5,688,887, 6,043,401, WO 03/020856 (equivalent to U.S. Patent Application Publication No. 2003/0055184), U.S. Patent Nos. 5,087,788, 6,414,090. No. 6,414,091, No. 4,704,491, No. 6,133,209, and No. 6,713,438.

However, at present, PAOs produced with metallocenes are not widely used in the market, especially in the lubricant market, due to their inefficient methods, manufacturing processes, high cost and / or property deficiencies. The present invention solves these problems and meets other needs by providing a new PAO with an excellent combination of properties and an improved method of producing it.

US Pat. No. 6,548,724 (equivalent to US 2001/0041817 and US Pat. No. 6,548,723) discloses the production of oligomeric oils used in combination with certain metallocene catalysts, typically methylalumoxane. In column 20, lines 40-44 of US Pat. No. 6,548,724, Example 10-11 is a Zee, Tree, or Tetra substitution on the cyclopentadienyl ring of the metallocene is a good yield and high viscosity polyalphaolefin ( It is disclosed that it is useful for the production of viscosities in the range of 20 to 5000 cSt at 100 ° C., but not good with pentaalkyl-substituted cyclopentadienyl rings. Examples 12 and 13 further show the production of polydecene with KV100 of 154 and 114.6 in the absence of hydrogen. Further, in Example 14, decene was converted to Cp ₂ ZrMe ₂ or (iPr-Cp) ₂ ZrCl ₂ , N, N-dimethylanilinium-tetra (phenyl) boron (N, N-dimethylanalinium tetra (phenyl)) at 100 ° C. or 110 ° C. The polymerization of decene is disclosed to polymerize borate) to produce polydecene with KV100 of 5.3 to 11.4.

PCT / US06 / 21231, filed on June 2, 2006, will benefit from the priority of US Patent Application No. 60 / 700,600, filed July 19, 2005, but with racemic metallocene and non-distributed It describes the production of liquids from monomers having 5 to 24 carbon atoms using coordinate anionic activators. Other references of interest include EP0284708, US Pat. Nos. 5,846,896, 5679812, EP0321852, US Pat. No. 4,962,262, EP0513380, US Patent Application Publication No. 2004/0230016, and US Pat. No. 6,642,169.

The present invention relates to a process for producing polyalpha-olefins having a KV ₁₀₀ of greater than 20 cSt and up to about 10,000 cSt, the process comprising:
Contacting one or more alpha-olefin monomers having 3 to 24 carbon atoms with an unbridged substituted bis (cyclopentadienyl) transition metal compound, wherein the compound has the formula:
(Cp) (Cp *) MX ₁ X ₂
Where M is a metal center and a Group 4 metal;
Cp and Cp * are each the same or different cyclopentadienyl ring bonded to M, 1) Cp and Cp * are both substituted with at least one non-hydrogen substituent R, or 2) Cp is Substituted with 2 to 5 substituents R, each substituent R being independently a radical group that is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, or Cp and Cp * are Any two adjacent R groups optionally linked to form a substituted, unsubstituted, saturated, partially unsaturated or aromatic ring or polycyclic substituent, the same or different cyclopenta A dienyl ring;
X ₁ and X ₂ are independently hydrogen, halogen, hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, silylcarbyl radical, substituted silylcarbyl radical, germylcarbyl radical Or a substituted germylcarbyl radical;
Or both X are linked and bonded to a metal atom to form a metal ring containing from about 3 to about 20 carbon atoms; or both may be an olefin, diolefin, or an aligned ligand; And under polymerization conditions, a non-coordinating anionic activator, and optionally an alkylaluminum compound, wherein the molar ratio of transition metal compound to activator is 10: 1 to 0.1: 1, and an alkylaluminum compound is present The molar ratio of alkylaluminum compound to transition metal compound is 1: 4 to 4000: 1; polymerization conditions are 1) hydrogen is present at a partial pressure of 0.1 to 300 psi based on the total pressure of the reactor, or The concentration of hydrogen is from 1 to 30,000 ppm by weight;
2) Alpha-olefin monomers having 3 to 24 carbon atoms are present in an amount of 10% by weight or more based on the total weight of catalyst / activator / alkylaluminum compound solution, monomers and all diluents or solutions present during the reaction;
3) provided that no ethylene is present in excess of 40% by weight of the monomer entering the reactor.

FIG. 1 shows the MWD of polyalphaolefins (PAO) produced according to the present invention, showing typical values and upper and lower limits. Line 1 ● represents PAO produced by a nonmetallocene catalyst, and y = 0.2223 + 1.02321og (x) R = 0.97035.

Line 2 indicates the upper limit of MWD according to the present invention, and y = 0.8 + 0.31og (x). Line 3 ▼ is a typical MWD of poly-1-butene produced by the method of the present invention, where y = 0.126263 + 0.493871 og (x) R = 0.91343.

Line 4 indicates the lower limit of the MWD according to the present invention, and y = 0.41667 + 0.7251 og (x). (1) shows Examples 1 to 9 (Table 1), where y = 0.66017 + 0.449221og (x) R = 0.99809.

FIG. 2 compares the selectivity of the dimer of the present invention with the selectivity of the dimer described in US Pat. No. 6,548,724. ● dimers selectivity of the present ^{invention, y = 350.68 * x Λ (} -1.5091) R = 0.98993 ( Examples 1 to 9, Table 1). Is the dimer selectivity y = 231.55 * x ^Λ (-0.90465) R = 0.93734 according to US Pat. No. 6,548,724.

FIG. 3 is a comparison of the fluid VI according to the present invention and the fluid VI disclosed in US Pat. No. 6,548,742. ● indicates VI of Examples 1 to 9 in Table 1. □ indicates the VI of the material produced in US Pat. No. 6,548,742.

FIG. 4 shows the pour point of the PAO fluid according to the present invention and the material produced in US Pat. No. 6,548,742. ● indicates the pour point of Examples 1 to 9 in Table 1. □ indicates the pour point of the material produced in US Pat. No. 6,548,742.

FIG. 5 shows the vinylidene content of Examples 10 to 21 (Table 3) versus the vinylidene content of Comparative Examples 14 to 17 (Table 4). -Represents the numerical values of Examples 10 to 21 in Table 3, poly 1-butene by catalyst A or B activated by NCA. □ shows Comparative Examples 14 to 17 in Table 4, and shows the value of poly-1-butene by the catalyst AB activated by MAO.

FIG. 6 shows the branched methyl content of Comparative Examples 10 to 21 (Table 3) versus the branched methyl content of Comparative Examples 14 to 17 (Table 4). ● represents the numerical values of Examples 10 to 21 in Table 3, and the numerical value of poly-1-butene by the catalyst A or B activated by NCA. □ shows Examples 14 to 17 in Table 4, and shows the value of poly-1-butene by Catalyst B activated by MAO. The straight line represents y = -3.4309Ln (x) + 29.567,
y = methyl molecule per 1000C, x = Kv by cSt at 100 ° C.

Detailed Description of the Invention

The new numbering system for the periodic table of elements used in this specification is the one specified in CHEMICAL AND ENGINEERING NEWS, 63 (5), 27 (1985).

Unless otherwise noted, all pressures in psi are in psig.

In the context of the present invention and the claims, when a polymer or oligomer includes an olefin, the olefin present in the polymer or oligomer is in the form of a polymerized or oligomerized olefin, respectively. Similarly, the term polymer is used to include homopolymers and copolymers, where a copolymer is any polymer that contains two or more chemically distinct monomers. Similarly, oligomers are used to mean including homo-oligomers and co-oligomers, which include any oligomer having two or more chemically defined monomers.

In this specification and in the claims, the term “polyalphaolefin”, “polyalphaolefin” or “PAO” includes homo-oligomers, co-oligomers, homopolymers and copolymers of C3 or larger alpha-olefin monomers. .

The PAOs of the present invention include oligomers, polymers or a combination of both. The PAO compositions of the present invention (whether oligomers, polymers or a combination of both) are liquids and have a M _w of 200,000 or less.

In the present specification and claims, the active species of the catalyst circuit may include neutral and ionic catalysts.

“Catalyst system” is defined to mean a catalyst precursor / activator pair, such as a metallocene / activator pair. When “catalytic system” is used for a pre-activated pair, it refers to an unactivated catalyst (pre-catalyst) with an activator and optionally a co-activator (such as a trialkylaluminum). When used for an activated pair, it refers to an activated catalyst and activator or other charge balancing fraction. In addition, the catalyst system may optionally include a co-activator and / or other charge balance fractions.

“Catalyst precursor” also often refers to precatalysts, catalysts, catalyst compounds, precursors, metallocenes, transition metal compounds, unactivated catalysts or transition metal complexes. These terms are used interchangeably. Activators and cocatalysts are also used interchangeably. A scavenger is a compound that is usually added to promote oligomerization or polymerization by scavenging impurities. Certain scavengers also act as activators and are sometimes referred to as co-activators. Coactivators that are not scavengers are also used with activators to form active catalysts with transition metal compounds. In certain embodiments, the cocatalyst may be premixed with a transition metal compound to form an alkylated transition metal compound, also referred to as an alkylated catalyst compound or an alkylated metallocene.

In the present specification and claims, non-coordinating anion (NCA) refers to an anion that does not coordinate to a catalytic metal cation or weakly bonds to a metal cation. The coordination of NCA is so weak that neutral Lewis bases such as olefins or acetylenically unsaturated monomers can displace it from the catalyst center. Any metal or metalloid capable of forming a weak coordination complex that coexists with the catalytic metal cation can be used or included in the non-coordinating anion. Suitable metals include, but are not limited to, aluminum, gold and platinum. Suitable metalloids include but are not limited to boron, aluminum, phosphorus and silicon. A subclass of non-coordinating anions includes stoichiometric activators, which can be either neutral or ionic. Ionic and stoichiometric ionic activators can be used interchangeably. Similarly, neutral stoichiometric activators and Lewis acid activators can be used interchangeably.

Furthermore, a reactor refers to any vessel in which a chemical reaction takes place.

“Isoalkyl” is a branched alkyl group or radical having at least one tertiary or quaternary carbon atom, and the branched alkyl group or radical is from at least one C ₁ along at least a portion of each chain. It has C ₁₈ alkyl branches.

Polyalphaolefins In a preferred embodiment, the present invention relates to liquid polyalphaolefins (PAO), which are based on the moles of all monomers present in the polyalphaolefin as determined by ¹³ C NMR. More than 50 mol%, preferably 55 mol% or more, preferably 60 mol% or more, preferably 65 mol% or more, preferably 70 mol% or more, preferably 75 mol% or more. Preferably it is 80 mol% or more, preferably 85 mol% or more, preferably 90 mol% or more, preferably 95 mol% or more, preferably 100 mol%.

In the present description and claims, a liquid is defined as a material that is fluid at room temperature, has a pour point below 25 ° C, and a kinematic viscosity at 100 ° C of 30,000 cSt or less.

In other embodiments, any of the polyalphaolefins described herein has a Group 4 metal (preferably Ti, Hf or Zr) of less than 300 ppm, preferably less than 200 ppm, preferably as measured by ASTM D 5185 Should be less than 100 ppm, less than 50 ppm, less than 10 ppm, or less than 5 ppm.

In other embodiments, any of the polyalphaolefins described herein has a Ti of preferably less than 300 ppm, preferably less than 200 ppm, preferably less than 100 ppm, preferably as measured by ASTM D 5185. It may contain less than 50 ppm, preferably less than 10 ppm, or preferably less than 5 ppm.

In other embodiments, any of the polyalphaolefins described herein preferably has an Hf of less than 300 ppm, preferably less than 200 ppm, preferably less than 100 ppm, preferably as measured by ASTM D 5185. It may contain less than 50 ppm, preferably less than 10 ppm, or preferably less than 5 ppm.

In other embodiments, any of the polyalphaolefins described herein has a Zr of preferably less than 300 ppm, preferably less than 200 ppm, preferably less than 100 ppm, preferably as measured by ASTM D 5185. It may contain less than 50 ppm, preferably less than 10 ppm, or preferably less than 5 ppm.

In other embodiments, any of the polyalphaolefins described herein preferably has a Group 13 metal (preferably B or Al) less than 100 ppm, preferably less than 50 ppm, as measured by ASTM D 5185. , Preferably less than 10 ppm, or preferably less than 5 ppm.

In other embodiments, any of the polyalphaolefins described herein is preferably less than 100 ppm, preferably less than 50 ppm, preferably less than 10 ppm, or preferably boron as measured by ASTM D 5185. Should contain less than 5 ppm.

In other embodiments, any of the polyalphaolefins described herein is preferably aluminum less than 600 ppm, preferably less than 500 ppm, preferably less than 400 ppm, preferably as measured by ASTM D 5185. May contain less than 300 ppm, preferably less than 200 ppm, preferably less than 100 ppm, preferably less than 50 ppm, preferably less than 10 ppm, or preferably less than 5 ppm.

In other embodiments, any of the polyalphaolefins described herein has an Mw (weight average molecular weight) of about 200,000, preferably about 250 to about 200,000, preferably about 280 to about 100,000, preferably From about 336 to about 150,000, and preferably from about 336 to about 100,000 g / mol.

In other embodiments, any of the polyalphaolefins described herein has an M _n (number average molecular weight) of less than 200,000, preferably from 250 to about 150,000, preferably from about 250 to about 125,000 and preferably It may be from about 280 to about 100,000 g / mol.

In other embodiments, any of the polyalphaolefins described herein has an M _w / M _n greater than 1 and less than 5, preferably less than 4, preferably less than 3, preferably less than 2.5, preferably Should be less than 2.

Alternatively, any of the polyalphaolefins described herein preferably have a M _w / M _n of preferably 1 to 3.5, alternatively 1 to 2.5.

In the present specification and claims, MWD is equivalent to M _w / M _n .

For many uses where excellent shear stability, thermal stability or thermal / oxidative stability is desired, it is preferred that the polyalphaolefins be produced with the narrowest possible MWD. Although PAO fluids with different viscosities, PAO fluids produced from the same feed or catalyst usually have different MWDs. In other words, the MWD of a PAO fluid depends on the viscosity of the fluid.

Usually low viscosity fluids have narrower MWD (smaller MWD values) and high viscosity fluids have wider MWD (larger MWD values). For most fluids with a Kv at 100 ° C. of less than 1000 cSt, the MWD is usually less than 2.5, typically around 2.0 ± 0.5.

For fluids with a viscosity at 100 ° C greater than 1000 cSt, the MWD is usually wide and usually greater than 1.8.

A typical range for the relationship between MWD and fluid viscosity at 100 ° C. is shown in FIG. The narrower the MWD of a normal fluid, the better its shear stability. Such narrow MWD fluids have low viscosity loss due to high stress or shear in the TRB test, have higher temperature, higher shear rate (HTHSR) viscosity under more severe conditions, thicker lubricant film, and better at the same time Excellent lubricity and wear protection. For some uses, shear stability or HTHSR viscosity is not a critical factor, and a wider MWD may produce better blending properties or other benefits.

Mw, Mn and MWD are measured by a method called size exclusion chromatography (SEC) or gel permeation chromatography (GPC). This method uses a medium to low molecular weight polymer, tetrahydrofuran is the solvent, polystyrene. Is used as a calibration standard. Unless otherwise noted, the Mn and Mw values used herein are values measured by GPC, not values calculated from kinematic viscosity at 100 ° C.

In a preferred embodiment of the invention, any of the polyalphaolefins described herein has a pour point of less than 10 ° C (according to ASTM D 97), preferably 0 ° C, preferably less than -10 ° C, preferably- Less than 20 ° C, preferably less than -25 ° C, preferably less than -30 ° C, preferably less than -35 ° C, preferably less than -40 ° C, preferably less than -55 ° C, preferably between -10 and -80 ° C, The temperature is preferably between -15 ° C and -70 ° C.

In a preferred embodiment of the invention, any of the polyalphaolefins described herein has a kinematic viscosity at 100 ° C. of greater than 20 and up to about 5000 cSt, preferably greater than 20 and about 3000 cSt, preferably 20 It should be larger than cSt and up to about 1500 cSt. In other embodiments of the invention, any of the PAOs described herein have a kinematic viscosity at 40 ° C. as measured by ASTM D 445 of from about 50 to about 500,000 cSt, preferably from about 75 cSt to about 100,000. It may be cSt, alternatively about 100 to about 8,000 cSt.

In certain preferred embodiments of the invention, the polyalpha-olefin fluid described herein may have a viscosity index (VI) greater than 60. VI is determined by ASTM D 2270-93 [1998]. The VI of a fluid usually depends on its viscosity and raw material composition. Higher VI is more desirable. When the viscosity of the fluid having the same raw material composition is high, VI is usually high.

A typical VI range for fluids derived from C ₃ or C ₄ or C ₅ linear alpha olefins (LAO) is 65 to 250. The typical VI range for fluids derived from C ₆ or C ₇ is 100 to 300, again this depends on the viscosity of the fluid.

The typical VI range for fluids obtained from C ₈ to C ₁₄ LAO, such as 1-octene, 1-nonene, 1-decene or 1-undecene or 1-dodecene, 1-tetra-decene, depends on viscosity. 120 to> 450.

More specifically, the VI range for fluids obtained from 1-decene or 1-decene equivalent feedstock is from about 100 to about 500, preferably from about 120 to about 400. When two or more alpha-olefins are used, for example, C ₃ + C ₁₀ , C ₃ + C ₁₄ , C ₃ + C ₁₆ , C ₃ + C ₁₈ , C ₄ + C ₈ , C ₄ + C ₁₂ , C ₄ + C ₁₆ , C ₃ + C ₄ + C ₈ , C ₃ + C ₄ + C ₈ , C ₄ + C ₁₀ + C ₁₂ , C ₄ + C ₁₀ + C ₁₄ , C ₆ + C ₁₂ , C ₆ + Combinations such as C ₁₂ + C ₁₄ , C ₄ + C ₆ + C ₁₀ + C ₁₄ , C ₄ + C6 + C8 + C ₁₀ + C ₁₂ + C ₁₄ + C ₁₆ + C ₁₈ are used as raw materials.

The VI of the product also depends on the fluid viscosity and the selection of the raw olefin composition. For use in the most severe conditions of the lubricant, it is better to use a fluid with a higher VI.

In other embodiments, the PAO fluid preferably does not contain very light fractions. These light fractions cause high volatility, unstable viscosity, poor oxidation and thermal stability. These fractions are removed in the final product. Generally, fluids with C20 or less carbon should be less than 1% by weight, more preferably C24 or less carbon fluid should be less than 1% by weight, more preferably C26 or less carbon fluid should be less than 1% by weight. . In general, the C20 or lower carbon fluid should be less than 0.5 wt%, more preferably the C24 or lower carbon fluid should be less than 0.5 wt%, more preferably the C26 or lower carbon fluid should be less than 0.5 wt%. Also, the lower the total amount of these light hydrocarbons, the better the fluid properties that can be determined by the Noack volatility test.

Preferably, the PAO fluid has a Noack volatility of less than 5 wt%, preferably less than 2 wt%, preferably less than 0.5 wt%.

In other embodiments, any of the polyalphaolefins described herein may have a kinematic viscosity at 100 ° C as measured by ASTM D 56 of greater than 20 to 5000 cSt and a flash point of 150 ° C or higher. good.

In other embodiments, any of the polyalphaolefins described herein may have a dielectric constant of 3 or less, typically 2.5 or less (as determined by ASTM D 924 at 23 ° C., 1 kHz).

In other embodiments, any of the polyalphaolefins described herein may have a specific gravity of 0.6 to 0.9 g / cm ³ , preferably 0.7 to 0.88 g / cm ³ .

PAOs produced by the present invention, especially medium to high viscosity PAOs (eg, KV ₁₀₀ greater than 20 cSt) are particularly high performance automotive engine oils, general industrial lubricants, various automotive or industrial applications. Suitable for preparation of gear oil, aircraft lubricant, hydraulic oil or lubricant, heat transfer fluid, etc. These can be obtained on their own or, for example, in Fischer-Tropsch hydrocarbon synthesis from Group I, II, Group II +, Group III, Group III + base feedstock, or CO / H ₂ syn gas. Lubricating base stock derived from hydroisomerization of the wax fraction produced, or other fluids such as other Group IV or Group V or Group VI base stocks in the range of 0.1% to 95% by weight. Can be used. These blend raw materials, when combined with additives, are used to prepare fully synthetic lubricants, partial composites, or as special additive components with base raw materials.

The kinematic viscosity values reported for the fluids used in the present invention are all measured at 100 ° C. unless otherwise noted. The dynamic viscosity is obtained by multiplying the measured kinematic viscosity by the density of the liquid. The unit of kinematic viscosity is m ² / s, usually converted to cSt or centistoke (1 cSt = 10 ⁻⁶ m ² or 1 cSt = 1 mm ² / sec).

Dimers of the olefin monomer to C ₂₄ are PAO produced from normal one or more C ₃ according to the present invention, trimers, tetramers or higher oligomers, C ₂₀ alpha-olefins preferably from one or more C ₄ It may be a monomer, preferably one or more C ₅ to C ₂₀ linear alpha-olefin monomers. Alternatively, alpha olefins having an alkyl substituent at least 2 carbons away from the olefinic double bond can also be used.

Typically, the PAO according to the present invention is usually a mixture of many different oligomers. In some embodiments, the smallest oligomer obtained from these alpha-olefins has from ₁₀ to ₂₀ carbon atoms. These small oligomers are usually greater than the number of carbon atoms is C _20, for example, typically used as a high functional fluids are separated from the higher oligomers with carbon number to C ₂₄ or higher. Corresponding paraffins after oligomeric olefins or hydrogenated to C ₂₀ These separated C ₁₀ are drilling fluids, solvents, paint thinners, etc., excellent biodegradability, toxicity, special applications requiring viscosity, etc. Can be used. In some cases, smaller oligomers up C ₄₀ produces a product having the most desirable properties is separated from the residual lubricating fraction. C ₂₀ high performance fluid fractions or higher grades than C ₃₀ usually have lower viscosities and require fuel efficient fuels, better biodegradability, lower temperature flow properties or lower volatility Can be advantageously used for various uses.

In the present invention, the oligomerization or polymerization process is usually used in such a way as to produce a final product with a kinematic viscosity at 100 ° C. greater than 20 cSt. The processes and catalysts used to produce these fluids are unique in that they produce polymers with a narrow molecular weight distribution. Because of this feature, the polymerization process involves a lubricant fraction product that contains a very small amount of light fractions of C ₂₀ or C ₂₄ or C ₂₈ or C ₃₀ or lower fractions, depending on the type of feedstock. Generate with very high selectivity. Furthermore, due to this narrow distribution, the final lubricant fraction does not contain excessive polymer fractions that cause instability under shear, heat, oxidative stress, etc.

The PAOs described herein further include other base ingredients (Groups I to VI) and antioxidants, antiwear agents, friction modifiers, dispersants, rust inhibitors, antifoam agents, extreme pressure additives, seals. It may be blended with additives including seal swell additives and optionally viscosity modifiers. For a description of typical additives, preparations and their use, see “Synthetics, Mineral Oils, and Bio-Based Lubricants, Chemistry and Technology”, Ed. LR. Rudnick, CRC Press, Taylor & Francis Group, Boca Raton, FL. And “Lubricant Additives”, Chemistry and Applications (“Lubricant Additives” Chemistry and Applications, edited by LR Rudnick, Marcel Dekker, Inc., New York, 2003 I can see it.

In another embodiment, the PAO produced according to the present invention has a volatility measured by Noack Volatility Test (ASTM D5800) of less than 25% by weight, preferably less than 20% by weight, less than 14% by weight, preferably 10 It may be less than wt%, preferably less than 5 wt%. Often oils have a Noack volatility of less than 2% by weight.

In other embodiments, the PAO produced directly from the oligomerization or polymerization process is an unsaturated olefin. The amount of unsaturation can be quantitatively determined by bromine number measurement by ASTM D 1159, proton or C-13 NMR. Proton NMR spectroscopy can also distinguish and quantitate unsaturated species of olefins: vinylidene, 1,2-2 substituted, trisubstituted or vinyl. In C-13 NMR spectroscopy, the olefin distribution calculated from the proton spectrum can be confirmed.

C-13 NMR spectroscopy can be performed more specifically with respect to the length of branching, but both proton and C-13 NMR spectroscopy are numerical values for the range of single chain branching (SCB) in olefin oligomers. Can be In the proton spectrum, SCB branch methyl resonance occurs in the 1.05-0.7 ppm range. SCBs of sufficiently different lengths are separated enough to give a branch length distribution or show uncomplicated and distinct methyl peaks. The remaining methylene and methine signals resonate in the range of 3.0-1.05 ppm. In order to relate the whole to the CH, CH ₂ and CH ₃ concentrations, each individual and whole needs to be modified with respect to proton diversity. The total methyl is divided by 3 to determine the number of methyl groups; the remaining aliphatic total is considered to contain one CH signal for each methyl group and the rest of the total contains a CH ₂ signal. The ratio of CH ₃ / (CH + CH ₂ + CH ₃ ) indicates the concentration of methyl groups.

For C-13 NMR analysis, the same logic applies except that no modification due to proton diversity is required. Furthermore, since the spectrum / structure resolution of C-13 NMR as compared with H-1 NMR is improved, ion differentiation is possible depending on the length of the branches. Typically, methyl resonances are grouped separately, methyl (20.5-15 ppm), propyl (15-14.3 ppm), butyl- and -longer branches (14.3-13.9 ppm), and ethyl (13.9-7 (ppm) branch concentrations can be obtained.

Olefin analysis can be easily performed by proton NMR, further dividing the olefin signal between 5.9 and 4.7 ppm by the olefin alkyl substitution pattern. Vinyl group CH protons resonate between 5.9-5.7 ppm, and vinyl group CH ₂ protons resonate between 5.3 and 4.85 ppm. 1,2-2 disubstituted olefinic protons resonate in the 5.5-5.3 ppm range. The peak of the trisubstituted olefin overlaps the vinyl group CH ₂ peak in the region of 5.3-4.85 ppm. The contribution of vinyl groups in this region is removed by subtraction based on twice the total of vinyl CH. 1,1-2 substituted- or vinylidene-olefins resonate in the 4.85-4.6 ppm region. Olefinic resonances can be normalized to obtain a mole percent olefin distribution when the proton diversity is modified, or the aliphatic region with modified diversity (as described above for methyl analysis). Contrast is obtained to obtain fraction concentrations (eg, olefins per 100 carbons).

