RU2804659C2 - Synthetic fluids with improved biodegradability - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to low viscosity poly-alpha-olefin compositions with good biodegradability, low pour point, high oxidation stability and low tendency to precipitate. A method is proposed for obtaining a poly-alpha-olefin-containing liquid having predetermined characteristics, including: a. reaction component alpha-olefin, including at least one alpha-olefin containing from 30 to 100 wt.% 1-tetradecene (C₁₄), in the presence of a catalytic system containing BF₃ and a promoter – alcohol alkoxylate to obtain a reacted bottom product and a residual amount of unreacted monomers; b. removal of the residual amount of unreacted monomers in the form of the upper fraction by distillation; and c. hydrogenation of at least a portion of said bottom product to obtain a hydrogenated liquid having a kinematic viscosity at 100°C, defined according to ASTM D-445, being 2.5 to 4.6 cSt, and in the implementation of which the content of dimer C₂₈ in containing poly-alpha-olefin liquid is more than 70 wt.% A lubricating composition and a finished fully or partially synthetic lubricating oil containing a poly-alpha-olefin liquid obtained by the proposed method are also proposed.

EFFECT: making compositions having a viscosity of 2.5-4.5 cSt in a selective manner without obtaining any co-forming products or without the need for subsequent mixing, from raw materials other than the limited production of decene.

13 cl, 13 tbl, 17 ex

Description

PREREQUISITES FOR CREATION OF THE INVENTION

1. Field of technology to which the invention relates

The present invention relates to low viscosity polyalpha-olefin (PAO) compositions characterized by good biodegradability, low pour point, high oxidation resistance and low sludge formation. More specifically, the present invention relates to a PAO-containing composition having improved kinematic viscosity at 100°C, and to an improved method for selectively producing the improved composition.

2. State of the art

Alpha olefin oligomers (also known as linear alpha olefins or vinyl olefins), processes for their preparation, and their use in synthetic and semi-synthetic lubricant compositions are known in the art. Several typical methods for preparing PAO oligomers include those described in the following publications: U.S. patents. No. 3682823; 3763244; 3769363; 3780123; 3798284; 3884988; 3097924; 3997621; 4045507 and 4045508.

Alpha olefin oligomers found to be useful as synthetic base fluids are typically derived primarily from linear terminal olefins containing about 8 to 14 carbon atoms, such as 1-octene, 1-decene, 1-dodecene, 1-tetradecene and mixtures thereof. One of the most widely used alpha olefins is 1-decene, which can be used alone or as a mixture with other alpha olefins. If linear alpha olefins are used, the oligomeric products include mixtures that contain varying amounts of dimers, trimers, tetramers, pentamers and higher oligomers. Oligomeric products are typically hydrogenated to improve their thermal stability and oxidation stability and must be further fractionated to be useful in specific applications. Such hydrogenated and fractionated oligomeric products are known to have excellent performance characteristics, long service life, low volatility, low pour points and high viscosity indices. It is desirable to develop a base fluid composition that has improved characteristics, including biodegradability, and requires a simpler process to obtain.

When preparing poly-alpha-olefin by conventional methods, the kinematic viscosity of the product can be adjusted by removing or adding higher or lower oligomers to obtain a composition having the viscosity required for a particular application. Typically, viscosities at 100° C. are required that range from 2 to 150 centistokes (cSt), with preferred viscosities ranging from 2 to 10 cSt.

These low viscosity fluids are particularly suitable for energy saving applications such as in engine lubricating oil to minimize friction and thus improve fuel economy. Their use alone or as a mixture with mineral oil can provide, for example, lubricating oils called SAE 0W-XX (SAE = Society of Automotive Engineers) or SAE 5W-XX motor oils.

Particularly in demand on the market are synthetic lubricant base stocks that have a kinematic viscosity at 100°C of 2.5 to 4.5 cSt, especially if they have this characteristic in combination with low Noack volatility and low loss point fluidity, acceptable viscosity at low temperatures and a high viscosity index. PAO having a kinematic viscosity of 4 cSt can be prepared by oligomerizing 1-decene using a Friedel-Crafts catalyst such as BF ₃ together with a promoter such as an alcohol.

However, the amount of 1-decene produced is limited because it is a by-product produced together with a large number of other alpha-olefins. There is a need to provide greater flexibility in producing synthetic base stocks using a wider range of alpha-olefins while still producing oligomers with substantially similar viscometric characteristics.

An additional difficulty associated with the preparation of oligomeric oils from 1-decene or other alpha-olefins is that in order to obtain oils having a given viscosity (for example, at 100°C equal to 2, 4, 6 or 8 cSt) containing the oligomeric product the mixture usually needs to be fractionated to give different fractions. Using the commercial preparation procedure described above, an oligomeric product-containing mixture is prepared, from which, after fractionation, related quantities of products having each viscosity value are obtained to meet market requirements. As a result, an excess of one product is often obtained in order to obtain the required amount of another product.

In addition, although commercially available PAO-containing products have a suitable balance of properties, products having specific viscosities that fall within a narrow range, for example, material having a viscosity of 4 cSt (mainly trimerdecene or C ₃₀ ), must be distilled from the complex mixtures of oligomers. The distillation procedure, in turn, results in a heavier co-product. Therefore, decene-derived PAOs having a viscosity of 4 to 5.5 cSt must be prepared by subsequently mixing a PAO having a viscosity of 4 cSt and a PAO having a higher viscosity.