Usually, the amount of unsaturation is highly dependent on fluid viscosity or fluid molecular weight. A low viscosity fluid has a high degree of unsaturation and a high bromine number. High viscosity fluids have a low degree of unsaturation and a low bromine number. If a large amount of hydrogen or high pressure hydrogen is used during the polymerization, the bromine number appears to be lower than when no hydrogen pressure is used. In the process of this invention, for 20 to 5000 cSt polyalphaolefins produced from 1-decene or other LAOs, the PAO as-synthesized usually has a bromine number of less than 25 to 1 depending on the fluid viscosity.

The type of olefinic unsaturation in the PAO fluid produced by the process of the present invention is unique as confirmed by ¹ H and ¹³ C-NMR. They contain a very high proportion of vinylidene olefins, CH ₂ ═CR ¹ R ² , tri- or di-substituted olefins, and a smaller proportion of other unsaturated species. The vinylidene content is preferably much higher than the vinylidene content of polyalphaolefins produced by conventional methods based on metallocenes used with MAO accelerators. FIG. 5 compares the mole% of vinylidene content of poly 1-butene according to the present invention with materials produced by the general method disclosed in US Pat. No. 6,548,724. In the present invention, the vinylidene content is greater than 65 mol%, or greater than 70% or greater than 80%. In general, the higher the amount of vinylidene unsaturation, the better. This is because these olefin species are further reacted and hydrogenated or functionalized. Many methods have been disclosed for maximizing the amount of vinylidene olefin, such as those described in US Pat. No. 5,286,823. Vinylidene olefins usually react faster with maleic anhydride in an ene reaction. These are very easily hydrogenated to make saturated hydrocarbons for high performance base feeds. Usually, the degree of hydrogenation affects the oxidative stability of the fluid. Fluids with higher levels of hydrogenation and at the same time lower bromine number are usually better in oxidation stability. The PAOs of the present invention have a high vinylidene content and therefore become more amenable to hydrogenation and form a low bromine fluid. The bromine number after hydrogenation is preferably less than 5, more preferably less than 3, more preferably less than 2, more preferably less than 1, more preferably less than 0.5, more preferably less than 0.1. Usually, the lower the bromine number, the better the oxidation stability.

The PAO produced according to the present invention also had a lower amount of methyl groups per 1000 carbons than PAO produced by known methods. FIG. 6 shows the amount of CH ₃ groups contained in PAO per 1000 carbons of poly 1-butene fluid by the catalyst and process of the present invention compared to known methods. The product according to the invention has a lower methyl content than that defined by the following equation:
(Methyl branches per 1000 carbons) = -3.4309 x Ln (kinematic viscosity with cSt at 100 ° C) + 29.567
Methyl branching is usually less desirable. The reason is that such branching depresses VI and / or reduces oxidative stability.

The PAO produced in the present invention is a liquid. In this specification and claims, a liquid is defined as a material that flows at room temperature, has a pour point of less than 25 ° C., and a kinematic viscosity at 100 ° C. of 30,000 cSt or less.

In certain preferred embodiments, the PAO produced in the present invention contains a very high amount of atactic polymer structure. In other words, most of the monomer units of PAO are in an atactic configuration. This atactic polymer is convenient for use in lubricants. In a preferred embodiment, the PAO produced according to the present invention is at least 50%, preferably at least 75%, preferably at least 85%, preferably at least 90%, as determined by C-13 NMR as described below. , Preferably at least 95%, preferably at least 99% atactic polymer structure.

In another embodiment, the invention further provides that the mm triplet determined by C-13 Nuclear Magnetic Resonance (NMR) spectroscopy described below is 90 mol% or less, preferably 80 mol% or less. , Preferably 70 mol% or less, preferably 60 mol% or less, preferably 50 mol% or less, preferably 40 mol% or less, preferably 30 mol% or less, preferably 20 mol% or less, preferably 10 mol% or less, It relates to PAO which is preferably 5 mol% or less.

In another embodiment, the invention further provides that the rr triplet determined by C-13 nuclear magnetic resonance spectroscopy as described below is 90 mol% or less, preferably 80 mol% or less, preferably 70 mol% or less, Preferably it is 60 mol% or less, preferably 50 mol% or less, preferably 40 mol% or less, preferably 30 mol% or less, preferably 20 mol% or less, preferably 10 mol% or less, preferably 5 mol% or less. Regarding PAO.

In another embodiment, the present invention further provides that the mr triplet determined by C-13 nuclear magnetic resonance spectroscopy described below is 20 mol% or more, preferably 30 mol% or more, preferably 40 mol% or more, Preferably, it relates to a PAO that is at least 50 mol%, preferably at least 55 mol%, preferably at least 60 mol%, preferably at least 70 mol%, preferably at least 75 mol%.

In another embodiment, the invention further provides that the mm / mr ratio determined by C-13 nuclear magnetic resonance spectroscopy as described below is less than 5, preferably less than 4, preferably less than 3, preferably 2 Less than, preferably less than 1 PAO.

As noted above, C-13 nuclear magnetic resonance is used to determine the stereoregularity of the polyalphaolefins of the present invention quantitatively in some cases and qualitatively in others. C-13 nuclear magnetic resonance can be used to determine not only the molar composition of the sample, but also the triplicate concentrations indicated by mm (meso, meso), mr (meso, racemic) and rr (racemic, racemic). .

These triplicate concentrations define whether the polymer is isotactic, atactic or syndiotactic. The spectrum of the PAO sample is obtained by the following method. About 100-1000 mg of PAO sample is dissolved in 2-3 ml of chloroform for analysis of C-13 NMR. About 10 mg / ml (solvent based) chromium acetylacetonate relaxation agent Cr (acac) 3 was added to the samples to improve the data acquisition rate. Spectrum analysis is by Kim, I .; Zhou, J.-M .; and Chung, H. “Journal of Polymer Science”: Part A: Polymer Chemistry 2000, 38 1687-1697 Performed according to the paper, augmented by the removal of its contributions to peaks used for identification and integration and analysis of end group resonances. The analysis was performed by Acorn NMR Inc.'s NutsPro NMR data analysis software using 85/15 Lorentzian / Gaussian alignment. The component peaks are organized as a cluster according to the mm, mr, and rr triplet arrangement and fit to the Bernoulli distribution. The tuning parameter for these fits is Pr, the monomer portion plus the racemic stereochemistry. See Polymer Sequence Determination, James C. Randall, for details on the transition from a set of triplicate measurements (as described above by Kim) to a statistical model (like Bernoulli distribution). See Academic Press, New York, 1977. For examples of measuring the stereoregularity of polydecene and polydodecene, see the Examples section of PCT patent application PCT / US2006 / 021231 filed on June 2, 2006.

In other embodiments herein, the 1,2-2 substituted olefin is present in the polyalpha-olefin product in less than Z mole%, Z = 8.420 * Log (V)-4.048, where V is 100. It is the kinematic viscosity of the polyalphaolefin represented by cSt measured at ° C. Z is preferably 7 mol% or less, preferably 5 mol% or less.

Please refer to PCT patent application PCT / US2006 / 021231 filed on June 2, 2006 for information on how to measure 1,2-2 substituted olefin content.

In other embodiments, the alpha-olefin is a unit of less than Z mol%,

Represented by the formula
Where j, k and m are each independently 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, n is an integer from 1 to 350, and Z = 8.420 * Log (V) −4.048, where V is the kinematic viscosity of polyalphaolefin measured by cSt measured at 100 ° C.

In certain preferred embodiments, the product produced according to the present invention has a selectivity for hydrocarbons having ₂₀ or more carbon atoms of 70% or more, preferably 80% or more, preferably 90% or more, more preferably 95% or more. , Preferably 98% or more, preferably 99% or more.

In one preferred embodiment, the productivity of the process is at least 1.5 kg total product per gram transition metal compound, preferably at least 2 kg total product per gram transition metal compound, preferably total product per gram transition metal compound. Amount of at least 3 kg, preferably at least 5 kg of total product per gram of transition metal compound, preferably at least 7 kg of total product per gram of transition metal compound, preferably at least 10 kg of total product per gram of transition metal compound, preferably transition The total product quantity per gram of metal compound should be at least 20 kg.

In another preferred embodiment, the productivity of the process is at least 1.5 kg of total product per gram of non-coordinating anionic active compound, preferably at least 2 kg of total product per gram of non-coordinating anionic active compound, Preferably, the total product amount per gram of non-coordinating anionic activator compound is at least 3 kg, preferably the total product amount is at least 5 kg per gram of non-coordinating anionic activator compound, preferably per gram of non-coordinating anionic activator compound The total product amount should be at least 7 kg, preferably at least 10 kg per gram of non-coordinating anionic activator compound, preferably at least 20 kg per product of gram of non-coordinating anionic activator compound.

Since metallocenes or non-coordinating anionic activators are usually more expensive components than other components in the catalyst system, it is of interest that metallocenes or non-coordinating anionic activators are highly productive. For economical operation, it is important to have a productivity of at least 1.5 kg per unit of transition metal compound or non-coordinating anion activator compound.

In one preferred embodiment, the product produced according to the present invention has a selectivity for hydrocarbons having ₂₄ or less carbon atoms of 60% or less, preferably 50% or less, preferably 40% or less, more preferably 20% or less. , Preferably 10% or less, preferably 5% or less, preferably 1% or less (% is% by weight unless otherwise specified).

In certain preferred embodiments, the product produced according to the present invention has a selectivity to a C ₁₀ dimer (ie, a C ₂₀ product) of 60% or less, preferably 50% or less, preferably 40% or less, more It is preferably 30% or less, preferably 10% or less, preferably 5% or less, preferably 1% or less (% is% by weight unless otherwise specified).

In certain preferred embodiments, the lubricant or high performance fluid produced according to the present invention has a selectivity of 10% or more, preferably 20% or more, preferably 40% or more, more preferably 50% or more, preferably 70. % Or more, preferably 80% or more, preferably 90% or more, preferably 95% or more (% is weight% unless otherwise specified).

Process The present invention relates to an improved process for producing polyalphaolefins. This improved process uses a metallocene catalyst with one or more non-coordinating anionic activators. The metallocene catalyst is a non-bridged, substituted bis (cyclopentadienyl) transition metal compound. One preferred class of catalysts includes highly substituted metallocenes with high catalyst productivity and a kinematic viscosity of the product measured at 100 ° C. greater than 20 cSt. Another class of preferred metallocenes is unbridged and substituted cyclopentadienyl, including unbridged and substituted or unsubstituted indene and / or fluorene. One feature of these processes described herein is that of the raw olefin and solvent (if used) or peroxide, oxygen-, sulfur-, and nitrogen-containing organic and / or acetylenic compounds. Treatment of a purged nitrogen gas stream to remove such catalyst poisons. This treatment increases catalyst productivity and usually increases catalyst productivity by more than 30%, more than 50%, more than 100%, more than 200%, more than 500%, more than 1000%, more than 2000% It is believed to increase a lot.

In many cases, if the feed olefin, solvent (if used), purge gas stream is not purified, no conversion will occur or very low conversion will be obtained (eg, less than 5%).

In one preferred embodiment, the present invention relates to a process (preferably a continuous or semi-continuous or batch process) that produces a polyalphaolefin having a kinematic viscosity at 100 ° C. greater than 20 cSt and up to about 10,000 cSt. Including:
1) contacting one or more alpha-olefin monomers having 3 to 24 carbon atoms with an unbridged, substituted bis-cyclopentadienyl transition metal compound having the following structural formula:

Where M is a Group 4 metal;
Each X is independently hydrogen, halogen, hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, silylcarbyl radical, substituted silylcarbyl radical, germylcarbyl radical, or substitution A germylcarbyl radical; or both X are linked and bonded to a metal atom to form a metal ring containing from 3 to 20 carbon atoms; or both X are olefins, diolefins or aligning ligands, Well;
R ¹ to R ¹⁰ are each independently a radical group that is hydrogen, heteroatom, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, provided that
At least one of R ¹ to R ⁵ is not hydrogen and at least one of R ⁶ to R ¹⁰ is not hydrogen, and two adjacent R groups are optionally linked, substituted or unsubstituted, Subject to formation of saturated, partially unsaturated or aromatic rings or polycyclic substituents; and non-coordinating anionic activators, and optionally alkyl-aluminum compounds, activators of transition metal compounds The molar ratio of the alkyl-aluminum compound to the transition metal compound is 1: 4 to 4000: 1 when the molar ratio to is 10: 1 to 0.1: 1 and the alkyl-aluminum compound is present, the polymerization conditions present Is:
i) Based on the total pressure in the reactor, the hydrogen partial pressure is 0.1 to 100 psi, or the hydrogen concentration is 1 to 30,000 ppm by weight or less;
ii) Alpha-olefin monomers having 3 to 24 carbon atoms are present in 10% or more by volume based on the total volume of catalyst / activator / alkyl aluminum compound solution, monomer and total diluent or solvent in the reactor;
iii) provided that no ethylene is present in excess of 40% by weight of the monomer feed olefin composition entering the reactor.

In a preferred embodiment, the present invention relates to a process for producing a liquid polyalphaolefin having a KV ₁₀₀ of 20 cSt or greater,
a) In the reaction zone, in the presence of hydrogen (preferably 10 to 10,000 ppm hydrogen by weight), one or more C3 to C20 alpha olefin monomers containing no more than 40% by weight of ethylene, with non-coordinating anions and transitions Contacting the metal compound, the transition metal compound comprising:

With the chemical formula
Where M is a Group 4 metal;
Each X is independently hydrogen, halogen, hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, silylcarbyl radical, substituted silylcarbyl radical, germylcarbyl radical, or substitution A germylcarbyl radical; or both X are linked and bind to a metal atom to form a metal ring structure containing from about 3 to about 20 carbon atoms; or both X are olefins, diolefins or aligned ligands. May be;
R ¹ to R ¹⁰ are each independently a radical group that is hydrogen, heteroatom, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, provided that 1) at least one of R ¹ to R ⁵ One is not hydrogen or an iso-alkyl group, and at least one of R ⁶ to R ¹⁰ is not hydrogen or isoalkyl, or 2) at least two of R ¹ to R ⁵ are not hydrogen, or 3) R ¹ To R ⁵ are not hydrogen, and at least two of R ⁶ to R ¹⁰ are not hydrogen, and any two adjacent R ¹ to R ⁵ are C4 to C20 cyclic or polycyclic Any two of the adjacent R ⁶ to R ¹⁰ groups may form a C4 to C20 cyclic or polycyclic subpart,
Optionally a co-activator, R ¹ R ² R ³ M, where M is aluminum or boron, and R ¹ , R ² and R ³ are the same or different Cl to C24 hydrocarbyl radicals and are trialkylaluminums A trialkyl boron compound or a mixture of different compounds. Here, continuous means a system that operates (or is scheduled to operate) without interruption or pause. For example, a continuous process that produces a polymer refers to a process in which reactants (eg, monomers and catalyst components and / or poison scavengers) are continuously introduced into the reactor and the polymer product is continuously removed. . Semi-continuous refers to a process in which the system is operated (or scheduled to operate) with periodic interruptions. For example, a semi-continuous process for producing a polymer is like a process in which reactants (eg, monomers and catalyst components and / or scavengers) are continuously introduced into one or more reactors and the polymer product is intermittently removed. Say things.

Batch processes are not continuous or semi-continuous processes. In a preferred embodiment of the invention, the oligomerization reaction temperature is controlled by several methods, such as continuous or semi-continuous operation, heat removal, catalyst feed rate, or addition of raw materials, or addition of solvent. Since catalyst solutions, feed olefins and / or solvents, and / or scavengers are usually added at room or atmospheric temperature, or previously cooled to the desired temperature, their addition to the reactor softens the heat of reaction and Helps maintain a constant reaction temperature. This mode of operation is usually in the range of 20 ° C. of the desired reaction temperature, usually in the range of 10 ° C., preferably in the range of 5 ° C., preferably in the range of 3 ° C., preferably in the range of 1 ° C. The temperature is controlled for a time exceeding 30 minutes, and preferably the total reaction time can be controlled.

Typically, the reactor contains a small amount of initiator and is preheated to within 10 ° C. of the desired reaction temperature during semi-continuous operation. This initiator may be a raw olefin, catalyst component, solvent or polyalpha-olefin heels from a previous run or a polyalphaolefin product from a previous run or any other suitable liquid. Typically, a portion of the raw olefin, solvent or the remainder of the previous run PAO or the previous run PAO product is a more preferred starter. When the reactor is at the desired temperature, the raw olefin, catalyst component, selected amount of hydrogen, solvent and other components may be added continuously at a selected rate. Some or all of the intended amount of co-activator or scavenger may be added to the starting liquid. Or optionally, some or all of the co-activator or scavenger can be added to the feed olefin or solvent stream to maximize effectiveness. When the polymerization reaction starts at the reaction temperature, heat is released. In order to keep the reaction temperature as constant as possible, it is removed by several methods described in the literature or generally known. One possible method for heat removal is to exchange heat by pumping this side stream through a heat exchanger and slightly cooling the side stream and pumping it back to the reaction zone. The reactor is continuously circulated through the flow of reactor contents. This circulation rate and the cooling rate of this side stream can be used to effectively control the temperature of the reaction zone. Alternatively, if the reaction rate is not high enough to maintain the reaction temperature, external heat is supplied to the reactor to maintain the desired temperature. Another method for keeping the reactor temperature constant is to control the feed rate of the raw olefin or solvent and the temperature of the raw olefin or solvent. After the reactant addition is complete, the reaction is continued for the desired time to obtain the highest feed olefin conversion.

In continuous operation mode, operation is similar to semi-continuous operation. However, once the reactor is filled to a predetermined level, a predetermined amount of reaction product mixture is withdrawn from the reactor, but the addition of all components continues.

The rate of raw material addition and the amount of reaction product removed from the reactor determine the reaction time or residence time. This may be predetermined in order to obtain high reactor throughput for high feed olefin conversion and economic operation.

This process requires a balance of several factors for optimal results. First, there is a selection of catalyst components. Non-bridged, substituted metallocenes activated by non-coordinating anions (NCAs) with small amounts of trialkylaluminum are effective catalysts. The metallocene component may be dihalide or dialkyl. However, the dialkyl form of the metallocene is usually an activating chemical component that interacts with the NCA activator to create an active catalyst. When metallocene dihalides are used, it is usually necessary to add a trialkylaluminum or other alkyl reagent to convert the dihalide form to the dialkyl form. In this case, the molar ratio of trialkylaluminum to metallocene may be any of 4 to 4000, and preferably 8 to 500. When metallocene dialkyl is used (for example,
bis (tetrahydroindenyl) zirconium dimethyl)
(bis (tetrahydroindenyl) zirconium dimethyl),
bis (1,2-dimethylcyclopentadienyl) zirconium dimethyl)
(bis (1,2-dimethylcyclopentadienyl) zirconium dimethyl),
bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl)
(bis (1,3-dimethylcyclopentadienyl) zirconium dimethyl),
bis (1,2,4-trimethylcyclopentadienyl) zirconium dimethyl)
(bis (1,2,4-trimethylcyclopentadienyl) zirconium dimethyl),
bis (tetramethylcyclopentadienyl) zirconium dimethyl)
(bis (tetramethylcyclopentadienyl) zirconium dimethyl), or
bis (methyl-3-n-butylcyclopentadienyl) zirconium dimethyl)
A small amount of trialkylaluminum (such as bis (methyl-3-n-butycyclopentadienyl) zirconium dimethyl) or many other dialkylmetallocenes) is used to create optimum catalyst productivity. In this case, the molar ratio of trialkylaluminum to metallocene is usually 2 to 500, preferably 3 to 200, more preferably 3 to 100 or 3 to 10. The amount of NCA is also important. The molar ratio of metallocene to NCA can range from 10 to 0.1. A more preferred molar ratio of metallocene to NCA is about 1: 1 or 0.5: 2.

Furthermore, the metallocene concentration is also important. In order to maximize maximum catalyst productivity, high selectivity to a range of lubricant products and the best temperature, operability, the preferred amount of metallocene per olefin feedstock is from 1 microgram (or 0.001 milligram) to 1 It is in the milligram range. If the amount of catalyst component used is too large, temperature control becomes difficult, product selectivity is adversely affected, and catalyst costs can be uneconomical.

The amount of hydrogen present in the reactor is also important. Usually, the smaller the amount of hydrogen, the better.

The hydrogen head pressure is usually less than 300 psi, preferably less than 50 psi, preferably less than 30 psi, preferably less than 20 psi, preferably less than 10 psi. Alternatively, the amount of hydrogen in the feed composition should be present at a concentration of 1 ppm to 30,000 ppm, preferably 10 to 10,000 ppm, preferably 10 to 1,000 ppm. Usually, low hydrogen pressure is maintained to boost activity. Surprisingly, it has been found that the hydrogen present in the reaction medium does not readily hydrogenate the starting alpha-olefin feed to the corresponding alkane at low hydrogen pressure or hydrogen concentration levels. In fact, it has been found that when hydrogen is present in the reaction medium, the productivity of the catalyst is greatly increased. This also produces olefinic polymers with high vinylidene content in the presence of low levels of hydrogen, which can then be functionalized by known methods, as described in US Pat. No. 6,043,401. This is desirable because it can be done. Accordingly, it is preferred to maintain the reactor hydrogen pressure below 300 psi, more preferably below 100 psi, preferably below 50 psi, preferably below 25 psi, preferably below 10 psi. The low hydrogen pressure is not only advantageous for producing unsaturated polymers, but is also important for minimizing the rate at which the feedstock is hydrogenated to low-value alkanes. Similarly, it is desirable that the amount of hydrogen be minimal, and preferred hydrogen should be present at least 1 psi, preferably at least 5 psi.

Usually it is practical to add 5 to 100 psi of hydrogen to the reactor.

The reaction time or residence time also affects the conversion rate of the raw olefin. Usually, the longer the reaction time or the longer the residence time, the higher the conversion rate of the raw material olefin. However, in order to balance the high conversion rate and the high capacity of the reactor, the reaction time or residence time is usually 1 minute to 30 hours, more preferably 5 minutes to 16 hours, and 10 minutes to 10 hours. Total residence time can be achieved using a single reactor, or a series of cascade or parallel reactors, or by controlling the feed rate of the reactants.

Select the metallocene activated by NCA and / or co-activator and use the amount of catalyst used, appropriate amount of trialkylaluminum as co-activator or scavenger, and the reaction operation including residence time or reaction time and hydrogen amount By selecting the conditions, polyalphaolefins are produced with a high catalyst productivity of more than 1.5 kg per metallocene per gram used. This high productivity makes the process economically and commercially attractive.

After the reaction is completed in semi-continuous or batch operation, or the product is removed from continuous operation, the crude product should add a small amount of oxygen, carbon dioxide, air, water, alcohol, acid or any other catalyst poison. It can be worked up by deactivating the catalyst by washing with dilute sodium hydroxide or hydrochloric acid solution and water and separating the organic layer. The organic layer usually contains unreacted olefin, olefin oligomer and solvent. The product fraction can be separated from the solvent and unreacted initiator olefins by distillation or other methods known in the art. These product fractions usually have one unsaturated double bond per molecule. The double bond is most often vinylidene and some of the remainder of the olefin is a 1,2-2 substituted or trisubstituted olefin. These olefins may be further functionalized or added to other functional liquids by well-known olefin functionalization reactions, for example, alkylation with CO / H ₂ etc. via aromatic compounds, maleic anhydride, hydroformylation reactions, etc. Suitable for functionalization. Residual fraction, which usually has little or no light hydrocarbons with less than 24 carbons, but if the residual fraction has a bromine number less than 2, it can be used as a lubricant-based feed or a high performance fluid. May be used. If the bromine number is greater than 2, it can be easily hydrogenated by a conventional lubricant hydrorefining process and converted to a fully saturated paraffin fluid with a bromine number less than 2, usually considerably less than 2. Usually, a lower bromine number is preferred because it means better oxidation stability. These hydrogenated, saturated hydrocarbon paraffins are used as high performance lubricant base materials or as high performance liquids after conditioning. Typical lubricants or functional fluid preparations are described in the following books and references cited therein: “Synthetic Lubricants and High-Performance Functional Fluids”, 2nd edition, LR Rudnick and Edited by RL Shubkin, Marcel Dekker, Inc., NY 1999.

Alternatively, the crude product obtained from the polymerization reactor can be finished by using a solid adsorbent to absorb the catalyst and scavenger components and components containing any other heteroatoms. This is the preferred method and is used in the examples below. In this method, the catalyst deactivator described above is added to the crude reaction, followed by the solid absorbent. Or alternatively, a solid absorbent such as, for example, alumina, acidic clay, Celite®, or any other known filter aid is added to the crude product. The slurry is agitated for a pre-set time, usually more than 5 minutes. The solid is then filtered and the filtrate is further distilled or fractionated. This method is described in more detail in copending patent application 60 / 831,995 filed July 19, 2006.

In another embodiment, the process further comprises contacting the PAO produced according to the present invention with hydrogen and a hydrogenation catalyst under typical hydrogenation conditions to produce a nearly saturated paraffinic PAO. .

Metallocene Catalyst Compounds In the context of the present invention and claims, “hydrocarbyl radical”, “hydrocarbyl” and “hydrocarbyl group” are used interchangeably throughout this specification. Similarly, “group”, “radical” and “substituent” are used interchangeably throughout this specification. In the context of the disclosure purpose, a “hydrocarbyl radical” is defined as a C ₁ -C ₁₀₀ radical and may be linear, branched or cyclic. When cyclic, the hydrocarbon radical may be aromatic or non-aromatic. “Hydrocarbon radical” is defined to include substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, silylcarbyl radicals, and germylcarbyl radicals, as these terms are defined below. A substituted hydrocarbyl radical is a radical in which at least one hydrogen atom is replaced by at least one functional group, such as NR * ₂ , OR *, SeR *, TeR *, PR * ₂ , AsR * ₂ , SbR * ₂ , SR *, BR * ₂ , SiR * ₃ , GeR * ₃ , SnR * ₃ , PbR * _3, etc., or at least one non-hydrocarbon atom or group is inserted into the hydrocarbyl radical A non-hydrocarbon atom or group is for example
-O-, -S-, -Se-, -Te-, -N (R *)-, = N-, -P (R *)-, = P-, -As (R *)-, = As -, -Sb (R *)-, = Sb-, -B (R *)-, = B-, -Si (R *) ₂ -,-Ge (R *) _2- , -Sn (R *) _2- , -Pb (R *) ₂ -etc.
R * is independently a hydrocarbyl, or hydrocarbyl radical, and two or more R * are linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic ring or polycyclic ring structure.

A hydrocarbyl radical is a radical in which one or more hydrocarbyl hydrogen atoms are replaced with at least one halogen (eg, F, Cl, Br, I) or a halogen-containing group (eg, CF ₃ ).

Substituted halocarbyl radicals are those in which at least one halocarbyl hydrogen or halogen atom has at least one functional group such as NR * ₂ , OR *, SeR *, TeR *, PR * ₂ , AsR * ₂ , SbR * ₂ , Substituted by SR *, BR * ₂ , SiR * ₃ , GeR * ₃ , SnR * 3, PbR * _3, etc. or at least one non-carbon atom or group is inserted into a halocarbyl radical, for example , -O-, -S-, -Se-, -Te-, -N (R *)-, = N-, -P (R *)-, = P-, -As (R *)-, = As-, -Sb (R *)-, = Sb-, -B (R *)-, = B-, -Si (R *) ₂ -,-Ge (R *) _2- , -Sn (R * ) _2- , -Pb (R *) _2- and the like, wherein R is independently a hydrocarbyl or halocarbyl radical, provided that at least one halogen atom remains in the original halocarbyl radical. Condition. Furthermore, two or more R * may be linked to form a substituted or unsubstituted saturated, partially unsaturated or aromatic ring or polycyclic structure.

A silylcarbyl radical (also referred to as silylcarbyl) is a group in which the silyl functional group is directly bonded to one or more indicated atoms. In this example, SiH ₃ , SiH ₂ R *, SiHR * ₂ , SiR * ₃ , SiH ₂ (OR *), SiH (OR *) ₂ , Si (OR *) ₃ , SiH ₂ (NR * ₂ ), SiH (NR * ₂ ) ₂ , Si (NR * ₂ ) ₃ , etc., R is independently a hydrocarbyl or halocarbyl radical, and two or more R * are linked to a substituted or unsubstituted saturated, partially unsubstituted Saturated or aromatic rings or polycyclic structures may be formed.

A germylcarbyl radical (also referred to as germylcarbyl) is a group in which a germyl functional group is bonded directly to one or more of the indicated atoms. Examples include GeH ₃ , GeH ₂ R *, GeHR * ₂ , GeR ⁵ ₃ , GeH ₂ (OR *), GeH (0R *) ₂ , Ge (OR *) ₃ , GeH ₂ (NR * ₂ ), GeH (NR * ₂ ) ₂ , Ge (NR * ₂ ) ₃ , R is independently a hydrocarbyl or halocarbyl radical, and two or more R * are linked to substituted or unsubstituted saturated, partially unsaturated Or an aromatic ring or a polycyclic ring structure may be formed.

A polar radical or group of polar groups is a group in which the heteroatom functional group is directly bonded to one or more of the indicated atoms. This includes heteroatoms of group 1-17 of the periodic table (excluding carbon and hydrogen) that are bonded to other elements either alone or by covalent or ionic bonds, van der Waals forces or hydrogen bonds. . Examples containing functional heteroatoms include carboxylic acids, acid halides, carboxylic esters, carboxylates, carboxylic anhydrides, aldehydes and their chalcogen (group 14) analogs, alcohols and phenols, ethers, peroxides and Hydrogen peroxide, carboxylic acid amides, hydrazides and imides, amidines and other nitrogen analogues of nitriles, amines and imines, azo groups (azos), nitro groups (nitros), other nitrogen compounds, sulfur-containing acids, selenium Includes acids, thiols, sulfides, sulfoxides, sulfones, phosphines, phosphates, other phosphorus compounds, silanes, boranes, borates, alanes, aluminates. Functional groups may also be considered broadly including organic polymeric supports or inorganic support materials such as alumina and silica. Preferred examples of polar groups include NR * ₂ , OR *, SeR *, TeR *, PR * ₂ , AsR * ₂ , SbR * ₂ , SR *, BR * ₂ , SnR * ₃ , PbR * _3, etc. R is independently a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl radical as defined above, and the two R * s are linked to a substituted or unsubstituted saturated, partially unsaturated or aromatic ring or polycyclic It may form a formula structure.

The terms "substituted or unsubstituted cyclopentadienyl ligand", "substituted or unsubstituted indenyl ligand", "substituted or unsubstituted fluorenyl ligand" and "substituted or unsubstituted tetrahydroindenyl ligand" , The substituent of the ligand may be hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl. Substituents may also be in cyclic structures with heterocyclopentadienyl, heteroindenyl, heterofluorenyl, or heterotetrahydroindenyl ligands, and these Each may be further substituted or unsubstituted.

In some embodiments, the hydrocarbyl radical is independently selected from: methyl, ethyl, ethenyl, and isomers of: propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, propenyl, butenyl Heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl , Octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, decocenyl, tricosenyl, tetracocenyl, pentacocenyl, hexacocenyl, heptacosenyl, octacocenyl, nonacosenyl, triaconenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octenyl, decynyl, octenyl Tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecinyl, octadecynyl, nonadecynyl, eicosinyl, heneicosinyl, docosinyl, tricosinyl, tetracosinyl, pentacosinyl, hexacosinyl, heptacoynyl, octacosinyl, nonaconyl, triaconyl, diethaconyl Nil, nonadienyl, and decadienyl. Also included are isomers of saturated, partially unsaturated and aromatic and polycyclic structures, in which case the radicals can undergo the types of substitution described above. Examples of these include phenyl, methylphenyl, dimethylphenyl, ethylphenyl, diethylphenyl, propylphenyl, dipropylphenyl, benzyl, methylbenzyl, naphthyl, anthracenyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, cyclohexane Including heptyl, cycloheptenyl, norbornyl, norbornenyl, adamantyl and the like. In this specification, when a radical is described, the radical species, and if the radical species is substituted as defined above, the radical species and all other other formed species. The radical of The described alkyl, alkenyl, and alkynyl radicals include all isomers, including cyclic isomers, where applicable, for example, butyl is n-butyl, 2-methylpropyl, 1-methylpropyl, tert- Butyl and cyclobutyl (and similarly substituted cyclopropyl); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, and neopentyl (and similarly substituted cyclobutyl and cyclopropyl) Butenyl includes 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl (and cyclobutenyl and cyclopropenyl) ) In the form of E and Z; Cyclic compounds include all isomeric forms, for example, methylphenyl includes orthomethylphenyl, meta-methylphenyl, para-methylphenyl, dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5 -Dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl may be included. Examples of cyclopentadienyl and indenyl ligands are described below as part of the ligand.

“Ring structure carbon atom” refers to a carbon atom that is part of a cyclic structure. In this definition, indenyl ligands have 9 cyclic carbon atoms; cyclopentadienyl ligands have 5 cyclic carbon atoms and fluorenyl ligands have 13 carbon atoms. Thus, indene corresponds to a Cp cyclic structure having two alkyl radical substituents, and fluorene corresponds to a Cp cyclic structure having four alkyl radical substituents. Furthermore, the cyclic structure may also be hydrogenated, for example, di-hydro- or tetra-hydro-indenyl ligands, di-hydro or tetra-hydro or octa-hydro-fluorenyl ligands are preferred. is there.

The metallocene compound (precatalyst) useful in the present invention is preferably a cyclopentadienyl derivative of titanium, zirconium and hafnium. Generally useful titanocene, zirconocene and hafnocene have the following chemical formula:
(CpCp ^* ) MX ₁ X ₂ (2)
Represented by
Where M is a metal center and is a Group 4 metal, preferably titanium, zirconium or hafnium, preferably zirconium or hafnium.

Cp and Cp * are the same or different cyclopentadienyl rings each bonded to M, 1) Cp and C are both substituted with at least one non-isoalkyl substituent, or 2) Cp is 2 to 5 And preferably both Cp and Cp * are substituted with 2 to 5 substituents R, wherein each substituent R is independently hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, A radical group that is silylcarbyl, or germylcarbyl, or Cp and Cp * and any adjacent two R * groups are optionally linked to a substituted or unsubstituted saturated, partially saturated or aromatic ring or The same or different cyclopentadienyl which may form a polycyclic substituent.

X ₁ and X ₂ are independently hydrogen, halogen, hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, silylcarbyl radical, substituted silylcarbyl radical, germylcarbyl radical Or both X are linked and bonded to a metal atom to form a metal ring structure containing about 3 to about 20 carbon atoms; or both X are olefins, diolefins or aligned A rank may be used.

Table A shows representative subsections that make up the metallocene component of Formula 2. This table is for illustrative purposes only and should not be construed as limiting its scope in any way. The possible combinations of each component and the other parts form a number of final components. Where hydrocarbyl radicals are disclosed, including alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl and aromatic radicals, these terms include all of its isomers.

For example, butyl includes n-butyl, 2-methylpropyl, tert-butyl and cyclobutyl; pentyl includes n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, neopentyl, cyclopentyl, and methyl Butenyl includes 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl E and Including the shape of Z;
This includes the case where radicals are bonded to other groups. For example, propylcyclopentadienyl includes n-propylcyclopentadienyl, isopropylcyclopentadienyl and cyclopropylcyclopentadienyl.

Usually, the ligands or groups shown in Table A include all isomers. For example, dimethylcyclopentadienyl includes 1,2-dimethylcyclopentadienyl and 1,3-dimethylcyclopentadienyl; methylindenyl includes 1-methylindenyl, 2-methylindenyl, 3- Including methylindenyl, 4-methylindenyl, 5-methylindenyl, 6-methylindenyl, and 7-methylindenyl; methylethylphenyl is orthomethylethylphenyl, metamethylethylphenyl, paramethylethylphenyl including. In order to obtain a member of the transition metal component, the types described in Table A may be arbitrarily selected and combined.

Table A
M: Titanium, zirconium, hafnium Cp, Cp *:
Methylcyclopentadienyldimethylcyclopentadienyltrimethylcyclopentadienyltetramethylcyclopentadienylethylcyclopentadienyldiethylcyclopentadienylpropylcyclopentadienyldipropylcyclopentadienylbutylcyclopentadienyldibutylcyclopenta Dienylpentylcyclopentadienyldipentylcyclopentadienylhexylcyclopentadienyldihexylcyclopentadienylheptylcyclopentadienyldiheptylcyclopentadienyloctylcyclopentadienyl dioctylcyclopentadienylnonylcyclopentadienyl Dinonylcyclopentadienyldecylcyclopentadienyldidecylcyclopentadienylundecylcyclopentadienyldodecylcyclo Ntadienyltridecylcyclopentadienyltetradecylcyclopentadienylpentadecylcyclopentadienylhexadecylcyclopentadienylheptadecylcyclopentadienyloctadecylcyclopentadienylnonadecylcyclopentadienyleicosylcyclopentadienyl Heneicosyl cyclopentadienyl docosyl cyclopentadienyl tricosyl cyclopentadienyl tetracosyl cyclopentadienyl pentacosyl cyclopentadienyl hexacosyl cyclopentadienyl heptacosyl cyclopentadienyl octacosyl Clopentadienyl nonacosyl cyclopentadienyl triacontyl cyclopentadienyl cyclohexacyclopentadienyl phenyl cyclopentadienyl diphenyl cyclopentadieni Triphenylcyclopentadienyltetraphenylcyclopentadienyltolylcyclopentadienylbenzylcyclopentadienylphenethylcyclopentadienylcyclohexylmethylcyclopentadienylnaphthylcyclopentadienylmethylphenylcyclopentadienylmethyltolylcyclopentadienyl Methylethylcyclopentadienylmethylpropylcyclopentadienylmethylbutylcyclopentadienylmethylpentylcyclopentadienylmethylhexylcyclopentadienylmethylheptylcyclopentadienylmethyloctylcyclopentadienylmethylnonylcyclopentadi Enylmethyldecylcyclopentadienylvinylcyclopentadienylpropenylcyclopentadienylbutenylcyclopentadienyl Indenylmethyl indenyl dimethyl indenyl trimethyl indenyl tetramethyl indenyl pentamethyl indenyl methyl propyl indenyl dimethyl propyl indenyl methyl dipropyl indenyl methyl ethyl indenyl methyl butyl indenyl ethyl indenyl propyl indenyl butyl indenyl pentyl Indenyl hexyl indenyl heptyl indenyl octyl indenyl nonyl indenyl decyl indenyl phenyl indenyl (fluorophenyl) indenyl
(Methylphenyl) indenylbiphenylindenyl (bis (trifluoromethyl) phenyl) indenylnaphthylindenylphenanthrylindenylbenzylindenylbenzindenylcyclohexylindenylmethylphenylindenylethylphenylindenylpropylphenylindenylmethyl Naphthyl indenyl ethyl naphthyl indenyl propyl naphthyl indenyl (methylphenyl) indenyl (dimethylphenyl) indenyl (ethylphenyl) indenyl (diethylphenyl) indenyl (propylphenyl) indenyl (dipropylphenyl) indenylmethyl tetrahydroindenyl ethyl tetrahydroindenyl Nylpropyltetrahydroindenylbutyltetrahydroindenylphenyltetrahydroindenyl Phenylmethyl) cyclopentadienyltrimethylsilylcyclopentadienyltriethylsilylcyclopentadienyltrimethylgermylcyclopentadienylcyclopenta [b] thienylcyclopenta [b] furanylcyclopenta [b] selenophenylcyclopenta [b] Tellurophenylcyclopenta [b] pyrrolylcyclopenta [b] phosphorylcyclopenta [b] arsolylcyclopenta [b] stivylmethylcyclopenta [b] thienylmethylcyclopenta [b] furanylmethylcyclopenta [b] seleno Phenylmethylcyclopenta [b] tellurophenylmethylcyclopenta [b] pyrrolylmethylcyclopenta [b] phosphorylmethylcyclopenta [b] arsylmethylcyclopenta [b] stivyldimethylcyclopenta [b] thienyldimethylcyclo Penta [b] furanyldimethylcyclopenta [b] pi Ryldimethylcyclopenta [b] phosphoryltrimethylcyclopenta [b] thienyltrimethylcyclopenta [b] furanyltrimethylcyclopenta [b] pyrrolyltrimethylcyclopenta [b] phosphorylethylcyclopenta [b] thienylethylcyclopenta [b ] Furanylethylcyclopenta [b] pyrrolylethylcyclopenta [b] phosphoryldiethylcyclopenta [b] thienyldiethylcyclopenta [b] furanyldiethylcyclopenta [b] pyrrolyldiethylcyclopenta [b] phosphoryltriethylcyclo Penta [b] thienyltriethylcyclopenta [b] furanyltriethylcyclopenta [b] pyrrolyltriethylcyclopenta [b] phosphorylpropylcyclopenta [b] thienylpropylcyclopenta [b] furanylpropylcyclopenta [b] pyrrole Rupropylcyclopenta [b] phosphoryldipropyl Clopenta [b] thienyldipropylcyclopenta [b] furanyldipropylcyclopenta [b] pyrrolyldipropylcyclopenta [b] phosphoryltripropylcyclopenta [b] thienyltripropylcyclopenta [b] furanyltripropylcyclopenta [b] b] pyrrolyltripropylcyclopenta [b] phosphorylbutylcyclopenta [b] thienylbutylcyclopenta [b] furanylbutylcyclopenta [b] pyrrolylbutylcyclopenta [b] phosphoryldibutylcyclopenta [b] thienyldibutylcyclo Penta [b] furanyldibutylcyclopenta [b] pyrrolyldibutylcyclopenta [b] phosphoryltributylcyclopenta [b] thienyltributylcyclopenta [b] furanyltributylcyclopenta [b] pyrrolyltributylcyclopenta [b] Phosphorylethylmethylcyclopenta [b] thienylethylmethy Rucyclopenta [b] furanylethylmethylcyclopenta [b] pyrrolylethylmethylcyclopenta [b] phosphorylmethylpropylcyclopenta [b] thienylmethylpropylcyclopenta [b] furanylmethylpropylcyclopenta [b] pyrrolylmethyl Propylcyclopenta [b] phosphorylbutylmethylcyclopenta [b] thienylbutylmethylcyclopenta [b] furanylbutylmethylcyclopenta [b] pyrrolylbutylmethylcyclopenta [b] phosphorylcyclopenta [c] thienylcyclopenta [ c] furanylcyclopenta [c] selenophenylcyclopenta [c] tellurophenylcyclopenta [c] pyrrolylcyclopenta [c] phosphorylcyclopenta [c] arsylcyclopenta [c] stivylmethylcyclopenta [c] Thienylmethylcyclopenta [c] furanylmethylcyclopenta [c] selenophenylmeth Cyclopenta [c] tellurophenylmethylcyclopenta [c] pyrrolylmethylcyclopenta [c] phosphorylmethylcyclopenta [c] arsolylmethylcyclopenta [c] stivolyldimethylcyclopenta [c] thienyldimethylcyclopenta [c ] Furanyldimethylcyclopenta [c] pyrrolyldimethylcyclopenta [c] phosphoryltrimethylcyclopenta [c] thienyltrimethylcyclopenta [c] furanyltrimethylcyclopenta [c] pyrrolyltrimethylcyclopenta [c] phosphorylethylcyclo Penta [c] thienylethylcyclopenta [c] furanylethylcyclopenta [c] pyrrolylethylcyclopenta [c] phosphoryldiethylcyclopenta [c] thienyldiethylcyclopenta [c] furanyldiethylcyclopenta [c] pyrrole Rudiethylcyclopenta [c] phosphoryltriethylcyclopenta [c] thieni Triethylcyclopenta [c] furanyltriethylcyclopenta [c] pyrrolyltriethylcyclopenta [c] phosphorylpropylcyclopenta [c] thienylpropylcyclopenta [c] furanylpropylcyclopenta [c] pyrrolylpropylcyclopenta [ c] phosphoryldipropylcyclopenta [c] thienyldipropylcyclopenta [c] furanyldipropylcyclopenta [c] pyrrolyldipropylcyclopenta [c] phosphoryltripropylcyclopenta [c] thienyltripropylcyclopenta [c] Furanyltripropylcyclopenta [c] pyrrolyltripropylcyclopenta [c] phosphorylbutylcyclopenta [c] thienylbutylcyclopenta [c] furanylbutylcyclopenta [c] pyrrolylbutylcyclopenta [c] phosphoryldibutylcyclopenta [c] thienyldibutylcyclopenta [c] furanyldibu Tylcyclopenta [c] pyrrolyldibutylcyclopenta [c] phosphoryltributylcyclopenta [c] thienyltributylcyclopenta [c] furanyltributylcyclopenta [c] pyrrolyltributylcyclopenta [c] phosphoryl

Ethylmethylcyclopenta [c] thienylethylmethylcyclopenta [c] furanylethylmethylcyclopenta [c] pyrrolylethylmethylcyclopenta [c] phosphorylmethylpropylcyclopenta [c] thienylmethylpropylcyclopenta [c] fura Nylmethylpropylcyclopenta [c] pyrrolylmethylpropylcyclopenta [c] phosphorylbutylmethylcyclopenta [c] thienylbutylmethylcyclopenta [c] furanylbutylmethylcyclopenta [c] pyrrolylbutylmethylcyclopenta [c Phosphorylpentamethylcyclopentadienyltetrahydroindenylmethyltetrahydroindenyldimethyltetrahydroindenyl In one preferred embodiment of the invention, when used with NCA, Cp is the same as Cp * and substituted cyclopentadienyl , Indenyl or tetrahi It is a Roindeniru ligand.

Preferred metallocene compounds (precatalysts) in the present invention provide a catalyst system specific for the production of PAO greater than 20 cSt, including:
bis (1,2-dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride)
bis (1,3-Dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride)
bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dichloride)
bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride)
bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride)
bis (l, 2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride)
bis (l-Methyl-2-ethylcyclopentadienyl) zirconium dichloride
(bis (l -methyl -2-ethylcyclopentadienyl) zirconium dichloride)
bis (l-methyl-2-n-propylcyclopentadienyl) zirconium dichloride
(bis (l-methyl-2-n-propylcyclopentadienyl) zirconium dichloride)
bis (l-methyl-2-n-butylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-2-n-butyllcyclopentadienyl) zirconium dichloride)
bis (l-Methyl-3-n-ethylcyclopentadienyl) zirconium dichloride
(bis (l-methyl-3-ethylcyclopentadienyl) zirconium dichloride)
bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-3-n-propylcyclopentadienytyzirconium dichloride)
bis (l-Methyl-3-n-butylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-3-n-butylcyclopentadienytyzirconium dichloride)
bis ((l-methyl-3-n-pentylcyclopentadienyl) zirconium dichloride
(bis (l-methyl-3-n-pentylcyclopentadienyl) zirconium dichloride)
bis (l, 2-dimethyl-4-ethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethyl-4-ethylcyclopentadienyl) zirconium dichloride)
bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) zirconium dichloride)
bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) zirconium dichloride)
bis (l, 2-diethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-diethylcyclopentadienyl) zirconium dichloride)
bis ((l, 3-diethylcyclopentadienyl) zirconium dichloride
(bis (l, 3-diethylcyclopentadienyl) zirconium dichloride)
bis (l, 2-di-n-propylcyclopentadienyl) zirconium dichloride
(bis (l, 2-di-n-propylcyclopentadienyl) zirconium dichloride)
bis (l, 2-di-n-butylcyclopentadienyl) zirconium dichloride
(bis (1,2-di-n-butylcyclopentadienyl) zirconium dichloride)
bis (1-Methyl-2,4-diethylcyclopentadienyl) zirconium dichloride
bis (1-methyl-2,4-diethylcyclopentadienyl) zirconium dichloride)
(bis (1,2-diethyl-4-n-propylcyclopentadienyl) zirconium dichloride
bis (1,2-diethyl-4-n-propylcyclopentadienyl) zirconium dichloride)
(bis (1,2-diethyl-4-n-butylcyclopentadienyl) zirconium dichloride
bis (l, 2-diethyl-4-n-butylcyclopentadienytyzirconium dichloride)
(bis (l-methyl-3-i-propylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-3-i-propylcyclopentadienyl) zirconium dichloride)
bis (l-ethyl-3-i-propylcyclopentadienyl) zirconium dichloride
(bis (l -ethyl -3-i-propylcyclopentadienyl) zirconium dichloride)
(1,2-Dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride
((l, 2-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride)
(1,3-Dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride
((1, 3-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride)
(1, 2-Dimethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride
((1, 2-dimethylcyclopentadienyl) (methylcyclopentadienyl) zirconiurn dichloride)
(1,2-Dimethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride
((1,2-dimethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride)
(1,2-Dimethylcyclopentadienyl) ((l, 2-di-n-butylcyclopentadienyl) zirconium dichloride
((1,2-dimethylcyclopentadienyl) (l, 2-di-n-butylcyclopentadienyl) zirconium dichloride)
(1,3-Dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride
((l, 3-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride)
(1,3-Dimethylcyclopentadienyl) (1,2-dimethylcyclopentadienyl) zirconium dichloride
((l, 3-dimethylcyclopentadienyl) (l, 2-dimethylcyclopentadienyl) zirconium dichloride)
(1,3-Dimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) zirconium dichloride
((1,3-dimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) zirconium dichloride)
bis (indenyl) zirconium dichloride
(bis (indenyl) zirconium dichloride)
bis (1-methylindenyl) zirconium dichloride
(bis (l -methylindenyl) zirconium dichloride)
bis (2-methylindenyl) zirconium dichloride
bis (4-methylindenyl) zirconium dichloride
bis (4,7-dimethylindenyl) zirconium dichloride
bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride
(bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride)
bis (4,5,6,7-tetrahydro-2-methylindenyl) zirconium dichloride (bis (4,5,6,7-tetrahydro-2-methylindenyl) zirconium dichloride)
bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) zirconium dichloride (bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) zirconium dichloride)
(Cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) zirconium dichloride
(cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) zirconium dichloride)
Preferred catalysts also include dihalogenated, dimethyl, diisobutyl, di-n-octyl or other dialkyl analogs of the above compounds zirconium and dichloride, hafnium dihalide, or dimethyl or dialkyl analogs of the above compounds.

Particularly preferred catalyst compounds include:
bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride),
bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride),
bis (l, 2,3-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dichloride),
bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride) and
bis (tetramethylcyclopentadienyl) zirconium dichloride
(bis (tetramethylcyclopentadienyl) zirconium dichloride),
bis (l-methyl-2-ethylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-2-ethylcyclopentadienyl) zirconium dichloride),
bis (l-methyl-3-ethylcyclopentadienyl) zirconium dichloride dichloride),
bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride
(bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride),
bis (l-Methyl-3-n-butylpyrupentadienyl) zirconium dichloride
(bis (l -methyl -3-n-butylclopentadienyl) zirconium dichloride)
bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride
(bis (4,5,6,7-tetrahydro indenyl) zirconium dichloride)
bis (indenyl) zirconium dichloride
(bis (indenyl) zirconium dichloride)
bis (l, 2-dimethyl) cyclopentadienyl) zirconium dimethyl
(bis (l, 2-dimethyl) cyclopentadienyl) zirconium dimethyl)
bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl
(bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl)
bis (l, 2,3-trimethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dimethyl)
bis (l, 2,4-trimethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dimethyl) and
bis (tetramethylcyclopentadienyl) zirconium dimethyl
(bis (tetramethylcyclopentadienyl) zirconium dimethyl)
bis (1-Methyl-2-ethylcyclopentadienyl) zirconium dimethyl
(bis (1-methyl-2-ethylcyclopentadienyl) zirconium dimethyl)
bis (1-methyl-3-ethylcyclopentadienyl) zirconium dimethyl
bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dimethyl
bis (l-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl
bis (4,5,6,7-tetrahydro indenyl) zirconium dichloride
bis (indenyl) zirconium dimethyl
(bis (indenyl) zirconium dimethyl) or its diisobutyl analogue. These metallocene dialkyl components may be present in the catalyst system by using preformed metallocene as an initiator. Sometimes they exist as a reaction product of a halogenated metallocene and a trialkylaluminum compound (coactivator / scavenger).

In other embodiments, the metallocene compound is not a racemate.

The activated catalyst precursor of the activator and catalyst forms an active catalyst for the polymerization or oligomerization of olefins when activated by an activator such as a non-coordinating anionic activator. Activators used are Lewis acid activators such as triphenyl boron, tris-perfluorophenyl boron, tris-perfluorophenyl aluminum and / or dimethylanilinium, tetraxperfluorophenylborate, triphenylcarbonium tetraxperfluorophenyl Contains ionic activators such as borate, dimethylanilinium tetraxperfluorophenylaluminate and the like.

Co-activators can alkylate transition metal complexes, so that active catalysts are formed when used in combination with activators. Co-activators include alumoxanes such as methylalumoxane, modified alumoxanes such as modified methylalumoxane, and trimethylaluminum, triisobutylaluminum, triethylaluminum, and triisopropylaluminum, trien-hexylaluminum, It includes alkyl aluminums such as tree n-octyl aluminum, tree n-decyl aluminum, or tree n-dodecyl aluminum.

If the pre-catalyst is not a dihydrocarbyl or dihydride complex, the co-activator is usually used in combination with a Lewis acid activator and an ionic activator. In some cases, a co-activator is used and added as a scavenger, alone or in multiple streams, to the feed stream or catalyst stream or reactor to inactivate impurities in the feed or reactor. In many cases, even when a dialkyl form of the metallocene component is used, a small amount of co-activator is added to the catalyst system or reactor system to further enhance the effect or to trap impurities in the reaction system. Is done.

Particularly preferred coactivators include alkylaluminum compounds represented by R ₃ Al, wherein each R is independently a C1 to C18 alkyl group, preferably each R is independently
Methyl, ethyl, n-propyl, iso-propyl, iso-butyl, n-butyl, t-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl, iso-hexyl, n-heptyl, to iso- Butyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, And a group consisting of iso-analogs thereof.

Ionic activators (sometimes used in combination with co-activators) may be used in the present invention. [Me ₂ PhNH] [B (C ₆ F ₅ ) ₄ ], [Ph ₃ C] [B (C ₆ F ₅ ) ₄ ], [Me ₂ PhNH] [B ((C ₆ H ₃ -3, 5- (CF ₃ ) ₂ )) ₄ ], [Ph ₃ C] [B ((C ₆ H ₃ -3,5- (CF ₃ ) ₂ )) ₄ ], [NH ₄ ] [B (C ₆ H ₅ ) Individual ionic activators such as ₄ ] or Lewis acid activators such as B (C ₆ F ₅ ) ₃ or B (C ₆ H ₅ ) ₃ can be used, where Ph is phenyl , And Me are methyl. When a preferred co-activator is used, it may be an alumoxane such as methylalumoxane, a modified alumoxane such as modified methylalumoxane, and triisobutylaluminum, trimethylaluminum, triethylaluminum, and triisopropylaluminum, An alkyl aluminum such as tree n-hexyl aluminum, tree n-octyl aluminum, tree n-decyl aluminum, or tree n-dodecyl aluminum. Ionized or stoichiometric activator, neutral or ionized, for example, (tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate (tri (n-butyl) ammoniumtetrakis (pentafluorophenyl) borate ,
Triperfluorophenyl boron metalloid precursor (trisperfluorophenyl boron metalloid precursor) or trisperfluoronaphthylboron metalloid precursor,
It is within the scope of the present invention to use polyhalogenated heteroborane anions (WO 98/43983), boric acid (US Pat. No. 5,942,459) or combinations thereof.

Examples of neutral stoichiometric activators include trisubstituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. Each of the three substituents is independently selected from alkyl, alkenyl, halogen, substituted alkyl, aryl, aryl halide, alkoxy, halide. Preferably the three groups are independently selected from mono- or polycyclic (including halogen substituted) aryl, alkyl and alkenyl compounds and mixtures thereof, preferably alkenyl groups having 1 to 20 carbon atoms, 1 to 20 And an alkyl group having 1 to 20 carbon atoms and an aryl group having 3 to 20 carbon atoms (including substituted aryl). More preferably, the three groups are alkyl groups having 1 to 4 carbons, phenyl, naphthyl or mixtures thereof. Even more preferably, the three groups may be halogenated, preferably fluorinated, aryl groups, most preferably the neutral stoichiometric activator is triperfluorophenyl boron or triperfluoronaphthyl boron. It is.

The ionic stoichiometric activator is related to the remaining ions of the ionized compound, but may include active protons that are not coordinated or that are loosely coordinated or some other cation. Such compounds are described in European Patent Publications EP-AO 570 982, EP-AO 520 732, EP-AO 495 375, EP-Bl-O 500 944, EP-AO 277 003 and EP-AO 277 004 and U.S. Patent No. 5,153,157. No. 5,198,401, No. 5,066,741, No. 5,206,197, No. 5,241,025, No. 5,384,299 and No. 5,502,124, and US patent application Ser. No. 08 / 285,380 filed Aug. 3, 1994. All of these documents are incorporated herein by reference.

An ionic catalyst can be formed by reacting a transition metal compound with an activator such as B (C ₆ Fe ₆ ) ₃ , and the activator is formed by reacting with the hydrolyzable ligand (X ′) of the transition metal compound. Upon reaction, an anion such as ([B (C ₆ F ₅ ) 3 (X ′)] ⁻ ) is formed, which stabilizes the cationic transition metal species produced by the reaction. The catalyst can and is preferably prepared with an activator component that is an ionic compound or composition. However, it is also contemplated in the present invention to prepare the active agent using a neutral compound.

Compounds useful as activator compounds in the preparation of the ionic catalyst system used in the process of the present invention include cations, which are preferably Bronsted acids capable of donating protons and are compatible. Contains non-coordinating anions, which are relatively large (bulky), can stabilize the active catalytic species formed when the two compounds are combined, and the anions are olefinic, diolefinic And very easily substituted by acetylenically unsaturated substrates or other neutral Lewis acids such as ethers, nitriles and the like. Two types of co-existing non-coordinating anions are disclosed in EPA 277,003 and EPA 277,004 published in 1988, ie 1) covalently coordinate to the central charged metal or metalloid core and protect it An anionic coordination complex containing a plurality of fat-soluble radicals, and 2) an anion containing a plurality of boron atoms such as carborane, metal carborane, and borane. In one preferred embodiment, the stoichiometric activator comprises a cation and an anion component and is represented by the following formula: (L **-H) ^{d +} (A ^d- ), wherein L ** is medium Lewis base; H is hydrogen; (L **-H) ^{d +} is a Bronsted acid, A ^d− is a non-coordinating anion having a charge of d ⁻ , and d is an integer of 1 to 3.

Cationic component (L **-H) ^{d +} can remove Bronsted acid such as proton or protonated Lewis base or protonated, or a small portion such as alkyl, aryl from the pre-catalyst after alkylation A reducing Lewis acid may be included.

The activated cation (L **-H) ^{d +} may be a Bronsted acid, which can donate a proton to the alkylated transition metal catalyst precursor, and the precursor is a transition metal cation. Ammonium, oxonium, phosphonium, silylium, and mixtures thereof, preferably methylamine ammonium, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N, N-dimethylaniline, methyl Phosphonium, dimethyl ether, diethyl ether, tethenium from diphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine and diphenylphosphine Oxonium from ethers such as trahydrofuran and dioxane, sulfonium from thioethers such as diethyl thioether and tetrahydrothiophene and mixtures thereof may be preferred. The activated cation (L **-H) ^{d +} is also a small portion such as silver, tropylium, carbonenium, ferrocenium, and mixtures thereof, preferably carbonium and ferrocenium, most preferably triphenylcarbonium. There may be.

The anionic component A ^d− has a component having the chemical formula [M ^{k +} Q _n ] ^{d −} , where k is an integer from 1 to 3; n is an integer from 2-6; nk = d; M is a periodic rate table An element selected from group 13, wherein Q is independently hydride, bridged or unbridged dialkylamide, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, And halo-substituted hydrocarbyl radicals, provided that Q has up to 20 carbon atoms and Q is a halide with a frequency not exceeding 1. Preferably each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. Suitable A ^d-examples include diboron compounds described also U.S. Pat. No. 5,447,895. This document is incorporated herein by reference.

An example of a boron compound that can be used as an activated cocatalyst in combination with a coactivator in the production of the improved catalyst of the present invention is a trisubstituted aluminum salt, examples of which include:
Trimethylammonium tetraphenylborate
(trimethylammoniurn tetraphenylborate),
Triethylammonium tetraphenylborate
(triethylammonium tetraphenylborate),
Tripropylammonium tetraphenylborate
(tripropylammonium tetraphenylborate),
Tri (n-butyl) ammonium tetraphenylborate
(tri (n-butyl) ammonium tetraphenylborate),
Tri (tert-butyl) ammonium tetraphenylborate
(tri (tert-butyl) ammoniurn tetraphenylborate),
N, N-dimethylanilinium tetraphenylborate
(N, N-dimethylanilinium tetraphenylborate),
N, N-diethylanilinium tetraphenylborate
(N, N-diethylanilinium tetraphenylborate),
N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate
(N, N-dimethyl- (2,4,6-trimethylanilinium) tetraphenylborate),
Trimethylammonium tetrakis (pentafluorophenyl) borate
(trimethylammonium tetrakis (pentafluorophenyl) borate),
Triethylammonium tetrakis (pentafluorophenyl) borate
(triethylammonium tetrakis (pentafluorophenyl) borate),
Tripropylammonium tetrakis (pentafluorophenyl) borate
(tripropylammonium tetrakis (pentafluorophenyl) borate),
Tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate
(tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate),
Tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate
(tri (sec-butylammonium tetrakis (pentafluorophenyl) borate),
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate
(N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate),
N, N-diethylanilinium tetrakis (pentafluorophenyl) borate
(N, N-diethylanilinium tetrakis (pentafluorophenyl) borate),
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate
(N _, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate).
Trimethylammonium tetrakis- (2,3,4,6-tetra (fluorophenyl) borate
(trimethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
Triethylammonium tetrakis- (2,3,4,6-tetra (fluorophenyl) borate
(triethylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
Tripropylammonium tetrakis- (2,3,4,6-tetra (fluorophenyl) borate
(tripropylammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
Tri (n-butyl) ammonium tetrakis- (2,3,4,6-tetra (fluorophenyl) borate
(tri (n-butyl) ammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
Dimethyl (tert-butyl) ammonium tetrakis- (2,3,4,6-tetra (fluorophenyl) borate
(dimethyl (tert-butyl) ammonium tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
N, N-dimethylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate
(N, N-dimethylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
N, N-diethylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl) borate
(N, N-diethylaniliniυm tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate
(N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
Trimethylammonium tetrakis (perfluoronaphthyl) borate
(trimethylammonium tetrakis (perfluoronaphthyl) borate),
Triethylammonium tetrakis (perfluoronaphthyl) borate
(triethylammonium tetrakis (perfluoronaphthyl) borate),
Tripropylammonium tetrakis (perfluoronaphthyl) borate
(tripropylammonium tetrakis (perfluoronaphthyl) borate),
Tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate
(tri (n-butyl) ammonium tetrakis (perfluoronaphthyl) borate),
Tri (tert-butyl) ammonium tetrakis (perfluoronaphthyl) borate
(tri (tert-butyl) ammonium tetxakis (perfluoronaphthyl) borate),
N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate
(N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate),
N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate
(N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate _,
N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate
(N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluoronaphthyl) borate),
Trimethylammonium tetrakis (perfluorobiphenyl) borate
(trimethylammonium tetrakis (perfluorobiphenyl) borate),
Triethylammonium tetrakis (perfluorobiphenyl) borate
(triethylammonium tetrakis (perfluorobiphenyl) borate),
Tripropylammonium tetrakis (perfluorobiphenyl) borate
(tripropylammonium tetrakis (perfluorobiphenyl) borate),
Tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate
(tri (n-butyl) ammonium tetrakis (perfluorobiphenyl) borate),
Tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate
(tri (tert-butyl) ammonium tetrakis (perfluorobiphenyl) borate),
N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate
(N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate),
N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate
(N, N-diethylanilinium tetrakis (perfluorobiphenyl) borate) _,
N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate
(N, N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (perfluorobiphenyl) borate),
Trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(trimethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
Triethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(triethylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
Tripropylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(tripropylammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
Tri (n-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(tri (n-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
Tri (tert-butyl) ammonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(tri (tert-butyl) ammonium tetrakis (3, 5-bis (trifluoromethyl) phenyl) borate),
N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
N, N-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(N, N-diethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
N, N-dimethyl (2,4,6-trimethylanilinium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(N, N-dimethyl- (2,4,6-trimethylanilinium) (tetrakis (3,5-bis (trifluoromethyl) phenyl) borate), and dialkyl ammonium salt, for example
Di- (iso-propyl) ammonium tetrakis (pentafluorophenyl) borate
(di- (iso-propyl) ammonium tetrakis (pentafluorophenyl) borate), and dicyclohexammonium tetrakis (pentafluorophenyl) borate
(dicyclohexylammonium tetrakis (pentafluorophenyl) borate); and other salts, such as
Tri (o-tolyl) phosphonium (tetrakis (pentafluorophenyl) borate
(tri (o-tolyl) phosphonium (tetrakis (pentafluorophenyl) borate),
Tri (2,6-dimethylphenyl) phosphonium (tetrakis (pentafluorophenyl) borate
(tri (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate),
Tropylium tetraphenylborate
(tropylium tetraphenylborate),
Triphenylcarbenium tetraphenylborate
(triphenylcarbenium tetraphenylborate),
Triphenylphosphonium tetraphenylborate
(triphenylphosphonium tetraphenylborate),
Triethylsilyl tetraphenylborate
(triethylsilylium tetraphenylborate),
Benzene (diazonium) tetraphenylborate,
Tropylium tetrakis (pentafluorophenyl) borate
(tropylium tetrakis (pentafluorophenyl) borate),
Triphenylcarbenium tetrakis (pentafluorophenyl) borate
(triphenylcarbenium tetrakis (pentafluorophenyl) borate),
Triphenylphosphonium tetrakis (pentafluorophenyl) borate
(triphenylphosphonium tetrakis (pentafluorophenyl) borate),
Triphenylsilyl tetrakis (pentafluorophenyl) borate
(triethylsilylium tetrakis (pentafluorophenyl) borate),
Benzene (diazonium) tetrakis (pentafluorophenyl) borate
(benzene (diazonium) tetrakis (pentafluorophenyl) borate),
Tropylium tetrakis (2,3,4,6-tetraolophenyl) borate
(tropylium tetrakis- (2,3,4,6-tetrafluorophenyl) borate),
Triphenylcarbenium (2,3,4,6-tetraolophenyl) borate
_{(triphenylcarbenium tetrakis- (2,3,4, 6- tetrafluorophenyl} ) borate),
Triphenylphosphonium tetrakis (2,3,4,6-tetraolophenyl) borate
(triphenylphosphonium tetrakis (2,3,4,6-tetrafluorophenyl) borate),
Triethylsilylium tetrakis (2,3,4,6-tetraolophenyl) borate
(triethylsilylium tetrakis (2,3,4,6-tetrafluorophenyl) borate),
Benzene (diazonium) tetrakis (2,3,4,6-tetraolophenyl) borate
(benzene (diazonium) tetrakis (2,3,4 , 6- tetrafluoroρhenyl) borate).
Tropylium tetrakis (perfluoronaphthyl) borate
(tropylium tetrakis (perfluoronaphthyl) borate),
Triphenylcarbenium tetrakis (perfluoronaphthyl) borate
(triphenylcarbenium tetrakis (perfluoronaphthyl) borate),
Triphenylphosphonium tetrakis (perfluoronaphthyl) borate
(triphenylphosphonium tetrakis (perfluoronaphthyl) borate),
Triethylsilylium tetrakis (perfluoronaphthyl) borate
(triethylsilylium tetrakis (perfluoronaphthyl) borate),
Benzene (diazonium) tetrakis (perfluoronaphthyl) borate
(benzene (diazonium) tetrakis (perfluoronaphthyl) borate),
Tropylium tetrakis (perfluorobiphenyl) borate
(tropylium tetrakis (perfluorobiphenyl) borate),
Triphenylcarbenium tetrakis (perfluorobiphenyl) borate
(triphenylcarbenium tetrakis (perfluorobiphenyl) borate),
Triphenylphosphonium tetrakis (perfluorobiphenyl) borate
(triphenylphosphonium tetrakis (perfluorobiphenyl) borate),
Triethylsilylium tetrakis (perfluorobiphenyl) borate,
Benzene (diazonium) tetrakis (perfluorobiphenyl) borate,
Tropylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate _{(tropylium tetrakis (3, 5- bis} (trifluoromethyl) phenyl) borate),
Triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate) _,
Triphenylphosphonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(triphenylphosphonium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
Triethylsilylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(triethylsilylium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate), and benzene (diazonium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(benzene (diazonium) tetrakis (3,5-bis (trifluoromethyl) phenyl) borate).
Most preferably, the ionic stoichiometric activator (L **-H) d ⁺ (A ^d- ) is
N, N-dimethylanilinium tetrakis (perfluorophenyl) borate
(N, N-dimethylanilinium tetrakis (perfluorophenyl) borate),
N, N-diethylanilinium tetrakis (perfluoronaphthyl) borate
(N, N-dimethylanilinium tetrakis (perfluoronaphthyl) borate),
N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate
(N, N-dimethylanilinium tetrakis (perfluorobiphenyl) borate),
N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate
(N, N-dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate),
Triphenylcarbenium tetrakis (perfluoronaphthyl) borate
(triphenylcarbenium tetrakis (perfluoronaphthyl) borate),
Triphenylcarbenium tetrakis (perfluorobiphenyl) borate
(triphenylcarbenium tetrakis (perfluorobiphenyl) borate),
Triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,
(triphenylcarbenium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate), or
Triphenylcarbenium tetra (perfluorophenyl) borate
(triphenylcarbenium tetra (perfluorophenyl) borate).

The catalyst precursor can also be activated with a cocatalyst or activator comprising a non-coordinating anion comprising a cyclopentadienyl ion free of metalloid. These are described in US Patent Publication No. 2002/0058765 Al published on May 16, 2002, and this invention requires the addition of a cocatalyst or catalyst precursor. A “coexistable” non-coordinating anion is an anion that does not degrade to neutrality when the initially formed complex decomposes. Further, the anion does not pass anionic substituents or fragments to the cation and does not generate neutral byproducts from the neutral transition metal compound and the anion. Preferred coordinating anions useful in the present invention are coexisting anions, which can be substituted by an ethylene or acetylenically unsaturated monomer during polymerization while stabilizing the transition metal complex in the sense of keeping its ionic charge +1. It is an anion with sufficient liability. This type of cocatalyst may be used with a scavenger such as, but not limited to, triisobutylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, triethylaluminum or trimethylaluminum. .

The process of the present invention also includes a co-catalyst compound or activator complex that is initially a neutral Lewis acid but reacts with an alkylated transition metal compound to form a cationic metal complex and a non-coordinating anion or zwitterionic complex. Can also be used. The alkylated metallocene compound is formed by the reaction of a catalyst precursor and a cocatalyst. For example, tri (pertafluorophenyl) boron or anilinium creates the cationic transition metal complexes of the present invention and is similar to group 4 metallocene compounds that act to extract hydrocarbyl ligands to stabilize non-coordinating anions. See European patents EP-A-0 427 697 and EP-A-0 520 732 which describe the object. See also EP-A-0 495 375 methods and compounds.

See US Pat. Nos. 5,624,878, 5,486,632, and 5,527,929 for the formation of zwitterionic complexes using analogs of Group 4 metallocene compounds.

Additional neutral Lewis acids are known to those skilled in the art and are suitable for removing formal anionic ligands. In particular, a paper by EY-X. Chen and TJ Marks, “Cocatalysts for metal-catalyzed olefin polymerization: activators, activation processes and the relationship between structure and activity” (Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes , and Structure-Activity Relationships), Chem. Rev., 100, 1391-1434 (2000).

The cation of the non-coordinating anion precursor is a Bronsted acid such as a proton, or a protonated Lewis base (except water), or a reducing Lewis acid such as ferrocenium or a silver cation, or sodium, magnesium or In the case of an alkali such as a cation of lithium or an alkaline earth metal cation, the molar ratio of catalyst-precursor-activator may be any ratio. Combinations with the described activator compounds can also be used for activation.

When an ionic or neutral stoichiometric activator (eg NCA) is used, the molar ratio of catalyst-precursor-activator is 1:10 to 1: 1; 1:10 to 10: 1; 1 : 10 to 2: 1; 1:10 to 3: 1; 1:10 to 5: 1; 1: 2 to 1.2: 1; 1: 2 to 10: 1; 1: 2 to 2: 1; 1: 2 From 3: 1; 1: 2 to 5: 1; 1: 3 to 1.2: 1; 1: 3 to 10: 1; 1: 3 to 2: 1; 1: 3 to 3: 1; 1: 3 to 5 : 1; 1: 5 to 1: 1; 1: 5 to 10: 1; 1: 5 to 2: 1; 1: 5 to 3: 1; 1: 5 to 5: 1; 1: 1 to 1: 1.2 It is.

The molar ratio of catalyst-precursor-activator is
1: 500 to 1: 1, 1: 100 to 100: 1; 1:75 to 75: 1; 1:50 to 50: 1; 1:25 to 25: 1; 1:15 to 15: 1; 1: 10 to 10: 1; 1: 5 to 5: 1, 1: 2 to 2: 1, 1: 100 to 1: 1; 1:75 to 1: 1; 1:50 to 1: 1; 1:25 1: 1; 1:15 to 1: 1; 1:10 to 1: 1; 1: 5 to 1: 1; 1: 2 to 1: 1; 1:10 to 2: 1.

Preferred activators and activator / co-activator combinations include trimethyl, triethyl, tri-n-propyl, tri-n-hexyl, tri-n-butyl, tri-n-octyl, tri-n-dodecyl, tri-n Trialkylaluminum and dimethylanilinium, including -isopropyl, tri-isobutyl or tri-isopentyl, tetrakis (pentafluorophenyl) borate, or tri (pentafluorophenyl) borate, and trimethylaluminum and dimethylanilinium, Tetrakis (pentafluorophenyl) borate or a mixture of tri (pentafluorophenyl) borate.

In certain embodiments, a mixture of methylalumoxane, modified methylalumoxane, or alkylalumoxane is also used by itself or as one of many cocatalyst compounds. However, often it is not necessary or desirable to use alumoxane. This is because alumoxane compounds are usually more expensive than trialkylaluminum or trialkylboron compounds.

In some embodiments, the scavenger compound is used with a stoichiometric activator. Typical aluminum or boron alkyl compounds useful as scavengers are usually represented by the general formula R ^X JZ ₂ where J is selected from aluminum or boron, R ^X is selected from C 1 to C 20 alkyl radicals, the same or different Each Z is independently a different monovalent anionic ligand such as R ^X or halogen (Cl, Br, I), alkoxide (OR ^X ). Most preferred aluminum alkyls include triethylaluminum, diethylanilinium chloride, tri-iso-butylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum, trimethylanilinium and the like. Preferred boron alkyls include triethylboron. The scavenger compound may also be alumoxane and modified alumoxane including methylalumoxane and modified methylalumoxane.

In other embodiments, the alkylalumoxane compounds (eg, methylalumoxane and modified methylalumoxane) are in the reaction zone, less than 3 milligrams per gram of olefin feed, preferably relative to olefin feed per gram. Less than 1 milligram, preferably less than 0.5 milligrams per gram of olefin feedstock.

Supported catalyst supported catalyst and / or supported catalyst system may be used to produce PAO. In order to make a homogeneous supported catalyst, the catalyst precursor is preferably dissolved in a selected solvent. The term “homogeneous supported catalyst” means that the catalyst precursor, activator, and / or activated catalyst has a distribution that is close to a uniform distribution on the accessible surface of the support, including the surface of the internal pores of the porous support. Say that will be. In some embodiments of the supported catalyst, the supported catalyst may be a homogeneous supported catalyst, and in other embodiments there is no such tendency to select.

Useful supported catalyst systems may be produced by any method effective to support other coordination catalysts, where effective means that the catalyst produced by such methods is a heterogeneous process. It can be used to oligomerize or polymerize olefins.

The catalyst precursor, activator, cocatalyst (if present), suitable solvent and support may be added in any order or simultaneously.

In some methods, the activator may be dissolved in a suitable solvent such as toluene and stirred with the support material for 1 minute to 10 hours to produce a supported catalyst. While the total solution volume (catalyst solution, activator solution, or both) may be greater than the pore volume of the support, in some embodiments the total solution volume required to form a gel or slurry is Limited (about 90% to 400% of the pore volume, preferably about 100 to 200%). The mixture is optionally heated to 30 to 200 ° C. during this time. The catalyst precursor may be added to the mixture as a solid, or may be added as a solution if a suitable solvent is used in the previous process. Alternatively, the mixture may be filtered and the resulting solid may be mixed with the catalyst precursor solution. Similarly, the mixture may be vacuum dried and mixed with the catalyst precursor solution. The resulting catalyst mixture is stirred for 1 minute to 10 hours and the supported catalyst is filtered from the solution and vacuum dried or evaporated to remove the solvent.

Alternatively, the catalyst precursor and activator are combined in a solvent to make a solution. The support is then added to this solution and the resulting mixture is typically stirred for 1 minute to 10 hours. The total activator / catalyst-precursor solution volume may be greater than the pore volume of the support. However, in certain embodiments, the total solution volume required to form a gel or slurry is limited (about 90% to 400%, preferably about 100 to 200% of the pore volume). After stirring, the remaining solvent is removed in vacuum, usually at ambient temperature and usually 10-16 hours, but the time may be long or short, and may be high or low.

The catalyst precursor may also be supported in the absence of the activator; in this case, the activator (and optionally the cocatalyst) is added to the liquid phase of the slurry process. For example, the catalyst precursor solution may be mixed with the support material for about 1 minute to 10 hours. The resulting pre-catalyst mixture may be filtered from the solution, dried under vacuum, or evaporated to remove the solvent.

The total catalyst-precursor solution volume may be greater than the pore volume of the support. However, in certain embodiments, the total solution volume required to form a gel or slurry is limited (about 90% to 400%, preferably about 100 to 200% of the pore volume).

Further, two or more different catalyst precursors may be placed on the same support by any of the support methods described above. Similarly, one or more activators and one cocatalyst may be placed on the same support.

Suitable solid particle supports usually comprise a polymeric or refractory oxide material, each preferably being porous. Any support material having an average particle size greater than 10 μm can be used in the present invention. In various embodiments, a porous support material is selected. For example, talc, inorganic oxides, inorganic chlorides such as magnesium chloride, and resin-based support materials such as polystyrene polyolefins, or polymer compounds or any other organic support material.

In some embodiments, an inorganic oxide material is selected as the support material, including a Group 2, 3, 4, 4, 5, 13, or 14 metal or metalloid oxide. In some embodiments, the catalyst support material is selected to include silicon, alumina, silica-alumina, and mixtures thereof. Other organic oxides may be used alone or in combination with silicon, alumina, silica-alumina. These are magnesia, titania, zirconia and the like. Lewis acid materials such as montmorillonite and similar clays may also be used as a support. In this case, the support can optionally also act as an activator component. However, additional active agents may also be used. In some cases, a special family of solid supports commonly known as MCM-41 may also be used. MCM-41 is a new type of unique crystalline support that can be adjusted with a second component to adjust pore size and acidity. See US Pat. No. 5,264,203 for a detailed description of this type of material and how to modify it.

The support material may be pretreated by a number of methods. The inorganic oxide may be calcined, chemically treated with a dehydroxylating agent such as an alkylaluminum, or an alumoxane such as methylalumoxane, or both.

As stated above, polymeric carriers are also preferably used in the present invention. For example,
See the description of WO 95/15815 and US Pat. No. 5,427,991.

The method disclosed in the present invention absorbs the catalyst compound, activator or catalyst system of the present invention or, in particular, if the polymeric support is made of porous particles, it allows the polymeric support to absorb them. In addition, they may be used with catalyst compounds, activators or catalyst systems, or they may be bonded to the polymer chain or chemically bonded through functional groups present in the polymer chain.

Useful catalyst supports may have a surface area of 10-700 m ² / g and / or a pore volume of 0.1-4.0 cc / g and / or an average particle size of 10-500 μm. In some embodiments, the surface area may be 50-500 m ² / g, and / or the pore volume may be 0.5-3.5 cc / g and / or the average particle size may be 20-200 μm. In other embodiments, the surface area may be 100-400 m ² / g, and / or the pore volume may be 0.8-3.0 cc / g and / or the average particle size may be 30-100 μm. Useful carriers usually have a pore size of 10-1000 angstroms, alternatively 50-500 angstroms, or 75-350 angstroms. The metallocene and / or metallocene / activator combination is usually deposited on the support at a loading level of 10-100 micromole catalyst precursor per gram of solid support; alternatively 20-80 micromole per gram of solid support or Deposited at 40-60 micromoles per gram of solid support. However, it may be higher or lower than those provided that the amount of the total solid catalyst precursor does not exceed the capacity of the supported pores.

The metallocene and / or metallocene / activator combination may be supported for bulk or slurry polymerization, or other required polymerization. Many support methods are known for catalysts, particularly alumoxane activated catalysts, in the olefin polymerization technology, all of which are preferably used in the present invention. See, for example, US Pat. Nos. 5,057,475 and 5,227,440. Examples of support ionic catalysts are described in WO 94/03056. US Pat. No. 5,643,847 and WO 96 / 04319A describe a particularly effective method. Either a polymer or an inorganic oxide may function as a support. See U.S. Patent Nos. 5,422,325, 5,427,991, 5,498,582 and 5,466,649 and International Publications WO 93/11172 and WO 94/07928.

In other preferred embodiments, the metallocene and / or activator (with or without support) may be combined with the alkylaluminum compound, preferably the trialkylaluminum compound, prior to entering the reactor. Preferably, the alkylaluminum compound is of the formula R ₃ Al, wherein each R is independently a Cl 2 to C 20 alkyl group; preferably the R group is independently selected from the group consisting of: :
Methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, n-butyl, pentyl, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl, isooctyl, n-octyl, nonyl, iso-nonyl N-nonyl, decyl, isodecyl, n-decyl, undecyl, isoundecyl, n-undecyl, dodecyl, isododecyl and n-dodecyl, preferably iso-butyl, n-octyl, n-hexyl and n-dodecyl. Preferably the alkylaluminum compound is selected from triisobutylaluminum, tri-n-octylanilinium, tri-n-hexylaluminum and tri-n-dodecylaluminum.

Monomer In certain preferred embodiments, the catalyst compounds described herein are used to polymerize or oligomerize any one or more unsaturated monomers. Preferred monomers include C ₃ to C ₂₄ olefin alpha olefins, preferably C ₃ to C ₂₀ olefin alpha olefins. In some embodiments, the preferred monomers, linear, branched or cyclic alpha-olefins, preferably alpha-olefins to C ₂₀ C _3, from preferably more preferably alpha-olefins and C ₁₄ from C ₄ C ₈ Contains C ₁₂ alpha olefins. Preferably the olefin monomer is, for example, one or more of 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 3-methyl-1-butene, It may be 4-methyl-1-pentene and 1-tetradecene.

In certain preferred embodiments, the process described herein comprises a homo-oligomer or co-oligomer (in the present specification and claims, a co-oligomer comprises 2, 3, 4 or more different monomer units). It may be used to generate Preferred oligomers produced in the present invention may include homo-oligomers or co-oligomers of any of the above C ₃ to C ₂₀ alpha olefin monomers. In certain preferred embodiments, the oligomer is a C ₈ to C ₁₂ alpha olefin homo-oligomer. Or, in other embodiments, the oligomer is a homo-oligomer of: propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1 -Undecene or 1-dodecene. Preferably, the oligomer is a 1-octene, 1-nonene, 1-decene homo-oligomer. In other embodiments, the oligomer comprises 2 or 3 or more monomers selected from C3 to C20 alpha-olefins.

See PCT application US2006 / 027591, especially page 8, paragraphs [0029] to page 16, [044] for information on the mixed raw materials used to produce PAO.

The alpha-olefin used to produce a PAO, but the present invention is a C ₃ containing C ₂₄ alpha-olefins is not limited to this, C ₁₄ alpha-olefins from C _3, for example, propylene, 1-butene, 1 -Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene and 1-tetradecene are preferred. Preferred groups of polyalphaolefins are polypropylene, poly-1-butene, poly-1-pentene, poly-1-hexene, poly-1-heptene, poly-1-octene, poly-1-nonene, poly-1-decene. Poly-1-undecene, poly-1-dodecene, poly-1-tridecene, and poly-1-tetradecene, but higher olefin dimers ranging from C ₁₂ to C ₁₈ are also present in the final product. You may do it.

Create In some embodiments, useful PAO is preferably C ₂₀ or more oligomeric or polymeric carbons made from to C ₂₀ C _3, and in other embodiments, from a C ₃ C ₁₄ It may be an oligomer or polymer having a carbon number of ₂₄ or more. Suitable olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1 -Contains tetradecene. In some embodiments, the olefin is propylene and the polymer product is a polypropylene pentamer and higher oligomer or polymer mixture thereof. In another embodiment, the olefin is 1-butene and the PAO is a mixture of 1-butene pentamer and higher oligomers thereof. In another embodiment, the olefin is 1-pentene and the PAO is a mixture of 1-pentene tetramer and pentamer and higher oligomers thereof. In another embodiment, the olefin is 1-hexene and the PAO is a mixture of 1-hexene tetramers and pentamers and higher oligomers thereof. In another embodiment, the olefin is 1-heptene and the PAO is a mixture of 1-heptene trimer and tetramer or higher oligomers. In another embodiment, the olefin is 1-octene and the PAO is a mixture of 1-octene trimers and tetramers and higher oligomers thereof.

In another embodiment, the olefin is 1-nonene and the PAO is a mixture of 1-nonene trimers and tetramers and higher oligomers thereof.

In another embodiment, the olefin is 1-decene and the PAO is a mixture of trimers and tetramers of 1-decetene and higher oligomers thereof.

In another embodiment, the olefin is 1-undecene and the PAO is a mixture of 1-undecene trimers and tetramers and higher oligomers thereof.

In another embodiment, the olefin is 1-dodecene and PAO is a mixture of 1-dodecene trimers and tetramers and higher oligomers thereof.

In other embodiments, the monomer comprises propylene and / or butene or a combination of propylene and / or butene with other alpha olefins or other olefins selected from C5 to C20.

When C 14 to C 20 large linear alpha olefins are used as feed, preferably these large olefins are used in a mixture containing other linear alpha olefins from C 3 to C 12. Although polymers or oligomers made from these large alpha olefins usually have a high VI, they also have a strong tendency to crystallize, thus reducing the low temperature fluidity of the fluid. It is usually more preferable to copolymerize these large alpha olefins with C3 to C12 small alpha olefins. The copolymer does not crystallize or solidify easily. Thus, the copolymer usually has excellent low temperature fluidity, high VI and good lubricating properties.

In certain preferred embodiments, the PAO comprises 2 or more monomers, alternatively 3 or more, alternatively 4 or more, alternatively 5 or more monomers. For example, C ₃ , C ₄ , C ₆ , C ₁₂ -alpha olefin mixture, C ₃ , C ₁₂ -alpha olefin mixture, C ₃ , C ₁₂ , C ₁₄ -alpha olefin mixture, C ₄ , C ₁₂ -alpha olefin mixture , C ₄ , C ₁₂ , C ₁₄ -alpha olefin mixture, C ₄ , C ₁₄ -alpha olefin mixture, C ₆ , C ₁₂ -alpha olefin mixture, C ₆ , C ₁₂ , C ₁₄ -alpha olefin mixture, C ₅ , C ₁₂ , C ₁₄ -Alpha olefin mixture, C ₆ , C ₁₀ , C ₁₄ -Alpha olefin mixture, C ₆ , C ₈ , C ₁₂ -Alpha olefin mixture, a C ₈ , C ₁₀ , C ₁₂ -Linear alpha olefin Mixture, or C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C _14- Linear alpha-olefin mixture, or C ₄ , C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ -linear alpha-olefin mixtures can be used as raw materials.

In other embodiments, the PAO contains less than 40% ethylene by weight. In copolymers with C ₃ to C ₆ alpha olefins, it may sometimes be desirable to include ethylene as one of the components. In this case, it is preferred that 1 to 40% by weight of ethylene is present in the raw material. In certain other embodiments, the feedstock is 40 wt% ethylene and 60 wt% 1-butene, or 30 wt% ethylene and 70 wt% 1-butene, or 20 wt% ethylene and 80 wt% 1-butene, 10 Wt% ethylene and 90 wt% 1-butene, or 5 wt% ethylene and 95 wt% 1-butene, or 40 wt% ethylene and 60 wt% propylene, or 30 wt% ethylene and 70 wt% propylene, or 20 wt% Contains ethylene and 80 wt% propylene, 10 wt% ethylene and 90 wt% propylene, 5 wt% ethylene and 95 wt% propylene.

The copolymers of C ₇ and C ₁₈ alpha-olefins, is preferably the amount of ethylene is small, 0 to 20% by weight of ethylene is preferable.

In certain preferred embodiments, any of the PAOs described herein may contain at least 60% by weight of 3 to 24 carbon atoms and 0.5 to 40% by weight ethylene, wherein polyalpha measured by C ¹³ NMR. At least 80% of the ethylene present in the olefin is in the 1 to 35 carbon range.

Preferably PAO described herein, by measuring C ¹³ NMR, 70 wt% 5 to 24 carbon atoms (preferably at least 80 wt%, preferably at least 85 wt%, preferably at least 90 wt%, preferably May contain at least 95 mol%) and 0.5 to 40 wt% ethylene, wherein at least 80% (preferably at least 85%, preferably at least 90%, preferably at least 95%) of the ethylene present in the polyalphaolefin. Preferably at least 98%, preferably 100%) is in the 1 to 35 carbon range (preferably 1 to 30, preferably 1 to 25, preferably 1 to 20, preferably 1 to 15, preferably 1 to 10, Preferably present in 1 to 5).
Furthermore, the arrangement of the ethylene sequences is random and there is no significant amount of very long polyethylene chains in the lubricant product.

The C ₃ to C ₂₀ alpha olefins used in the present invention can be produced directly from the ethylene growth process used in some commercial production processes, or by Fischer-Tropsch hydrocarbon synthesis from CO / H ₂ synthesis gas, or It can be produced by metathesis of internal olefins and ethylene, or by cracking of crude oil, or by Fischer-Tropsch synthetic wax or any other alpha-olefin synthesis method at high temperature. Preferred feedstocks of the present invention are preferably at least 10% by weight alpha olefin, preferably at least 20% by weight alpha olefin, at least 50% by weight alpha olefin, at least 70% by weight alpha olefin, at least 80% by weight alpha olefin (preferably linear alpha olefin) Olefin), at least 90% by weight alpha olefin (preferably linear alpha olefin), or 100% alpha olefin (preferably linear alpha olefin).

The raw olefin may have a very low concentration. For example, suitable raw materials for the wax cracking reaction contain alpha-olefins in the range of 10 to 90% by weight and can be used in the present invention. Furthermore, the feed stream from the Fischer-Tropsch synthesis process has an alpha-olefin content of 2 to 50% by weight. These are all suitable as raw material olefins. However, even if the other components are internal olefins, branched olefins, paraffins, cyclic paraffins, aromatics (eg, toluene and / or xylene), mixtures containing alpha olefins may also be used as raw materials for the present invention. it can. These components are believed to have a diluting effect and have essentially no detrimental effect on the polymerization of alpha-olefins. In other words, the process described herein does not selectively convert the alpha olefin in the mixture and react the other components.

This technique completely eliminated the need to separate alpha olefins from the mixture and selectively react them with a polymerization or oligomerization catalyst system to separate the alpha olefins from the remaining components in the mixture feed stream. This is economically advantageous, for example, in a process using a Fischer-Tropsch synthetic olefin product stream comprising alpha-olefins, internal olefins, branched olefins and the corresponding alkanes. Such mixtures can be used in accordance with the oligomerization techniques described herein and can be selectively reacted with alpha olefins. There is no need for a separate step of isolating the alpha olefin.

Other examples using this process use alpha olefins produced by metathesis of internal olefins and ethylene, which may contain some internal olefins. This mixed olefin feed can be reacted in the same manner as the polymerization / oligomerization process of the present invention, but it selectively converts alpha olefins to lubricant products. In this way, alpha olefins can be used for base feed synthesis without separation from internal olefins or other types of hydrocarbons. This can provide a significant improvement in the cost of the process. The raw olefins are “Routes to Alpha” in Chapter 3 of the Alpha Olefins Applications Handbook (edited by GR Lappin and JD Sauer, published by Marcel Dekker, Inc. NY, 1989). as described -Olefins "), it may be a mixture of olefins emissions produced from C ₄ from other linear alpha-olefins containing _{C. 2O} alpha-olefins.

In one preferred embodiment, the PAO produced in the present invention is a monomer having a branch at least 2, preferably 3 carbons away from alpha unsaturation, such as 4-methyl-1-decene, 4-ethyl- It may contain l-decene, or 4-methyl-1-hexene, 4-methyl-1-pentene, and the like. These olefins may be present in the linear alpha olefins obtained from the manufacturing process or may be added intentionally. Copolymers of slightly branched alpha olefins and fully linear alpha olefins have improved low temperature properties.

In some embodiments, when 1-butene is used as a feed or as a feed olefin with other alpha olefins, the 1-butene may be pure 1-butene prepared by any commercially available process. .

Alternatively, 1-butene may exist as one of the components in petrochemical plants or mixed C ₄ amounts readily obtained from operation of refineries. US Pat. No. 5,859,159 A discusses in more detail about BB flow (butane-butene flow), or C ₄ flow, such as raffinate 1 or raffinate 2 flow. Steam cracking of light naphtha in these mixtures C ₄ stream ethylene / propylene production processes, which iso N殆- MTBE process butene is removed, fcc-operation and / or other petroleum refining processes that produce C ₄ stream Can be obtained from When these C ₄ stream is used as a raw material, only the 1-butene is removed and the reaction by the catalyst system. Other C ₄ components, cis-, trans-2-butene, iso - butene, n- butane and iso - butane Merely serves as a diluent does not react or interfere with the polymerization catalyst. These mixtures C ₄ stream consisting of interest to produce a copolymer of 1-butene poly-1-butene, higher alpha-olefins of the ethylene or other C ₅ from C _20, an economical source.

In other embodiments, pure propylene from a chemical plant can be used when propylene is used as a feed or as one of the feed olefins including other alpha olefins. Alternatively, a mixed stream of propylene and propane (PP stream) can be used in a similar manner. Propylene selectively polymerizes and propane acts as a diluent and does not participate in the reaction. This PP stream may contain propylene in any amount between 10% and 95% by weight. In other embodiments, a mixture of PP and C ₄ streams may be used as the starting olefin or one of the starting olefin feeds.

Many polymerization oligomerization processes and reactor types used for polymerization / oligomerization process solutions, slurries, and metallocene catalyzed polymerizations or oligomerizations such as bulk polymerization or oligomerization processes can be used in the present invention. In some embodiments, when a solid or supported catalyst is used, a slurry or continuous fixed bed or plug flow process is preferred. In certain preferred embodiments, the monomer contacts the metallocene compound and the activator and / or coactivator / capture agent in a liquid phase, bulk layer, or slurry layer, preferably a continuous stirred tank reactor or continuous tube type. Contact in the reactor is good. In certain preferred embodiments, any temperature in the reactor used in the present invention is from -10 ° C to 250 ° C, preferably 10 ° C to 220 ° C, preferably 10 ° C to 180 ° C, preferably 10 ° C to 170 ° C. It should be ℃. In a preferred embodiment, the pressure of the reactor used in the present invention may be 0.1 to 100 atmospheres, preferably 0.5 to 75 atmospheres, preferably 1 to 50 atmospheres. In other embodiments, the monomer, metallocene and active agent are contacted for a residence time of 1 minute to 30 hours, more preferably 5 minutes to 16 hours, more preferably 10 minutes to 10 hours. In other embodiments, the solvent or dilution is present in the reactor, preferably butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, toluene, o -Xylene, m-xylene, p-xylene, mixed xylene, ethylbenzene, isopropylbenzene and n-butylbenzene; preferably toluene and / or xylene and / or ethylbenzene, linear paraffin (eg Isopar® solvent) ExxonMobil Chemical Company, commercially available from Houston, Texas) or an isoparaffin solvent (eg, Isopar® solvent, available from ExxonMobil Chemical Company, Houston, Texas). These solvents or diluents are usually pretreated by the same method as the raw material olefin (for example, for removal of polar impurities). These solvents usually do not participate actively in the polymerization reaction. However, they provide a diluent effect in the polymerization reaction. The concentration of the solvent usually ranges from 0% to 80% by weight, alternatively from 10% to 60% by weight, and alternatively from 20% to 40% by weight. In commercial production, it is preferable to have as little solvent as possible.

Typically, the process of the present invention contacts one or more transition metal compounds, one or more activators, cocatalysts or scavengers and one or more monomers to produce a polymer or oligomer. These catalysts may be supported, and the supported catalysts are particularly useful in known slurry, solution, or bulk mode operation in single, series or parallel reactors. If the catalyst, activator, or coactivator is a soluble compound, the reaction can be carried out in solution mode. Even if one of the components does not completely dissolve in the reaction medium or raw material solution at the start of the reaction or at a later stage of the reaction, a solution or slurry type operation can be performed.

In either case, the catalyst components are dissolved or suspended in toluene or other readily available aromatic solvent, or aliphatic solvent or feed alpha-olefin stream, and under an inert atmosphere (usually nitrogen, Or under a controlled atmosphere of argon) to allow polymerization or oligomerization. Polymerization or oligomerization may be carried out in a batch mode, in which case all components are added to the reactor, allowing the reaction to be performed as a partial or complete conversion up to a pre-scheduled level of conversion. To do. Subsequently, the catalyst is deactivated by any possible method, such as exposure to air or water, or addition of an alcohol or solvent containing an inert agent, or addition of a solid absorbent. The catalyst component can then be separated by conventional water washing or filtration if a solid absorbent is used. Polymerization or oligomerization may also be carried out in semi-continuous operation, in which case the feed and catalyst system components may be added to the reactor continuously and simultaneously, maintaining a constant ratio of catalyst system components to feed olefins. . Once all the raw materials and catalyst components have been added, the reaction can proceed to a predetermined stage. The reaction is then stopped by deactivating the catalyst in the same manner as described for batch operation. Polymerization or oligomerization can also be carried out in a continuous operation, in which the feed and catalyst system segments are added to the reactor continuously and simultaneously to maintain a constant ratio of catalyst system components to feed olefins. The reactor product is withdrawn from the reactor continuously as in a typical continuous stirred tank reactor (CSTR) operation. The residence time of the reactants is controlled by a predetermined conversion level and catalyst concentration. Thereafter, the product taken out is usually cooled in another reactor in the same manner as in other operations. In certain preferred embodiments, any of the PAO production processes described herein are continuous processes. Preferably the continuous process comprises the following steps:
a) continuously introducing a feed stream containing at least 10 mol% of one or more C ₃ to C ₂₄ alpha-olefins into the reactor;
b) continuously introducing the metallocene compound and the activator into the reactor;
c) Polyalphaolefin is continuously removed from the reactor.

In another embodiment, the continuous process is based on the total reactor pressure, and the partial hydrogen pressure in the reactor is 0.1 to 300 psi (2068 kPa), preferably 0.5 to 200 psi (1379 kPa), preferably 1.0. To 150 psi (1034 kPa), preferably 2.0 to 100 psi (690 kPa), preferably 3 to 50 psi (345 kPa) or less, preferably 5 to 25 psi (173 kPa), preferably 1 to 10 psi (69 kPa) maintaining step. Alternatively, if hydrogen is present, the hydrogen is from 1 to 30,000 ppm by weight in the reactor, preferably 3,000 ppm or less, preferably 150 ppm or less, preferably 750 ppm or less, preferably 500 ppm or less, It is preferably 250 ppm or less, preferably 100 ppm or less, preferably 50 ppm or less, preferably 25 ppm or less, preferably 10 ppm or less, preferably 5 ppm or less. During the polymerization or oligomerization reaction, no or little hydrogen is consumed. Therefore, excess hydrogen gas is refluxed after the reaction is completed.

In other embodiments, if ethylene is present in the reactor, the ethylene partial pressure is usually below 1000 psi, preferably below 500 psi, preferably below 200 psi, preferably below 50 psi, Preferably it is lower than 30 psi, preferably lower than 10 psi. In other embodiments, if propylene, PP stream, C4 stream, 1-butene or 1-pentene is present in the reactor, the total partial pressure of these components is usually below 1000 psi, preferably 500 It may be maintained below psi, preferably below 200 psi, preferably below 50 psi, preferably below 30 psi, preferably below 10 psi. As discussed above, the total reactor pressure may be higher than the total partial pressure of the gaseous feed due to the presence of other inert gases such as nitrogen or argon.

A preferred reactor size is 2 ml or more. In general, it is preferred to use reactors larger than 1 liter in commercial production. The production facility may be a single reactor or several reactors may be arranged in series or in parallel to maximize its productivity, product characteristics and general process efficiency. Reactors and associated equipment are usually pretreated to increase reaction efficiency and catalyst effectiveness. The reaction is usually carried out in an inert atmosphere, and the catalyst system and feed components are not contacted with any catalyst deactivator or poison that is usually a polar oxygen, nitrogen, sulfur, or acetylene compound.

In the present invention, one or more reactors arranged in series or in parallel may be used. Transition metal compounds, activators and, if necessary, co-activators are sent as a solution or slurry to the solvent or alpha-olefin feed stream, activated or pre-activated immediately before being sent separately to the reactor You may send to a reactor as a solution or a slurry. Polymerization / oligomerization is alternatively carried out in a single reactor, in which case the monomer or several monomers, catalyst / activator / co-activator, optionally scavenger, and optionally modifier are in succession. Either added to a single reactor or carried out in series reactor operation, in which case each component mentioned above is added sequentially to two or more serially connected reactors. The catalyst component may be added to the first reactor in series. The catalyst component may also be added to both reactors, with one component added to the first reactor and the other component added to the other reactor. In certain preferred embodiments, the precatalyst is activated in the reactor in the presence of the olefin. In another embodiment, the precatalyst in the form of a dichloride metallocene is pretreated with an alkylaluminum reagent, in particular triisobutylaluminum, tri-n-hexaluminum and / or tri-n-octylaluminum. And then charged into a reactor containing other catalyst components, or previously activated by other catalyst components, thereby obtaining a fully activated catalyst, which is fed to a reactor containing raw olefins Is done. In other alternative embodiments, the pre-catalyzed metallocene is mixed with an activator and / or a co-activator, and the activated catalyst is combined with a feed olefin stream comprising a scavenger or co-activator. It is thrown into. In other alternative embodiments, all or part of the co-activator is premixed with the feed olefin and charged to the reactor at the same time as the other catalyst solution containing the metallocene and the activator and / or co-activator. The

In some embodiments, small amounts of scavenger poisons, such as trialkylaluminum (trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum) or methylalum Xane is added to the feed olefin stream to further improve the catalytic activity.

In certain preferred embodiments, the monomer is contacted with an alkylaluminum compound, preferably a trialkylaluminum compound, before being charged to the reactor. In another preferred embodiment, the metallocene and / or activator is combined with an alkylaluminum compound, preferably a trialkylaluminum compound, before being charged to the reactor. Preferably, the alkylaluminum compound is represented by the chemical formula R ₃ Al, wherein each R is independently a Cl to C20 alkyl group, preferably the R group is independently selected from the group consisting of: :
Methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, n-pentyl, hexyl, isohexyl, n-hexyl, heptyl, octyl, isooctyl, n-octyl, nonyl, isononyl, n-nonyl, decyl, isodecyl N-decyl, undecyl, isoundecyl, n-undecyl, dodecyl, isododecyl and n-dodecyl, preferably isobutyl, n-octyl, n-hexyl and n-dodecyl. Preferably the alkylaluminum compound is selected from triisobutylaluminum, tri-n-octylaluminum, tri-n-hexylaluminum and tri-n-dodecylaluminum.

In certain embodiments of any process described herein, the raw olefin and / or solvent is treated to remove catalyst poisons, such as peracids, oxygen or nitrogen containing organic compounds, or acetylenic compounds. The The raw olefin, solvent if used, or purge gas (usually nitrogen) is purified by conventional purification techniques. In the case of a liquid raw material, the liquid is usually degassed in a vacuum for 1 to 60 minutes in order to remove dissolved gas. Alternatively, the raw olefin, solvent or purge gas is purified through an activated molecular sieve (3A, 4A, 5A or 13X molecular sieve), or a commercial absorption bed consisting of activated alumina, silica or other purified solids. These purified solids can remove a small amount of water, alcohol, nitrogen or all other polar impurities. Alternatively, the raw olefin, solvent or purge gas is purified through an activated oxygen removal solid catalyst (deoxygenation catalyst), which typically contains copper, chromium and / or other metal oxides with low oxidation state including. U.S. Pat. No. 6,9797,52 describes the purification of raw materials. Depending on the quality of the raw material and the desired level of raw material purification, one or more of the methods described above can be used in combination to obtain the best results.

In the present invention, usually, such a treatment increases the productivity of the catalyst by at least 20% to 1000% or more as compared to the case where such a treatment is not performed. The improved process also includes special treatment of raw olefins to remove catalyst poisons, such as peracids, oxygen, sulfur or nitrogen containing organic compounds, or other minor impurities. This treatment can greatly increase the productivity of the catalyst (usually greater than 10 times). Preferably, the raw olefin contacts the molecular sieve, activated alumina, silica gel, oxygen scavenging catalyst or refining clay to reduce the heteroatom-containing compounds contained in the raw material to preferably less than 50 ppm, preferably less than 10 ppm. Let

The catalyst composition may be used individually or mixed with other known polymerization catalysts to produce polymer or oligomer blends. By selecting monomers and catalysts, polymer or oligomer blends can be produced under conditions similar to those using separate catalysts. Polymers with large MWD are obtained from and are realized from polymers made with mixed catalyst systems. Sometimes it may be advantageous to produce a fluid with a large MWD, which may improve the blend characteristics of the fluid. The mixed catalyst may contain two or more catalyst precursors and / or two or more activators.

In general, when using a metallocene catalyst, the reaction proceeds smoothly if the raw material olefin, solvent, and diluent are pretreated and care is taken so that impurities are not mixed into the catalyst component stream and the reactor. In certain embodiments, when a metallocene catalyst is used, the complete catalyst system may further include one or more scavenging compounds, particularly when it is immobilized on a support. Here, the trapping compound refers to a compound that removes polar impurities from the reaction environment. These impurities adversely affect catalyst activity and stability. The purification step is usually used before introducing the reaction components into the reaction vessel. However, such steps can hardly be polymerized or oligomerized without the use of certain capture compounds. Usually, the polymerization process still uses at least a small amount of scavenging compound (as described above).

Typically, the capture compounds are those of the Group 13 organometallic compounds of U.S. Pat. Such organometallic compounds. Typical compounds include triethylaluminum, triethylborane, tri-iso-butylaluminum, diisobutylaluminum hydride, methylalumoxane, isobutylalumoxane, and tri-n-octylaluminum. These scavenging compounds with bulky or C ₆ -C ₂₀ linear hydrocarbyl substituents attached to the metal or metalloid center usually reduce adverse interactions with the active catalyst. These examples include triethylaluminum, but more preferably bulky compounds such as tri-iso-butylaluminum, tri-iso-prenylaluminum, and tri-n-hexylaluminum, tri-n-octylaluminum, Includes long chain linear alkyl-substituted aluminum compounds such as tri-n-dodecylaluminum. Alumoxane may also be included in the amount of scavenger along with other active agents such as methylalumoxane, [Me ₂ HNPh] ⁺ [B (pfp) ₄ ] ⁻ or B (pfp) ₃ , where pfp is perfluoro Phenyl (C ₆ F ₅ ), Me is methyl and Ph is phenyl.

The PAOs described herein can also be produced in a homogeneous solution process. Usually this involves polymerization or oligomerization in a continuous reactor where the formed polymer and starting monomer and the catalyst material fed are stirred to reduce or prevent concentration or temperature gradients. . Temperature control in the reactor is usually controlled by the polymerization heat and the reactor coating or cooling coil or reactant cooling side stream to cool the reactor contents, automatic cooling, raw material pre-cooling, evaporation of the liquid medium (dilution) Agents, monomers or solvents) or combinations of those mentioned above. Adiabatic reactors using precooled feed can also be used. The temperature of the reactor depends on the catalyst used and the desired product. High temperatures tend to create low molecular weights and low temperatures tend to create high molecular weights, but this is not a strict rule. In general, the reactor temperature can vary between -10 ° C and 250 ° C, preferably between 10 ° C and 220 ° C, preferably between 10 ° C and 180 ° C, preferably between 10 ° C and 170 ° C.

In general, it is of interest to control the reaction temperature as tightly as possible within a predetermined range. For example, to produce a fluid with a narrow molecular weight distribution to obtain the highest possible shear stability, control reactor temperature and minimize temperature fluctuations throughout the reactor during the entire reaction time. Is useful. If multiple reactors are used in series or in parallel, it is useful to keep the temperature constant within a predetermined width so as to minimize the spread of the molecular weight distribution. The reaction temperature, swing profile, variation can be adjusted to produce a fluid with a broad molecular weight distribution, or the second reactor temperature is preferably the second reactor temperature as in series operation. The reactor temperature should be higher. In parallel reactor operation, the temperatures of the two reactors are independent. Alternatively, MWD can also be intentionally broadened using multiple types of metallocene catalysts.

The pressure in any reactor used in the present invention is about 0.1 to 100 atmospheres (1.5 psi to 1500 psi), preferably 0.5 to 75 atmospheres (8 psi-1125 psi), most preferably 1.0 to 50 atmospheres (15 psi to 750 psi). The reaction under a nitrogen atmosphere, or a quantity of hydrogen, or other volatile components are cases, for example, propylene, PP stream, 1-butene, C ₄ stream, be carried out under a partial pressure of 1-pentene it can. In some cases, a small amount of hydrogen is added to the reactor to improve catalyst productivity. The amount of hydrogen is preferably at a level that improves catalyst productivity, but should be maintained at a level not high enough to induce hydrogenation of olefins, particularly alpha olefins. The reason is that conversion of alpha-olefins to saturated paraffins has a very detrimental effect on process efficiency. The hydrogen partial pressure is preferably kept low and should be less than 300 psi, preferably less than 100 psi, preferably less than 50 psi, preferably less than 25 psi, preferably less than 10 psi.

In certain particularly preferred embodiments, the hydrogen concentration in the reactor in any of the processes described herein is less than 30,000 ppm, preferably less than 5,000 ppm, preferably less than 1,000 ppm, preferably less than 500 ppm. Preferably less than 100 ppm, preferably less than 50 ppm, preferably less than 10 ppm.

The reaction time or reactor residence time depends on the type of catalyst normally used, the amount of catalyst used, and the level of conversion desired.

Different metallocenes have different activities. Usually, the greater the degree of alkyl substitution on the cyclopentadienyl ring, the better the catalyst productivity. For example, the following catalysts have a desirable high productivity and stability over unsubstituted metallocenes:
(bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride)
((bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride),
(bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride)
(bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride),
(bis (l-methyl-3-n-butylcyclopentadienyl) zirconium dichloride)
(bis (l -methyl-3-n-butylcyclopentadienyl) zirconium dichloride),
(bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride)
(bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride),
(bis (l-ethyl-3-n-butylcyclopentadienyl) zirconium dichloride)
(bis (l-ethyl-3-n-butylcyclopentadienyl) zirconium dichloride),
(bis (l-methyl-3-n-hexylcyclopentadienyl) zirconium dichloride)
(bis (1 -methyl-3 -n- hexylcyclopentadienyl) zirconium dichloride),
(bis (l, 2-cyclopentadienyl) zirconium dichloride)
(bis (l, 2-diethylcyclopentadienyl) zirconium dichloride),
(bis (l, 3-diethylcyclopentadienyl) zirconium dichloride)
(bis (l, 3-diethylcyclopentadieny) zirconium dichloride),
(bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride) or
(bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride)
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride)
(bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride), or
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dichloride)
(bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride),
(l, 2,3,4-tetramethylcyclopentadienyl) (l, 3-dimethylcyclopentadienyl) zirconium dichloride) or
(1,2,3,4-tetramethylcyclopentadienyl) (l, 3-dimethylcyclopentadienyl)
zirconium dichloride)
(l, 2,4-trimethylcyclopentadienyl) (l, 3-dimethylcyclopentadienyl) zirconium dichloride) or
(1,2,4-trimethylcyclopentadienyl) (l, 3-dimethylcyclopentadienyl) zirconium dichloride)
(bis (l, 2-indenyl) zirconium dichloride) or
(bis (indenyl) zirconium dichloride)
(bis (l, -methylindenyl) zirconium dichloride) or
(bis (l-methylindenyl) zirconium dichloride)
(bis (2-imethylenendenyl) zirconium dichloride) or
(bis (2-methylindenyl) zirconium dichloride)
(bis (l, 2-dimethylindenyl) zirconium dichloride) or
(bis (l, 2-dimethylindenyl) zirconium dichloride)
(bis (4-methylindenyl) zirconium dichloride)
(bis (4-methylindenyl) zirconium dichloride), or
(bis (4,7-dimethylindenyl) zirconium dichloride)
(bis (4,7-dimethylindenyl) zirconium dichloride) or
(bis (tetrahydroindenyl) zirconium dichloride)
(bis (tetrahydroindenyl) zirconium dichloride),
(bis (2-methyl-tetrahydroindenyl) zirconium dichloride) or
(bis (2-methyl-tetrahydroindenyl) zirconium dichloride)
(bis (l, 2-indenyl) zirconium dichloride)
(bis (l, 2-dimethyl-tetrahydroindenyl) zirconium dichloride) or
(bis (l, -methyl-tetrahydroindenyl) zirconium dichloride)
(bis (l-methyl-tetrahydroindenyl) zirconium. dichloride) or
(bis (4-methyl-tetrahydroindenyl) zirconium dichloride)
(bis (4-methyl-tetrahydroindenyl) zirconium dichloride),
(bis (4,7-dimethyl-tetrahydroindenyl) zirconium dichloride) or (bis (4,7-dimethyl-tetrahydroindenyl) zirconium dichloride) or their dialkyl analogues.

The amount of catalyst component normally used is a determining factor. When the amount of the catalyst used is large, a high conversion rate tends to be obtained in a short reaction time. However, a large amount of catalyst used makes the production process uneconomical, makes it difficult to control the heat of reaction, and makes it difficult to control the reaction temperature. Thus, it is useful to select a catalyst to minimize the amount of metallocene and activator required to maximize maximum catalyst productivity. If the catalyst system is an ionic promoter with a metallocene plus Lewis acid or NCA component, the metallocene used is usually in the range of 0.01 milligrams to 500 milligrams (or 0.5 milligrams) of metallocene component per gram of alpha-olefin feedstock. A usually preferred range is usually from 0.1 milligrams to 100 milligrams of metallocene component per gram of alpha-olefin feedstock. Furthermore, the molar ratio of NCA activator to metallocene should be 0.1 to 10, preferably 0.5 to 5. Preferably 0.5 to 3. If an alkylaluminum compound coactivator is used, the molar ratio of Al to metallocene should be from 1 to 1000, preferably from 2 to 500, preferably from 4 to 400.

Typically, it is desirable to make the conversion of the raw alpha-olefin as large as possible (close to 100%) with as short a reaction time as possible. However, in CSTR operation, it can sometimes be beneficial to perform the reaction with optimal conversion, and the conversion is less than 100%. There may also be a desire for products that are partially converted or as narrow as possible in the MWD. This is because it is possible to avoid the expansion of MWD by partial conversion. If the reaction performs alpha olefin conversion at conversions below 100%, the unreacted initiator and solvent / diluent after separation from other products can be refluxed to increase the efficiency of the overall process.

Desirable residence times for any of the processes described herein range from 1 minute to 30 hours, more preferably from 5 minutes to 16 hours, more preferably from 10 minutes to 10 hours.

Any of these processes can be used in a single reactor, parallel or series reactor configuration. The liquid process involves contacting the olefin monomer with the catalyst system described above and a suitable diluent or solvent, allowing the monomer to react for a time sufficient to produce the desired polymer or oligomer. Both aliphatic and aromatic hydrocarbon solvents are preferably used. Aromatics such as toluene, xylene, ethylbenzene, propylbenzene, cumene, t-butylbenzene are suitable for use. Alkanes such as hexane, heptane, pentane, isopentane, and octane, Norpar, or Isopar solvents (available from ExxonMobil Chemical Company, Houston, Texas) are also suitable.

Usually, toluene is most suitable for dissolving the catalyst components. Norpar, Isopar or hexane is preferred as the reaction diluent. Often, a mixture of toluene and Norpar, or toluene and Isopar is used as a diluent or solvent. In order to simplify the process and increase the efficiency of the reactor, it is preferable to add as little solvent or diluent as possible to the reactor. When producing high viscosity fluids at low temperatures, solvents or diluents are sometimes added to facilitate transfer of reaction heat, stirring, product handling, filtration, and the like. Usually less than 50% by weight of additional solvent or diluent is added to the reactor, preferably 30% by weight, preferably 20% by weight, preferably 10% by weight, preferably no solvent is added to the reactor system Is good. The reaction system usually contains a small amount of solvent or diluent resulting from the catalyst, activator or coactivator / scavenger solution.

These processes can be carried out in a continuous stirred tank reactor or plug flow reactor, or two or more reactors operated in series or in parallel. These reactors may or may not have an internal cooling device, and the monomer feed may or may not be cooled. See the general disclosure of US Pat. No. 5,705,577 for general process conditions.

When a solid supported catalyst is used for the conversion, the slurry polymerization / oligomerization process is usually operated in the same temperature, pressure and residence time ranges as described above. In slurry polymerization or oligomerization, a suspension of solid catalyst, promoter, monomer and comonomer is added. The suspension containing the diluent is removed intermittently or continuously from the reactor. The catalyst is then separated from the product by filtration, centrifugation or precipitation. The fluid is then distilled to remove solvent, unreacted components, or light products. Some or all of the solvent and unreacted or light components can be refluxed for reuse.

If an unsupported solution catalyst is used, the product is still soluble, suspended or mixed catalyst components at the end of the reaction or when the product is removed from the reactor (eg in the case of CSTR). It may contain. These components are preferably inactivated or removed. Either conventional catalyst deactivation methods or water wash methods can be used to remove the catalyst components. Typically, the reaction is deactivated by adding a stoichiometric amount or excess of air, humidity, alcohol, isopropanol, and the like. The mixture is then washed with dilute sodium hydroxide or water to remove the catalyst components.

The residual organic layer is then distilled to remove the solvent and can be refluxed for reuse. Distillation can further remove any light reaction products from _C18 and lower carbons. These light components can further be used as diluents for the reaction. Or because these light olefin products have vinylidene unsaturation and are most suitable for further functionalization and conversion to high performance fluids, they can be used as olefinic feedstocks for other chemical synthesis. Alternatively, these light olefin products can be hydrogenated for use as high quality paraffinic solvents.

Polymerization or oligomerization in the presence of a very small amount of hydrogen is also advantageous in that it provides a polymer or oligomer with a high proportion of unsaturated double bonds. These double bonds can easily be converted to functional fluids with multiple functional characteristics. An example of the conversion of these polymers with MW greater than 300 can be found in the production of ashless dispersants, where the polymer is reacted with maleic anhydride to produce succinic anhydride PAO, which further comprises amines, alcohols Can be reacted with a polyether alcohol and converted to a dispersant. Examples of such transformations are described in “Lubricant Additives: Chemistry and Application”, edited by Leslie R. Rudnick, Marcel Dekker, Inc. 2003, pages 143-170.

In other embodiments, any polyalphaolefin produced by the present invention is hydrogenated. In particular polyalphaolefins are preferably treated as described above. The heteroatom-containing compound is less than 600 ppm and is contacted with hydrogen and a hydrogenation catalyst to produce a polyalphaolefin having a bromine number less than 2. In certain preferred embodiments, the treated polyalphaolefins contain less than 100 ppm, preferably 10 ppm, of heteroatom-containing compounds. (The hetero starting material-containing compound is a compound containing at least one atom other than carbon and hydrogen.) Preferably, the hydrogenation catalyst is selected from the group consisting of supported 7, 8, 9, and 10 metals, preferably The hydrogenation catalyst is selected from the group consisting of one or more of Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo, and W, and is supported on silica, alumina, clay, titania, zirconia. Or supported on mixed metal oxides or on mesoporous materials, typically known as MCM-41 materials or related materials (as described in US Pat. No. 5,264,203). good.

A preferred hydrogenation catalyst may be nickel supported on diatomaceous earth, or platinum or palladium supported on alumina or MCM-41, or cobalt molybdenum supported on alumina. Typically, a catalyst with a high nickel content, for example 60% Ni on a diatomaceous earth catalyst, or a supported catalyst with a high amount of Co-Mo is used. Alternatively, the hydrogenation catalyst is diatomaceous earth, silica, alumina, clay, or nickel supported on silica-alumina. Alternatively, the catalyst is Pd or Pt supported on MCM-41 or related materials.

In some preferred embodiments, polyalphaolefin 350 ⁰ C of hydrogen and a hydrogenation catalyst and 25 ° C, preferably from contacting at 300 ⁰ C from 100 ° C. In another preferred embodiment, the polyalphaolefin is contacted with hydrogen and the hydrogenation catalyst for 5 minutes to 100 hours, preferably 5 minutes to 24 hours. In another preferred embodiment, the polyalphaolefin is contacted with hydrogen and the hydrogenation catalyst at a pressure of 25 psi to 2500 psi, preferably 100 to 2000 psi. In another preferred embodiment, the hydrogenation process reduces the number of mm triplets in the polyalphaolefin by 1 to 80%. More information on PAO hydrogenation can be found in US Pat. No. 5,573,657 and “Lubricant Base Oil Hydrogen Refining Processes” (“Lubricant Base Oil and See Wax Processing (Lubricant Base Oil and Wax Processing), pages 119-152, Avilino Sequeira, Jr., Marcel Dekker, Inc., NY, 1994)).

This hydrogenation process can be carried out in a batch operated slurry reactor, or continuous stirred tank reactor (CSTR), in which the hydrogenation catalyst is from 0.001% to 20% by weight, preferably 0.01% by weight of the PAO feed. % To 10% by weight. Hydrogen and polyalphaolefin are added to the reactor in succession, thereby allowing for a selected residence time, usually 5 minutes to 10 hours, allowing complete hydrogenation of the unsaturated olefin. The amount of catalyst added is usually very small but is sufficient to compensate for catalyst deactivation. The catalyst and hydrogenated PAO are continuously removed from the reactor. The product mixture is filtered, centrifuged, or precipitated to remove the solid hydrogenation catalyst. The catalyst is regenerated and reused. Hydrogenated PAO can be used as is, or further distilled or fractionated into specific component compositions if necessary.

In some cases, if the hydrogenation catalyst does not show catalyst deactivation over a long period of operation, a stirred tank hydrogenation process can be carried out, in which case a fixed amount of catalyst, usually all reactants. 0.1 to 10% by weight of the reactor is maintained in the reactor, only hydrogen and PAO feed need be added at a continuous feed rate, and only hydrogenated PAO is withdrawn from the reactor.

The hydrogenation process can also be accomplished by a fixed bed process in which a solid catalyst is placed inside a tubular reactor and heated to the reactor temperature. Hydrogen and PAO feed can be fed simultaneously or countercurrently through the top or bottom of the reactor, thereby maximizing contact between hydrogen, PAO and catalyst and allowing for the best thermal management.

PAO and hydrogen feed rates are adjusted to provide adequate residence time, thereby fully hydrogenating unsaturated olefins in the feed and / or allowing conversion of mm triplets in the process as desired. Like that. The hydrogenated PAO fluid can be used as is, or can be further distilled or fractionated to obtain the appropriate components if necessary. Usually the final hydrocarbon PAO fluid has a bromine number less than 2.

When new polyalphaolefins are blended alone or with other fluids, they have unique lubricating properties.

In another embodiment, the new lubricants of the present invention are PAOs produced according to the present invention, as well as I to VI groups having a viscosity range of 1.5 to 100 cSt at 100 ° C. to prepare a suitable viscosity grade. Including one or more other base ingredients, including a base stock. In addition, one or more additives may be added: thickeners, VI improvers, antioxidants, anti-wear additives, detergent / dispersant / inhibitor (DDI) packages, and / or rust inhibitors. . In certain preferred embodiments, the PAO of the present invention comprises one or more dispersants, detergents, friction modifiers, tack friction modifiers, demulsifiers, chromophores (dyes), and / or haze suppression. You may combine with an agent. These well-prepared lubricants can be used in automotive crankcase oil (engine oil), industrial oil, grease, hydraulic, gear oil, heat transfer fluid or gas turbine engine oil. These are examples of additives in finished lubricant formulations. “Synthetic Lubricants and High-Performance Functional Fluids”, 2nd edition, for further information on the use of PAO in the formulation of fully synthetic, semi-synthetic or partially synthetic lubricants or functional fluids As described in L. Rudnick et al., Marcel Dekker, Inc., NY (1999). More information on additives used in product formulations can be found in Lubricants and Lubrications, edited by T. Mang and W. Dresel, Wiley-VCH GmbH, Weinheim 2001 publication.

In other embodiments, the invention relates to:
1. A process for producing a liquid polyalphaolefin (PAO) having a KV ₁₀₀ of greater than 20 cSt and up to about 10,000 cSt (30 to 7500 cSt, preferably 40 to 5000 cSt), the process comprising:
Contacting one or more alpha-olefin monomers having 3 to 24 carbon atoms with a non-bridged substituted bis (cyclopentadienyl) transition metal compound, the compound comprising:
(Cp) (Cp *) MX ₁ X ₂
Wherein M is a metal center and is a Group 4 metal, preferably Ti, Hf or Zr, more preferably Hf or Zr;
Cp and Cp * are each the same or different cyclopentadienyl ring bonded to M, 1) Cp and Cp * are both substituted with at least one non-hydrogen substituent R, or 2) Cp is Substituted with 2 to 5 substituents R, each substituent R being independently a radical group that is hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, or Cp and Cp * The same or different cyclopenta, optionally any two adjacent R groups linked to form a substituted, unsubstituted, saturated, partially unsaturated or aromatic cyclic or polycyclic substituent A dienyl ring;
X ₁ and X ₂ are independently hydrogen, halogen, hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, silylcarbyl radical, substituted silylcarbyl radical, germylcarbyl A radical or a substituted germylcarbyl radical;
Or both X are linked and bonded to a metal atom to form a metal ring containing from about 3 to about 20 carbon atoms; or both together can be an olefin, diolefin or an aligned ligand; And under polymerization conditions, a non-coordinating anionic activator, and optionally an alkylaluminum compound, wherein the molar ratio of transition metal compound to activator is 10: 1 to 0.1: 1, and an alkylaluminum compound is present The molar ratio of alkylaluminum compound to transition metal compound is from 1: 4 to 4000: 1;
The polymerization conditions are
i) Hydrogen is present at a partial pressure of 0.1 to 300 psi based on the total pressure of the reactor, or the concentration of hydrogen is 1 to 30,000 ppm or less by weight (preferably 1 to 20,000 ppm or less by weight);
ii) alpha-olefin monomer having 3 to 24 carbon atoms is present in an amount of 10% by weight or more based on the total weight of catalyst / activator / alkylaluminum compound solution, monomer and all diluents or solvents present during the reaction;
iii) provided that no ethylene is present in excess of 40% by weight of the monomer entering the reactor.

2. The process of paragraph 1, wherein Cp and Cp * are both substituted with at least one non-isoalkyl substituent, wherein the isoalkyl substituent is defined as CH (R *) ₂ , wherein each R * is independently from C ₁ C _{20 is} an alkyl group.

3. The process of paragraph 1 or 2, wherein both Cp and Cp * are substituted with 2 to 5 non-hydrogen substituents.

4). 4. The process of any one of paragraphs 1 to 3, wherein both Cp and Cp * are substituted with 2 to 5 non-hydrogen substituents.

5. 5. The process of any one of paragraphs 1 to 4, wherein the transition metal compound is a non-bridged, substituted bis (cyclopentadienyl) transition metal compound represented by the following chemical formula:

Where M is a Group 4 metal, preferably Ti, Hf or Zr, more preferably Hf or Zr;
Each X is independently hydrogen, halogen, hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, silylcarbyl radical, substituted silylcarbyl radical, germylcarbyl radical, or substitution A germylcarbyl radical; or both X are linked and bonded to a metal atom to form a metal ring containing from 3 to 20 carbon atoms; or both X together are an olefin, diolefin, or aligning ligand. Preferably each X is independently a C1 to C20 hydrocarbyl or halogen, more preferably each X is independently a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, or dodecyl group. Or halogen is chloride or bromide;
R ¹ to R ¹⁰ are each independently a radical group that is hydrogen, heteroatom, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, provided that at least one of R ¹ to R ⁵ is Not hydrogen, at least one of R ⁶ to R ¹⁰ is not hydrogen, and two adjacent R groups are optionally linked, substituted or unsubstituted, saturated, partially unsaturated or aromatic ring Or, provided that it forms a polycyclic substituent, preferably R1 to R10 are selected from hydrogen, C1 to C30 hydrocarbyl, substituted C1 to C30 hydrocarbyl groups or heteroatoms.

6). The process of paragraph 5 further includes: 1) at least one of R ¹ to R ⁵ is not hydrogen and is a non-iso-alkyl substituent, and at least one of R ⁶ to R ¹⁰ is not hydrogen and is non-iso-alkyl Or 2) at least two of R ¹ to R ⁵ are not hydrogen, or 3) at least two of R ¹ to R ⁵ are not hydrogen, and at least two of R ⁶ to R ¹⁰ are Not hydrogen.

7). The process of paragraph 5 or 6, wherein 3 or 4 or ⁵ of R ¹ to R ⁵ are not hydrogen.

8). The process of paragraph 5 or 6, wherein 3 or 4 or 5 of R ⁶ to R ¹⁰ are not hydrogen.

9. The process according to any one of items 5 to 8, wherein one of R ¹ to R ⁵ is isoalkyl, at least one of R ¹ to R ⁵ is not hydrogen, and if R ⁶ If one of R ¹⁰ is isoalkyl, at least the other of R ⁶ to R ¹⁰ is not hydrogen.

10. The process according to any one of Items 5 to 9, wherein none of R ¹ to R ¹⁰ is an isoalkyl group.

11. 10. The process of any one of paragraphs 5-9, wherein two adjacent R groups form one of an indenyl, tetrahydroindenyl, substituted indenyl, substituted tetrahydroindenyl, fluorenyl, or substituted fluorenyl group.

12 The process according to any one of Items 1 to 11, wherein PAO has a pour point of 10 ° C or less, preferably 0 ° C, preferably -15 ° C or less, preferably -25 ° C or less. good.

13. The process of any one of paragraphs 1-12, wherein the polyalphaolefin has a Mw / Mn of 1 to 3.5, preferably a Mw / Mn of 1 to 2.6.

14 14. The process according to any one of items 1 to 13, wherein the polyalphaolefin is polydecene.

15. 15. The process according to any one of items 1 to 14, wherein the polyalphaolefin has a bromine number of 1.8 or more.

16. 16. The process of any one of paragraphs 1-15, wherein the polyalphaolefin has a vinylidene content greater than 50 mol% and a kinematic viscosity at 100 ° C. of less than 3000 cSt.

17. The process according to any one of items 1 to 16, wherein the polyalphaolefin is
It has a methyl content below X, where X = −3.4309 Ln (kinematic viscosity at 100 ° C., cSt) +29.567.

18. 18. The process of any one of paragraphs 1-17, further comprising the step of obtaining a polyalphaolefin and subsequently hydrogenating the polyalphaolefin, wherein the polyalphaolefin is at least one C3 to C24 alpha. The hydride product has a bromine number not exceeding 1.8, containing at least 50 mol% of olefin monomers.

19. 19. The process of any one of paragraphs 1-18, wherein the polyalphaolefin has a kinematic viscosity at 40 ° C. of 50 to 100,000 cSt.

20. Item 20. The process of any one of Items 1-19, wherein the polyalphaolefin has a viscosity index of 50 or greater, preferably 100 to 450.

21. Item 21. The process of any one of Items 1 to 20, wherein the polyalphaolefin has a weight average molecular weight of 250 to 200,000 g / mol, preferably 250 to 100,000 g / mol. .

22. Item 2. The process according to any one of Items 1 to 21, wherein the monomer having 3 to 24 carbon atoms is present in an amount of 60% by weight or more, preferably 70% by weight or more.

23. 23. The process of any one of paragraphs 1 to 22, wherein the polyalphaolefin is selected from the group consisting of: propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1 -Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene 1-uneicosene, 1-docosene, 1-tricosene, 1-tetracocene, 1-pentacocene, 1-hexacocene, 4-methyl-1-pentene, 4-phenyl-1-butene, and 5-phenyl-1-pentene; preferably poly The alpha olefin is selected from the group consisting of: propylene, 1-butene, 1-pentene, 1-hexene, 1-he Ten, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene,
1-pentadecene, and 1-hexadecene; more preferably the polyalphaolefin is selected from the group consisting of: 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene And more preferably the polyalphaolefins include octene, decene, and dodecene; alternatively the polyalphaolefins are hexene, decene, and dodecene, or hexene, decene, and tetradecene; or butene, hexene, and Dodecene; or propylene, butene and dodecene.

24. 24. The process according to any one of items 1 to 23, wherein the polyalphaolefin has a flash point of 150 ° C. or higher.

25. 25. The process according to any one of items 1 to 24, wherein the polyalphaolefin has a specific gravity of 0.6 to 0.9 g / cm ³ .

26. 26. The process of any one of paragraphs 1 to 25, wherein the ethylene, propylene and butene monomers are present in an amount less than 1% by weight.

27. The process of any one of paragraphs 1 to 43, wherein the propylene and / or butene monomer is present at least 1% by weight, preferably up to 100% by weight in pure polypropylene or butene or a combination of both. Is good.

28. 45. The process of any one of paragraphs 1 to 44, wherein ethylene is less than 30 wt%, preferably less than 20 wt%, preferably less than 10 wt%, preferably less than 5 wt%, based on the weight of the raw material. Preferably it is present in less than 1% by weight.

29. 29. The process according to any one of items 1 to 28, wherein the monomer having 3 to 24 carbon atoms is present in an amount of 60 mol% or more, preferably 70 mol% or more.

30. 30. The process of any one of paragraphs 1 to 29, wherein the process further includes:
1) optionally treating the polyalphaolefin to reduce the heteroatom-containing compound to less than 600 ppm;
2) optionally separating the polyalphaolefin from the solvent or diluent and other light product parts;
3) contacting the polyalphaolefin with hydrogen and a hydrogenation catalyst; and 4) obtaining a conventional polyalphaolefin with a bromine number of less than 1.8.

31. 30. The process of paragraph 30, wherein the polyalphaolefin is treated to remove heteroatom-containing compounds prior to contacting with hydrogen and / or the hydrogenation catalyst, preferably the treated polyalphaolefin is less than 100 ppm heterogeneous. Preferably, the treated polyalphaolefins contain less than 10 ppm of heteroatom containing compounds.

32. The process of any one of paragraphs 1 to 31, wherein a scavenger is present and the scavenger comprises methylalumoxane and / or modified methylalumoxane.

33. Item 33. The process of any one of Items 1 to 32, wherein the non-coordinating anion activator comprises one or more of the following:
N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate
(N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate),
N, N-dialkylanilinium tetrakis (pentafluorophenyl) borate
(N, N-dialkylanilinium tetrakis (pentafluorophenyl) borate),
Tetrakis (pentafluorophenyl) borate
(tetrakis (pentafluorophenyl) borate),
Tri (pentafluorophenyl) borate
(tri (pentafluorophenyl) borate),
Tri-alkylammonium tetrakis (pentafluorophenyl) borate
(tri-alkylammonium tetrakis (pentafluorophenyl) borate),
Tetra-alkylammonium tetrakis (pentafluorophenyl) borate
(tetrai-alkylammonium tetrakis (pentafluorophenyl) borate),
N, N-dimethylanilinium tetrakis (perfluorophenyl) borate
(N, N-dimethylanilinium tetrakis (perfluorophenyl) borate),
N, N-dialkylanilinium tetrakis (perfluorophenyl) borate
(N, N-dialkylanilinium tetrakis (perfluorophenyl) borate),
Trityltetrakis (perfluorophenyl) borate
(trityl tetrakis (perfluorophenyl) borate),
Tri (perfluorophenyl) borate
(tri (perfluorophenyl) borate),
Tri-alkylammonium tetrakis (perfluorophenyl) borate
(tri-alkylammonium tetrakis (perfluorophenyl) borate),
Tetra-alkylammonium tetrakis (perfluorophenyl) borate
(tetrai-alkylammonium tetrakis (perfluorophenyl) borate),
Here, the alkyl group is preferably a C1 to C18 alkyl group.

34. 34. The process of any one of paragraphs 1 to 33, wherein the transition metal comprises one or more of the following:
(bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride)
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride)
bis (1,3-Dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride)
bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dichloride)
bis (1,2,3,4-tetrahydroindenyl) zirconium dichloride
(bis (1,2,3,4-tetrahydroindenyl) zirconium dichloride)
bis (tetramethylcyclopentadienyl) zirconium dichloride
(bis (tetramethylcyclopentadienyl) zirconium dichloride)
bis (pentamethylcyclopentadienyl) zirconium dichloride
(bis (pentamethylcyclopentadienyl) zirconium dichloride)
bis (indenyl) zirconium dichloride
(bis (indenyl) zirconium dichloride)
bis (l, 2,4-trimethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dimethyl)
bis (l, 2,3-trimethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dimethyl)
bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl
(bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl)
bis (tetramethylcyclopentadienyl) zirconium dimethyl
(bis (tetramethylcyclopentadienyl) zirconium dimethyl)
bis (pentamethylcyclopentadienyl) zirconium dimethyl
(bis (pentamethylcyclopentadienyl) zirconium dimethyl) or
bis (1,2,3,4-tetrahydroindenyl) zirconium dimethyl.

35. The process of any one of paragraphs 1 to 33, wherein the transition metal comprises one or more of the following:
bis (1,2-dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride))
bis (1,3-Dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride)
bis (1,2,3-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dichloride)
bis (1,2,4-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride)
bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride)
bis (l, 2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3,4,5-pentamethylcyclopentadienyl) zirconium dichloride)
bis (l-Methyl-2-ethylcyclopentadienyl) zirconium dichloride
(bis (l -methyl -2-ethylcyclopentadienyl) zirconium dichloride)
bis (l-methyl-2-n-propylcyclopentadienyl) zirconium dichloride
(bis (l-methyl-2-n-propylcyclopentadienyl) zirconium dichloride)
bis (l-methyl-2-n-butylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-2-n-butyllcyclopentadienyl) zirconium dichloride)
bis (l-methyl-3-ethylcyclopentadienyl) zirconium dichloride
(bis (l-methyl-3-ethylcyclopentadienyl) zirconium dichloride)
bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-3-n-propylcyclopentadienytyzirconium dichloride)
bis (l-Methyl-3-n-butylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-3-n-butylcyclopentadienytyzirconium dichloride)
bis ((l-methyl-3-n-pentylcyclopentadienyl) zirconium dichloride
(bis (l-methyl-3-n-pentylcyclopentadienyl) zirconium dichloride)
bis (l, 2-dimethyl-4-ethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethyl-4-ethylcyclopentadienyl) zirconium dichloride)
bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) zirconium dichloride)
bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) zirconium dichloride)
bis (l, 2-diethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-diethylcyclopentadienyl) zirconium dichloride)
bis (l, 3-diethylcyclopentadienyl) zirconium dichloride
(bis (l, 3-diethylcyclopentadienyl) zirconium dichloride)
bis (l, 2-di-n-propylcyclopentadienyl) zirconium dichloride
(bis (l, 2-di-n-propylcyclopentadienyl) zirconium dichloride)
bis (l, 2-di-n-butylcyclopentadienyl) zirconium dichloride
(bis (1,2-di-n-butylcyclopentadienyl) zirconium dichloride)
bis (1-Methyl-2,4-diethylcyclopentadienyl) zirconium dichloride
(bis (1-methyl-2,4-diethylcyclopentadienyl) zirconium dichloride)
bis (1,2-diethyl-4-n-propylcyclopentadienyl) zirconium dichloride
(bis (1,2-diethyl-4-n-propylcyclopentadienyl) zirconium dichloride)
bis (1,2-diethyl-4-n-butylcyclopentadienyl) zirconium dichloride
(bis (l, 2-diethyl-4-n-butylcyclopentadienytyzirconium dichloride)
bis (l-methyl-3-i-propylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-3-i-propylcyclopentadienyl) zirconium dichloride)
bis (l-ethyl-3-i-propylcyclopentadienyl) zirconium dichloride
(bis (l -ethyl -3-i-propylcyclopentadienyl) zirconium dichloride)
(1,2-Dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride
(l, 2-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride)
(1,3-Dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride
(1, 3 -dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride)
(1, 2-Dimethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dichloride
(1, 2-dimethylcyclopentadienyl) (methylcyclopentadienyl) zirconiurn dichloride)
(1,2-Dimethyldimethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride
(1,2-dimethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dichloride)
(1,2-Dimethyldimethylcyclopentadienyl) (l, 2-di-n-butylcyclopentadienyl) zirconium dichloride
(1,2,2-dimethylcyclopentadienyl) (l, 2-di-n-butylcyclopentadienyl) zirconium dichloride)
(1,3-Dimethyldimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride
(l, 3-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dichloride)
(1,3-Dimethyldimethylcyclopentadienyl) (1,2-dimethylcyclopentadienyl) zirconium dichloride
(l, 3-dimethylcyclopentadienyl) (l, 2-dimethylcyclopentadienyl) zirconium dichloride)
(1,3-Dimethyldimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) zirconium dichloride
(1,3-dimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) zirconium dichloride)
bis (indenyl) zirconium dichloride
(bis (indenyl) zirconium dichloride)
bis (1-methylindenyl) zirconium dichloride
(bis (l -methylindenyl) zirconium dichloride)
bis (2-methylindenyl) zirconium dichloride
bis (4-methylindenyl) zirconium dichloride
bis (4,7-dimethylindenyl) zirconium dichloride
bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride
(bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride)
bis (4,5,6,7-tetrahydro-2-methylindenyl) zirconium dichloride (bis (4,5,6,7-tetrahydro-2-methylindenyl) zirconium dichloride)
bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) zirconium dichloride (bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) zirconium dichloride)
(Cyclopentadienyl) (4,5,6,7-tetrahydro-4,7-dimethylindenyl) zirconium dichloride
(cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) zirconium dichloride)
bis (l, 2-dimethyl) cyclopentadienyl) zirconium dimethyl
(bis (l, 2-dimethyl) cyclopentadienyl) zirconium dimethyl)
bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl
(bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl)
bis (l, 2,3-trimethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2,3-trimethylcyclopentadienyl) zirconium dimethyl)
bis (l, 2,4-trimethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2, 4-trimethylcyclopentadienyl) zirconium dimethyl)
bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2,3,4,5-tetramethylcyclopentadienyl) zirconium dimethyl)
bis (l, 2,3,4-pentamethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2,3,4,5-pentamethylcyclopentadienyl) zirconium dimethyl)
bis (1-Methyl-2-ethylcyclopentadienyl) zirconium dimethyl
(bis (1-methyl-2-ethylcyclopentadienyl) zirconium dimethyl)
bis (1-Methyl-2-n-propylcyclopentadienyl) zirconium dimethyl
(bis (1-methyl-2-n-propylcyclopentadienyl) zirconium dimethyl)
bis (1-Methyl-2-n-butylcyclopentadienyl) zirconium dimethyl
(bis (1-methyl-2-n-butylcyclopentadienyl) zirconium dimethyl)
bis (1-methyl-3-ethylcyclopentadienyl) zirconium dimethyl
bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dimethyl
bis (l-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl
bis (l, 2-dimethyl-4-ethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2-dimethyl-4-ethylcyclopentadienyl) zirconium dimethyl)
bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) zirconium dimethyl
(bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) zirconium dimethyl)
bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) zirconium dimethyl
(bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) zirconium dimethyl)
bis (l, 2-diethylcyclopentadienyl) zirconium dimethyl
(bis (l, 2-diethylcyclopentadienyl) zirconium dimethyl)
bis ((l, 3-diethylcyclopentadienyl) zirconium dimethyl
(bis (l, 3-diethylcyclopentadienyl) zirconium dimethyl)
bis (l, 2-di-n-propylcyclopentadienyl) zirconium dimethyl
(bis (l, 2-di-n-propylcyclopentadienyl) zirconium dimethyl)
bis (l, 2-di-n-butylcyclopentadienyl) zirconium dimethyl
(bis (1,2-di-n-butylcyclopentadienyl) zirconium dimethyl)
bis (1-Methyl-2,4-diethylcyclopentadienyl) zirconium dimethyl
(bis (1-methyl-2,4-diethylcyclopentadienyl) zirconium dimethyl)
bis (1,2-Diethyl-4-n-propylcyclopentadienyl) zirconium dimethyl
(bis (1, 2-diethyl-4-n-propylcyclopentadienyl) zirconium dimethyl)
bis (1,2-Diethyl-4-n-butylcyclopentadienyl) zirconium dimethyl
(bis (l, 2-diethyl-4-n-butylcyclopentadienytyzirconium dimethyl)
bis (l-methyl-3-i-propylcyclopentadienyl) zirconium dimethyl
(bis (l -methyl-3-i-propylcyclopentadienyl) zirconium dimethyl)
bis (l-ethyl-3-i-propylcyclopentadienyl) zirconium dimethyl
(bis (l -ethyl -3-i-propylcyclopentadienyl) zirconium dimethyl)
(1,2-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl
(l, 2-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl)
(1,3-Dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl
(1, 3 -dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl)
(1,2-Dimethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dimethyl
(1, 2-dimethylcyclopentadienyl) (methylcyclopentadienyl) zirconium dimethyl)
(1,2-Dimethyldimethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dimethyl
(1,2-dimethylcyclopentadienyl) (ethylcyclopentadienyl) zirconium dimethyl)
(1,2-dimethyldimethylcyclopentadienyl) ((l, 2-di-n-butylcyclopentadienyl) zirconium dimethyl
(1, 2-dimethylcyclopentadienyl) (l, 2-di-n-butylcyclopentadienyl) zirconium dimethyl)
(1,3-Dimethyldimethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl
(l, 3-dimethylcyclopentadienyl) (cyclopentadienyl) zirconium dimethyl)
(1,3-dimethyldimethylcyclopentadienyl) (1,2-dimethylcyclopentadienyl) zirconium dimethyl
(l, 3-dimethylcyclopentadienyl) (l, 2-dimethylcyclopentadienyl) zirconium dimethyl)
(1,3-Dimethyldimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) zirconium dimethyl
(1,3-dimethylcyclopentadienyl)-(1,3-diethylcyclopentadienyl) zirconium dimethyl)
bis (indenyl) zirconium dimethyl
(bis (indenyl) zirconium dimethyl)
bis (1-methylindenyl) zirconium dimethyl
(bis (l -methylindenyl) zirconium dimethyl)
bis (2-methylindenyl) zirconium dimethyl
bis (4-methylindenyl) zirconium dimethyl
bis (4,7-dimethylindenyl) zirconium dimethyl
bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl
(bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl)
bis (4,5,6,7-tetrahydro-2-methylindenyl) zirconium dimethyl
bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) zirconium dimethyl (bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) zirconium dimethyl)
(Cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) zirconium dimethyl
(cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) zirconium dimethyl)
35. The process of any one of paragraphs 1 to 33, wherein the transition metal comprises one or more of the following:
bis (1,2-Dimethylcyclopentadienyl) hafnium dichloride
(bis (l, 2-dimethylcyclopentadienyl) hafnium dichloride))
bis (1,3-Dimethylcyclopentadienyl) hafnium dichloride
(bis (l, 3-dimethylcyclopentadienyl) hafnium dichloride)
bis (1,2,3-trimethylcyclopentadienyl) hafnium dichloride
(bis (l, 2,3-trimethylcyclopentadienyl) hafnium dichloride)
bis (1,2,4-trimethylcyclopentadienyl) hafnium dichloride
(bis (l, 2,4-trimethylcyclopentadienyl) hafnium dichloride)
bis (l, 2,3,4-tetramethylcyclopentadienyl) hafnium dichloride
(bis (l, 2,3,4-tetramethylcyclopentadienyl) hafnium dichloride)
bis (l, 2,3,4,5-pentamethylcyclopentadienyl) hafnium dichloride
(bis (l, 2,3,4,5-pentamethylcyclopentadienyl) hafnium dichloride)
bis (l-Methyl-2-ethylcyclopentadienyl) hafnium dichloride
(bis (l -methyl-2-ethylcyclopentadienyl) hafnium dichloride)
bis (l-methyl-2-n-propylcyclopentadienyl) hafnium dichloride
(bis (l-methyl-2-n-propylcyclopentadienyl) hafnium dichloride)
bis (l-Methyl-2-n-butylcyclopentadienyl) hafnium dichloride
(bis (l -methyl-2-n-butyllcyclopentadienyl) hafnium dichloride)
bis (l-Methyl-3-ethylcyclopentadienyl) hafnium dichloride
(bis (l-methyl-3-ethylcyclopentadienyl) hafnium dichloride)
bis (l-Methyl-3-n-propylcyclopentadienyl) hafnium dichloride
(bis (l -methyl-3-n-propylcyclopentadienytyhafnium dichloride)
bis (l-Methyl-3-n-butylcyclopentadienyl) hafnium dichloride
(bis (l -methyl-3-n-butylcyclopentadienytyhafnium dichloride)
bis ((l-methyl-3-n-pentylcyclopentadienyl) hafnium dichloride
(bis (l-methyl-3-n-pentylcyclopentadienyl) hafnium dichloride)
bis (l, 2-Dimethyl-4-ethylcyclopentadienyl) hafnium dichloride
(bis (l, 2-dimethyl-4-ethylcyclopentadienyl) hafnium dichloride)
bis (l, 2-Dimethyl-4-n-propylcyclopentadienyl) hafnium dichloride
(bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) hafnium dichloride)
bis (l, 2-Dimethyl-4-n-butylcyclopentadienyl) hafnium dichloride
(bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) hafnium dichloride)
bis (l, 2-diethylcyclopentadienyl) hafnium dichloride
(bis (l, 2-diethylcyclopentadienyl) hafnium dichloride)
bis (l, 3-diethylcyclopentadienyl) hafnium dichloride
(bis (l, 3-diethylcyclopentadienyl) hafnium dichloride)
bis (l, 2-di-n-propylcyclopentadienyl) hafnium dichloride
(bis (l, 2-di-n-propylcyclopentadienyl) hafnium dichloride)
bis (l, 2-di-n-butylcyclopentadienyl) hafnium dichloride
(bis (1,2-di-n-butylcyclopentadienyl) hafnium dichloride)
bis (1-Methyl-2,4-diethylcyclopentadienyl) hafnium dichloride
(bis (1-methyl-2,4-diethylcyclopentadienyl) hafnium dichloride)
bis (1,2-diethyl-4-n-propylcyclopentadienyl) hafnium dichloride
(bis (1,2-diethyl-4-n-propylcyclopentadienyl) hafnium dichloride)
bis (1,2-diethyl-4-n-butylcyclopentadienyl) hafnium dichloride
(bis (l, 2-diethyl-4-n-butylcyclopentadienytyhafnium dichloride)
bis (l-methyl-3-i-propylcyclopentadienyl) hafnium dichloride
(bis (l -methyl-3-i-propylcyclopentadienyl) hafnium dichloride)
bis (l-ethyl-3-i-propylcyclopentadienyl) hafnium dichloride
(bis (l -ethyl -3-i-propylcyclopentadienyl) hafnium dichloride)
(1,2-Dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dichloride
(l, 2-dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dichloride)
(1,3-Dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dichloride
(1, 3 -dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dichloride)
(1,2-Dimethylcyclopentadienyl) (methylcyclopentadienyl) hafnium dichloride
(1, 2-dimethylcyclopentadienyl) (methylcyclopentadienyl) zirconiurn dichloride)
(1, 2-Dimethyldimethylcyclopentadienyl) (ethylcyclopentadienyl) hafnium dichloride
(1,2-dimethylcyclopentadienyl) (ethylcyclopentadienyl) hafnium dichloride)
(1,2-Dimethyldimethylcyclopentadienyl) (l, 2-di-n-butylcyclopentadienyl) hafnium dichloride
(1, 2-dimethylcyclopentadienyl) (l, 2-di-n-butylcyclopentadienyl) hafnium dichloride)
(1,3-Dimethyldimethylcyclopentadienyl) (cyclopentadienyl) hafnium dichloride
(l, 3-dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dichloride)
(1,3-dimethyldimethylcyclopentadienyl) (1,2-dimethylcyclopentadienyl) hafnium dichloride
(l, 3-dimethylcyclopentadienyl) (l, 2-dimethylcyclopentadienyl) hafnium dichloride)
(1,3-dimethyldimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) hafnium dichloride
(1,3-dimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) hafnium dichloride)
bis (indenyl) hafnium dichloride
(bis (indenyl) hafnium dichloride)
bis (1-methylindenyl) hafnium dichloride
(bis (l -methylindenyl) hafnium dichloride)
bis (2-methylindenyl) hafnium dichloride
bis (4-methylindenyl) hafnium dichloride
bis (4,7-dimethylindenyl) hafnium dichloride
bis (4,5,6,7-tetrahydroindenyl) hafnium dichloride
(bis (4,5,6,7-tetrahydroindenyl) hafnium dichloride)
bis (4,5,6,7-tetrahydro-2-methylindenyl) hafnium dichloride
bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) hafnium dichloride (bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) hafnium dichloride)
(Cyclopentadienyl) (4,5,6,7-tetrahydro-4,7-dimethylindenyl) hafnium dichloride
(cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) hafnium dichloride)
bis (l, 2-dimethyl) cyclopentadienyl) hafnium dimethyl
(bis (l, 2-dimethyl) cyclopentadienyl) hafnium dimethyl)
bis (l, 3-dimethyl) cyclopentadienyl) hafnium dimethyl
(bis (l, 3-dimethyl) cyclopentadienyl) hafnium dimethyl)
bis (l, 2,3-trimethylcyclopentadienyl) hafnium dimethyl
(bis (l, 2,3-trimethylcyclopentadienyl) hafnium dimethyl)
bis (l, 2,4-trimethylcyclopentadienyl) hafnium dimethyl
(bis (l, 2, 4-trimethylcyclopentadienyl) hafnium dimethyl)
bis (l, 2,3,4-tetramethylcyclopentadienyl) hafnium dimethyl
(bis (l, 2,3,4,5-tetramethylcyclopentadienyl) hafnium dimethyl)
bis (l, 2,3,4-pentamethylcyclopentadienyl) hafnium dimethyl
(bis (l, 2,3,4,5-pentamethylcyclopentadienyl) hafnium dimethyl)
bis (1-Methyl-2-ethylcyclopentadienyl) hafnium dimethyl
(bis (1-methyl-2-ethylcyclopentadienyl) hafnium dimethyl)
bis (1-Methyl-2-n-propylcyclopentadienyl) hafnium dimethyl
(bis (1-methyl-2-n-propylcyclopentadienyl) hafnium dimethyl)
bis (1-Methyl-2-n-butylcyclopentadienyl) hafnium dimethyl
(bis (1-methyl-2-n-butylcyclopentadienyl) hafnium dimethyl)
bis (1-methyl-3-ethylcyclopentadienyl) hafnium dimethyl)
bis (l-methyl-3-n-propylcyclopentadienyl) hafnium dimethyl
bis (1-methyl-3-n-butylcyclopentadienyl) hafnium dimethyl
bis (l, 2-Dimethyl-4-ethylcyclopentadienyl) hafnium dimethyl
(bis (l, 2-dimethyl-4-ethylcyclopentadienyl) hafnium dimethyl)
bis (l, 2-Dimethyl-4-n-propylcyclopentadienyl) hafnium dimethyl
(bis (l, 2-dimethyl-4-n-propylcyclopentadienyl) hafnium dimethyl)
bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) hafnium dimethyl
(bis (l, 2-dimethyl-4-n-butylcyclopentadienyl) hafnium dimethyl)
bis (l, 2-diethylcyclopentadienyl) hafnium dimethyl
(bis (l, 2-diethylcyclopentadienyl) hafnium dimethyl)
bis ((l, 3-diethylcyclopentadienyl) hafnium dimethyl
(bis (l, 3-diethylcyclopentadienyl) hafnium dimethyl)
bis (l, 2-di-n-propylcyclopentadienyl) hafnium dimethyl
(bis (l, 2-di-n-propylcyclopentadienyl) hafnium dimethyl)
bis (l, 2-di-n-butylcyclopentadienyl) hafnium dimethyl
(bis (1,2-di-n-butylcyclopentadienyl) hafnium dimethyl)
bis (1-Methyl-2,4-diethylcyclopentadienyl) hafnium dimethyl
(bis (1-methyl-2,4-diethylcyclopentadienyl) hafnium dimethyl)
bis (1,2-diethyl-4-n-propylcyclopentadienyl) hafnium dimethyl
(bis (1,2-diethyl-4-n-propylcyclopentadienyl) hafnium dimethyl)
bis (1,2-Diethyl-4-n-butylcyclopentadienyl) hafnium dimethyl
(bis (l, 2-diethyl-4-n-butylcyclopentadienytyhafnium dimethyl)
bis (l-methyl-3-i-propylcyclopentadienyl) hafnium dimethyl
(bis (l -methyl-3-i-propylcyclopentadienyl) hafnium dimethyl)
bis (l-ethyl-3-i-propylcyclopentadienyl) hafnium dimethyl
(bis (l -ethyl -3-i-propylcyclopentadienyl) hafnium dimethyl)
(1,2-Dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dimethyl
(l, 2-dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dimethyl)
(1,3-Dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dimethyl
(1, 3 -dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dimethyl)
(1,2-Dimethylcyclopentadienyl) (methylcyclopentadienyl) hafnium dimethyl
(1, 2-dimethylcyclopentadienyl) (methylcyclopentadienyl) hafnium dimethyl)
(1,2-Dimethyldimethylcyclopentadienyl) (ethylcyclopentadienyl) hafnium dimethyl
(1,2-dimethylcyclopentadienyl) (ethylcyclopentadienyl) hafnium dimethyl)
(1,2-Dimethyldimethylcyclopentadienyl) ((l, 2-di-n-butylcyclopentadienyl) hafnium dimethyl
(1, 2-dimethylcyclopentadienyl) (l, 2-di-n-butylcyclopentadienyl) hafnium dimethyl)
(1,3-Dimethyldimethylcyclopentadienyl) (cyclopentadienyl) hafnium dimethyl
(l, 3-dimethylcyclopentadienyl) (cyclopentadienyl) hafnium dimethyl)
(1,3-Dimethyldimethylcyclopentadienyl) (1,2-dimethylcyclopentadienyl) hafnium dimethyl
(l, 3-dimethylcyclopentadienyl) (l, 2-dimethylcyclopentadienyl) hafnium dimethyl)
(1,3-Dimethyldimethylcyclopentadienyl) (1,3-diethylcyclopentadienyl) hafnium dimethyl
(1,3-dimethylcyclopentadienyl)-(1,3-diethylcyclopentadienyl) hafnium dimethyl)
bis (indenyl) hafnium dimethyl
(bis (indenyl) hafnium dimethyl)
bis (1-methylindenyl) hafnium dimethyl
(bis (l -methylindenyl) hafnium dimethyl)
bis (2-methylindenyl) hafnium dimethyl
bis (4-methylindenyl) hafnium dimethyl
bis (4,7-dimethylindenyl) hafnium dimethyl
bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl
(bis (4,5,6,7-tetrahydroindenyl) hafnium dimethyl)
bis (4,5,6,7-tetrahydro-2-methylindenyl) hafnium dimethyl
bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) hafnium dimethyl (bis (4,5,6,7-tetrahydro-4,7-dimethylindenyl) hafnium dimethyl)
(Cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) hafnium dimethyl
(cyclopentadienyl) (4,5,6,7-tetrahydroindenyl) hafnium dimethyl)
36. The process of any one of paragraphs 1 to 33, wherein the transition metal comprises one or more of the following:
bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2-dimethylcyclopentadienyl) zirconium dichloride),
bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride
(bis (l, 3-dimethylcyclopentadienyl) zirconium dichloride),
bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,4-trimethylcyclopentadienyl) zirconium dichloride)
bis (tetramethylcyclopentadienyl) zirconium dichloride
(bis (tetramethylcyclopentadienyl) zirconium dichloride),
bis (l-methyl-2-ethylcyclopentadienyl) zirconium dichloride
(bis (l -methyl-2-ethylcyclopentadienyl) zirconium dichloride),
bis (l-methyl-3-ethylcyclopentadienyl) zirconium dichloride dichloride),
bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dichloride,
bis (l-methyl-3-n-butylcyclopentadienyl) zirconium dichloride
(bis (l -methyl -3-n-butylclopentadienyl) zirconium dichloride)
bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride
(bis (4,5,6,7-tetrahydro indenyl) zirconium dichloride)
bis (indenyl) zirconium dichloride
(bis (indenyl) zirconium dichloride)
bis (l, 2-dimethyl) cyclopentadienyl) zirconium dimethyl
(bis (l, 2-dimethyl) cyclopentadienyl) zirconium dimethyl)
bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl
(bis (l, 3-dimethyl) cyclopentadienyl) zirconium dimethyl)
bis (tetramethylcyclopentadienyl) zirconium dimethyl
(bis (tetramethylcyclopentadienyl) zirconium dimethyl)
bis (1-Methyl-2-ethylcyclopentadienyl) zirconium dimethyl
(bis (1-methyl-2-ethylcyclopentadienyl) zirconium dimethyl)
bis (1-methyl-3-ethylcyclopentadienyl) zirconium dimethyl
bis (l-methyl-3-n-propylcyclopentadienyl) zirconium dimethyl
bis (l-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl
bis (4,5,6,7-tetrahydro indenyl) zirconium dichloride
bis (indenyl) zirconium dimethyl
(bis (indenyl) zirconium dimethyl),
37. The process of any one of paragraphs 1 to 36, wherein an alkylaluminum compound is present, wherein the alkylaluminum compound is represented by the formula R ′ ₃ Al, wherein each R ′ is independently methyl, ethyl N-propyl, iso-propyl, iso-butyl, n-butyl, t-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n -Octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and these Selected from the group consisting of iso-analogs.

38. The process of any one of paragraphs 1 to 37, wherein the process is a continuous process, preferably a continuous process comprising:
a) continuously introducing into the reactor a feed stream comprising at least 10% by weight of one or more C3 to C10 alpha-olefins;
b) continuously introducing the transition metal compound and the activator into the reactor;
c) optionally introducing a co-activator into the reactor; and
d) Continuously remove the polyalpha-olefin from the reactor.

39. 40. The process of paragraph 38, wherein the process further includes:
1) Optionally, continuously treat polyalphaolefins to reduce heteroatom-containing compounds below 600 ppm;
2) optionally continuously fractionating the polyalphaolefin to separate the light and heavy portions, the heavy portions containing 20 or more carbons;
3) Continuously contacting the polyalphaolefin with hydrogen and a hydrogenation catalyst; and 4) Obtaining a normal polyalphaolefin with a bromine number continuously less than 1.8.

40. 40. The process according to any one of items 1 to 39.
The temperature in the reactor is -10 ° C to 250 ° C, preferably 10 ° C to 220 ° C, preferably 20 ° C to 180 ° C, preferably 40 ° C to 150 ° C, preferably 30 ° C to 100 ° C. good.

41. 41. The process according to any one of items 1 to 40, wherein the monomer, catalyst compound and activator are contacted with a residence time of 5 minutes to 100 hours, preferably 10 minutes to 20 hours. good.

42. The process of any one of paragraphs 1 to 41, wherein a solvent or diluent is present, preferably the solvent or diluent is propane, butane, 2-butene, isobutene, pentane, hexane, heptane, octane. , Nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, benzene, toluene, o-xylene, m-xylene, p-xylene, mixed xylene, ethylbenzene, isopropylbenzene and n-butylbenzene It is good to be done.

43. 43. The process of any one of paragraphs 1-42, wherein the monomer is contacted with a transition metal compound and an activator in a reactor, and the reactor is a continuous stirred tank reactor.

44. Item 44. The process of any one of Items 1 to 43, wherein the catalyst residue is removed from the product by contact with a solid adsorbent.

45. 45. The process of any one of paragraphs 1 to 44, wherein the monomer is contacted with a transition metal compound and an activator in a liquid phase or a slurry phase.

46. 46. The process of any one of paragraphs 1 to 45, wherein the monomer is contacted with an alkylaluminum compound before being introduced into the reactor and / or the metallocene and / or activator is prior to entering the reactor. In combination with an alkylaluminum compound, preferably the alkylaluminum compound is selected from triisobutylaluminum, trie-n-octylaluminum, trie-n-hexylaluminum, trie-n-decylaluminum, trie-n-dodecylaluminum.

47. 47. The process of any one of paragraphs 1 to 46, wherein the polyalphaolefin is contacted with hydrogen and a hydrogenation catalyst, preferably the hydrogenation catalyst is from supported Group 7, 8, 9, and 10 metals. Preferably, the hydrogenation catalyst is selected from the group consisting of one or more of Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo, and W, silica, alumina, Supported on clay, titania, zirconia, mesoporous material, MCM-41 material, or mixed metal oxide, preferably the hydrogenation catalyst is diatomaceous earth, silica, alumina, clay, mesoporous material, MCM-41 or silica It may be nickel supported on alumina.

48. 48. The process of any one of paragraphs 1-47, wherein the polyalphaolefin is contacted with hydrogen and a hydrogenation catalyst at 25 ° C to 350 ° C.

49. 49. The process of any one of paragraphs 1 to 48, wherein the product produced comprises 60 wt% or less of C10 dimer, preferably 40 wt% or less of C10 dimer. .

50. 50. The process of any one of paragraphs 1 to 49, wherein the process further includes:
1) contacting the polyalphaolefin with a solid adsorbent to remove catalyst residues from the polyalphaolefin;
2) optionally treating the polyalphaolefin to reduce the heteroatom-containing compound to less than 600 ppm;
3) optionally fractionating the polyalphaolefins and separating the light and heavy parts, the heavy parts containing 20 or more carbons;
4) contacting the polyalphaolefin with hydrogen and a hydrogenation catalyst; and 5) obtaining a conventional polyalphaolefin with a bromine number of less than 1.8.

51. 51. The process of any one of paragraphs 1 to 50, wherein the process productivity is at least 1.5 kg product per gram of transition metal compound and / or the process productivity is non-coordinating anion per gram unit. At least 1.5 kg of product for the active agent.

52. 52. The process according to any one of items 1 to 51, wherein the process is semi-continuous.

53. 53. The process according to any one of items 1 to 52, wherein the temperature of the reaction zone does not rise above the 20 ° C. width during the reaction, preferably the temperature of the reaction zone rises above the 10 ° C. width during the reaction. Preferably, the temperature of the reaction zone does not rise above 5 ° C during the reaction, and preferably the temperature of the reaction zone does not rise above 3 ° C during the reaction.

54. 54. The process of any one of paragraphs 1 to 53, wherein the liquid polyalphaolefin product has a dimer of X wt% or less, wherein X wt% = 0.8 x [231.55 x (100 ° C. fluid Kv ^CSt ) ( ^-0.9046 )].

55. 55. The process of any one of paragraphs 1 to 54, wherein the liquid polyalphaolefin product has a mm or rr triplet portion of less than 40 moles, preferably the mm or rr triplet portion is less than 30 moles and less than 20 moles. There should be.

56. 56. The process of any one of paragraphs 1 to 55, wherein the liquid polyalphaolefin product has an mr triple of 50 mol% or more.

57. 56. The process of any one of paragraphs 1 to 56, wherein the liquid polyalphaolefin product does not have a melting point that can be measured by DSC.

58. 58. The process of any one of paragraphs 1 to 57, wherein the 1,2,2 substituted olefin is present in the polyalpha-olefin product in less than Z moles, Z = 8.420 * Log (V)-4.048, wherein V is the kinematic viscosity of the polyalphaolefin represented by cSt measured at 100 ° C., and Z is preferably 7 mol% or less, preferably 5 mol% or less.

59. 59. The process of any one of paragraphs 1 to 58, wherein the alpha-olefin has a unit represented by the following formula of less than Z-mol%:

Where j, k and m are each independently 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22, n is an integer from 1 to 350, and Z = 8.420 * Log (V) −4.048,
V is the kinematic viscosity due to cSt of polyalphaolefin measured at 100 ° C.

Examples Fluid properties were measured by the following standard methods and their commonly known methods, unless otherwise noted: Kinematic viscosities 40 ° C and 100 ° C cSt, ASTM D445 method; pour point ASTM Method according to D97; and viscosity index, method according to ASTM D 2270.

The following examples are for illustrative purposes and do not limit the invention.

1-decene used in all experiments was activated by calcining 1 liter of raw material with 20 grams of activated 13X molecular sieve (molecular sieve was calcined at 200 ° C. under a purged nitrogen flow for at least 4 hours. ) And 10 grams of Oxi-Clear catalyst (purchased from Altech Associates, Inc., Deerfield, IL) and mixed in a glove box under a dry nitrogen inert atmosphere for at least 2 days. The molecular sieve and deoxygenation catalyst were then removed by filtration in a glove box, and purified 1-decene was obtained. Alternatively, the feed was purified through a single bed of activated 13X molecular sieve in a nitrogen atmosphere.

The data in Table 1 was obtained as follows. The following continuous operation was carried out. 1-decene (40 ml / min) feed and metallocene catalyst, (bis (l-methyl-3-n-butylcyclopentadienyl) zirconium dimethyl) (bis (l-methyl-3-n-
butylcyclopentadienyl) zirconium dimethyl), and NCA activator, N, N-dimethylanilinium-tetrakis (pentafluorophenyl) borate, in toluene (2.482 ml / min) 1 micromol / ml solution of each and 4 micromol / ml (2.482 ml / min) of tri-n-octyl aluminum were fed into a 1 liter autoclave at a constant reaction temperature with stirring at 1000 rpm. It was. The reaction temperature was determined and controlled to be within ± 3 ° C of the temperature. The reaction residence time was 20 minutes. The product was continuously removed from the reactor and collected for characterization. The crude product was then treated with a small amount of water to deactivate the catalyst. The catalyst residue was removed by adding a small amount of solid-absorbing alumina, and the solid alumina was removed by filtration.

* Indicates that the reaction was carried out in series and a residual amount of hydrogen remained in the apparatus, so there was a slight amount of hydrogen in the reaction system.

Examples 1-7 are comparative PAOs in contrast to the PAOs of Examples 8 and 9 illustrating the present invention.

A crude product containing a known amount of n-hexadecane as an internal standard was analyzed by a gas chromatograph HP5890 model with a 30 m DBI column. This column separates hydrocarbons by boiling point. Column conditions: set by program to heat to 300 ⁰ C at initial temperature 70 ° C / 0 min, 10 ° C / min and maintain for 30 min. The conversion weight% of 1-decene, the weight% selectivity to the decene dimer and the high C ₃₀ or higher hydrocarbon lubrication fraction were calculated using gas chromatographic data using the internal standard method.

The crude product is fractionated in vacuo to remove light solvents such as toluene or hexane, and further fractionated in a high vacuum at 150 ° C. and below 0.1 mTorr to remove all of the unreacted decene and decene dimer C ₂₀ parts. Was removed.

Conversion and selectivity to C ₂₀ or lubricant portions by distillation method consistent with the results of the GC analysis. The kinematic viscosity at 40 ° C. and 100 ° C., VI, pour point and GPC of the lubricant part were measured by the standard methods described above. Catalyst productivity was calculated based on the weight of the total product or the weight of the lubricant product relative to the amount of metallocene and catalyst per gram used.

It should be noted that the processes in Table 1 all have high catalyst productivity, ranging from 4650 g to 8596 g product per gram catalyst (metallocene + activator). Lower selectivity to desired high selectivity and mild C ₂₀ parts with respect to the lubricant portion was observed in these runs.

Comparing Comparative Example 1-9 in Table 1 with Comparative Example 1-13 in Table 2 based on US Pat. No. 6,548,724, the present invention shows very low selectivity for dimer C20 through the VI range shown in FIG. I understand that.

This lower weight% C20 is particularly noticeable for products with viscosities greater than 20 cSt. Low selectivity for C20 means high selectivity for the lubricant part, which is desirable.

Examples of the present invention always produce less than 80% of the dimer of the comparative example. On average, the amount of dimer according to the comparative example of the prior art is defined by the following formula:
(Dimer weight%) = 231.55 × (kinematic viscosity at 100 ° C., cSt) ^(−0.90465) .

The upper limit of dimer weight% in the examples of the present invention is defined by the following formula:
(Dimer weight%) is 0.8 × 231.55 × [(kinematic viscosity at 100 ° C., cSt) ^(−0.90465) ] or less.

By using a metallocene with NCA as the catalyst, Examples 7-9 in Table 1 have a fairly high catalyst productivity, with product yields ranging from 4651 to 6477 g per gram of catalyst in fluids greater than 20 cSt. It is. In contrast, Examples 10, 12, and 13 of US Pat. No. 6,548,724 also produce fluids greater than 20 cSt, but with lower catalyst productivity, product yields 243 to 1197 per gram of catalyst. It is in the range of g.

The process of the present invention has higher catalyst productivity and a lower proportion of undesirable C20 by-products or results in higher production of lubricant. However, the quality of the lubricant does not change. The data in Table 1 shows that Examples 7-9 have very high VI, very low pour point and very narrow MWD. Narrow MWD is of interest in the sense of having excellent shear stability. These product characteristics are comparable to the high VI products of Examples 10, 12 and 13 of US Pat. No. 6,548,724. The following two graphs (FIGS. 3 and 4) show a comparison of VI and pour point between Example 1-9 in Table 1 and Examples 1 to 13 of US Pat. No. 6,548,724.

Formation of alpha-olefins greater than 20 cSt from 1-butene
100 g of pure 1-butene or 1-butene in a butene mixture was charged to a 600 ml autoclave at room temperature, followed by hydrogen (if hydrogen was present). The reactor was then heated to the reaction temperature. At the reaction temperature, a catalyst containing all catalyst components (metallocene, activator and triisobutylaluminum scavenger) was added to the reactor in two to three steps in order to keep the reactor temperature as constant as possible. The reaction was cooled after 16 hours and the lubricant product was separated in a manner similar to the run in Table 1. The results of the synthesis of poly-1-butene are summarized in Table 3. This data indicates that the catalytic activity is considerably higher than 1,200 g of product production per g of catalyst.

In a comparative example, methylalumoxane (MAO) activated metallocene was used as a catalyst for 1-butene polymerization, similar to the 1-butene polymerization procedure used in US Pat. No. 6,548,724. The results are summarized in Table 4.

Catalyst B = bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride
(bis (l, 2,3,4-tetramethylcyclopentadienyl) zirconium dichloride)
Catalyst C = bis (ethylcyclopentadienyl) zirconium dichloride
(bis (ethylcyclopentadienyl) zirconium dichloride)
As can be seen from the data, this catalyst system showed very low catalyst productivity—catalyst productivity ranging from 300 to 500 g product per g of catalyst. Compared to this, the embodiment of the present invention has a high catalyst productivity, and the lubricant production amount per g of the catalyst is usually higher than 1000 g.

The poly-1-butenes obtained in the present invention in Table 3 (Examples 10 to 21) are also very similar to the chemical composition of the poly-1-butene in Comparative Example shown in Table 4 analyzed by proton and ¹³ C NMR. Different. These are summarized in Table 3A and Table 4A, respectively.

When the mole% of vinylidene in the oligomer / polymer is plotted against the kinematic viscosity at 100 ° C. (FIG. 5), the amount of vinylidene olefin in the product is greater in the present invention than in the example based on competing methods. Clearly high. Similarly, when the amount of methyl branching per 1000 C is plotted against the kinematic viscosity at 100 ° C. (FIG. 6), the present invention shows that the amount of additional methyl branching is greater than in the example shown in the related art. Kaya is low. All these data indicate that the catalyst system of the present invention does not create additional methyl branches. The additional methyl branch produced in the process usually reduces the VI of the product and increases volatility, which is undesirable.

The production reaction of polyalphaolefins greater than 20 cSt from propylene was carried out in the same manner as in the case of 1-butene described above, except that polyethylene was used as a raw material. The results are shown in Table 5. This data shows that the use of metallocene and NCA in the presence of hydrogen produces a polyalpha-olefin lubricant product with high viscosity, high catalyst productivity and good lubricant properties (high VI and low pour point). Show.

Again, these data in Table 5 indicate that propylene has been converted to a functional fluid with good VI, high catalyst productivity, low selectivity for the light portion, and high selectivity for the lubricant portion.

All documents mentioned herein, including all priority documents and / or test procedures, are hereby incorporated by reference in their entirety as long as they do not conflict with the present specification. It will be apparent from the foregoing general description and specific embodiments that the forms of the invention herein have been described and illustrated but may be different without departing from the spirit and scope of the invention. Modification is possible. Accordingly, it is not intended that the present invention be limited thereby. Similarly, the term “comprising” is considered to have the same meaning as “including” for the purposes of Australian law.

Claims (8)

Liquid polyalpha having a kinematic viscosity of 100 ° C. to 10,000 cSt greater than 20 cSt (KV ₁₀₀₎ - A process for producing olefin (PAO), said process comprising:
a) contacting one or more alpha- olefin monomers having 3 to 24 carbon atoms with the following (1) and (2) constituting the catalyst,
(1) Non-bridged substituted bis (cyclopentadienyl) transition metal compound, which is represented by the formula (Cp) (Cp *) MX ₁ X _{2 in} which M is a metal center, Metal;
Cp and Cp * are each the same or different cyclopentadienyl ring attached to M;
1) Cp and Cp * are both substituted with at least one non-hydrogen substituent R, or 2) Cp is substituted with 2 to 5 substituents R, each substituent R being independently a hydrocarbyl Is a radical group that is a substituted hydrocarbyl, halocarbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl, or Cp and Cp * are optionally linked by any two adjacent R groups, substituted, unsubstituted, saturated The same or different cyclopentadienyl rings forming partially unsaturated or aromatic cyclic or polycyclic substituents;
X ₁ and X ₂ are independently hydrogen, halogen, hydride radical, hydrocarbyl radical, substituted hydrocarbyl radical, halocarbyl radical, substituted halocarbyl radical, silylcarbyl radical, substituted silylcarbyl radical, germylcarbyl A radical or a substituted germylcarbyl radical;
Or both X are linked and bonded to a metal atom to form a metal ring containing from 3 to 20 carbon atoms;
Or both together may be an olefin, diolefin, or an aligned ligand; and
(2) A non-coordinating anion activator and an alkylaluminum compound, the molar ratio of the transition metal compound to the activator being 10: 1 to 0.1: 1, and the molar ratio of the alkylaluminum compound to the transition metal compound being 1: 4 To 4000: 1; and
The alkylaluminum compound is represented by the formula R ′ ₃ Al, wherein each R ′ is independently methyl, ethyl, n-propyl, iso-propyl, iso-butyl, n-butyl, t-butyl, n-pentyl, iso-pentyl, neopentyl, n-hexyl, iso-hexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n- Selected from the group consisting of tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, and iso-analogs thereof,
The polymerization conditions applied are: 1) Hydrogen is present at a partial pressure of 0.1 to 300 psi based on the total pressure of the reactor, or the hydrogen concentration is 1 to 30,000 ppm or less by weight;
2) Alpha- olefin monomers having 3 to 24 carbon atoms are present in an amount of more than 10% by weight based on the total weight of catalyst / activator / alkylaluminum compound solution, monomers and all diluents or solvents present during the reaction. ;
3) provided that no ethylene is present in excess of 40% by weight of the monomer entering the reactor: and 4) a catalyst productivity greater than 4,650 g total product per gram catalyst, Based on the total grams of transition metal compound and activator; and
liquid polyalpha with b) a kinematic viscosity of 100 ° C. to 10,000 cSt greater than 20 cSt (KV ₁₀₀₎ - to produce olefin (PAO), the liquid polyalpha - olefin product has an X wt% or less of the dimer , Where X (wt%) = 0.8 * 231.55 * [KV ₁₀₀ (cSt unit)] ^(−0.90465) . Cp and Cp * are substituted with both at least one non-isoalkyl substituents, isoalkyl substituents are defined by CH (R *) _2, each R * is an alkyl group of C _{1 to} C ₂₀ independently The process of claim 1. The process of claim 1 wherein M is titanium, zirconium or hafnium. The process of claim 1 wherein each X is a C1 to C20 hydrocarbyl or halogen. The process of claim 1, wherein two adjacent R groups form one of an indenyl, tetrahydroindenyl, substituted indenyl, substituted tetrahydroindenyl, fluorenyl, or substituted fluorenyl group. The poly-alpha - olefins according to claim 1 having at least one characteristic of the following process:
a) Mw / Mn from 1 to 3.5;
b) a bromine number of 1.8 or more;
c) a vinylidene content greater than 50 mol%;
d) methyl content below y , where y = −3.4309 * Ln [KV ₁₀₀ (cSt units)] + 29.567 ;
e) Viscosity index greater than 50;
f) a weight average molecular weight of 250 to 200,000 g / mol;
g) Flash point above 150 ° C;
h) Specific gravity of 0.6 to 0.9 g / cm ³ . The poly-alpha - olefin is contacted with hydrogen and a supported 7, 8, 9, and a hydrogenation catalyst selected from the group consisting of Group 10 metals, the process of claim 1. A process according to claim 1, further 1) polyalpha - olefin is contacted with the solid adsorbent catalyst residues polyalpha - removed from olefins;
It is less than 600ppm was treated olefin heteroatom-containing compound - 2) optionally a poly-alpha;
3) poly-alpha - fractionating the olefin, the light and heavy portions were separated, heavy fraction comprises more than 20 carbon atoms;
4) poly-alpha - contacting olefins with hydrogen and a hydrogenation catalyst; and 5) polyalpha having bromine number less than 1.8 - includes obtaining an olefin, said process.

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