Therefore, it is necessary to obtain compositions having a viscosity of 2.5-4.5 cSt, which have characteristics similar to or better than decene-based oils, from raw materials different from decene due to its limited production quantity. It is also necessary to obtain the above compositions having a viscosity of 2.5-4.5 cSt, in a selective manner without obtaining any co-products or without the need for subsequent mixing.

Poly-alpha-olefins formed from other linear alpha-olefins are known in the art.

It is known that poly-alpha-olefins formed from pure tetradecene have, in particular, a higher pour point and better viscosity characteristics at -40°C.

It has been shown that in the case of poly-alpha-olefin trimers obtained under the same conditions, the viscosity index increases with increasing chain length of the starting alpha-olefin. In contrast, volatility decreases with increasing chain length of the parent alpha-olefin. Considering that high viscosity index and low volatility are necessary characteristics of a lubricant, a method of using long carbon chain alpha olefins to produce polyalpha olefins has long been needed.

Unfortunately, it is known that pour point and low temperature viscosity also increase with increasing chain length of the parent alpha olefin. For example, poly-alpha-olefins - trimers of decene (Cu) are liquid to a temperature below 65°C. In contrast, poly-alpha-olefins are trimers of tetradecene ( _C14 ) according to ^{one publication (1 Source} : "Synthetic Lubricant Base Stock Processes and Products" Margaret M. Wu, Suzzy C. Ho, and T. Rig Forbus) are frozen solids at -20°C.

Shubkin's publication shows that even compositions comprising tetradecene oligomers containing a substantial amount of tetradecene dimer are frozen solids at temperatures ranging from -18 to -20°C. ² ( ² Shubkin et Al., "Tailor Making Polyalphaolefins" in Engine oils and Automotive Lubrication; ed. Wilfred Bartz, 1993, pub Verlag)

It is known that to enable the use of a base component in SAE 5W motor oils, the oil must be liquid at -30°C to meet the cold cranking criterion. The requirement for SAE 0W oils is even more stringent, namely that the base stock must be liquid at -35°C to meet cold cranking criteria.

Many industrial oils also require a Brookfield viscosity at -40°C, which precludes the use of any base stocks that have poor low temperature fluidity, such as those derived from tetradecene.

Prior art methods for producing PAOs that are suitable for use as base liquid compositions have numerous disadvantages, and there remains a need for more improved PAO-containing compositions and improved methods for producing these polyalpha-olefins. The present invention solves these problems by providing a one-step process for producing a low viscosity poly-alpha-olefin and a composition having a low pour point, good low temperature viscometric properties, a high viscosity index and good biodegradability.

SUMMARY OF THE INVENTION

The present invention relates to low viscosity polyalpha-olefin (PAO)-containing compositions characterized by good biodegradability, low pour point, high oxidation stability and low sludge formation tendency, and more precisely, the present invention relates to a PAO-containing composition having a kinematic viscosity at 100°C ranging from about 2.5 to 4.5 cSt.

The present invention also relates to an improved method for selectively preparing the above composition by oligomerization of 1-tetradecene in the absence or presence of a second comonomer, using a catalyst system containing BF ₃ and an alcohol alkoxylate promoter. The process of the present invention provides a C ₂₈ dimer (or codimer) selectivity of greater than 70% and does not require additional fractionation (after removal of residual unreacted monomer) to achieve selective production of the preferred product. The present invention also provides compositions useful for the preparation of ultra-low viscosity motor oils (e.g., 0W-16) and blended compositions with Group III oils and gas-to-liquid (GTL) oils, improving the low temperature performance of such compositions .

The present invention also relates to a process for producing a highly biodegradable, low viscosity oil useful as a lubricant in environmentally sensitive applications such as marine vessel lubrication and the like.

The performance of said low viscosity oil can be further improved by using conventional lubricating oil additives at a total level of up to about 35 wt. %, and preferably ranging from 0.1 to 30 wt. %. Such additives include, for example, dispersants, antioxidants, anti-wear additives, anti-foam additives, corrosion inhibitors, detergent additives, seal swell additives and viscosity index improvers. These types of additives are well known in the art. Although such additives themselves may have significant biodegradability, this is not a requirement.

Preferred embodiments of the above low viscosity oil additives include zinc dialkyldithiophosphates, calcium arylsulfonates, alkaline calcium arylsulfonates, barium phenolates, barium oxide neutralized phosphorus pentasulfide reaction products and terpenes derived from high molecular weight olefins, hindered alkylphenols, methylene bis -dialkylphenols, dibutyl tin sulfide, dibutyl hydrophosphonate, tricresyl phosphate, high molecular weight alkyl succinimides formed from ethylene polyamines such as tetraethylene polyamine, sulfur bridged alkyl phenols, sulfonated fatty acid esters and amides, silicones and dialkyl esters. Proprietary combinations of such additives, “additive combinations,” that are designed for specific base oils and applications are marketed by a variety of companies, including Afton Corporation, Lubrizol, or Infineum. Viscosity Index (VI) improvers are commercially available separately.

The fluids of the present invention can be used in conjunction with other base oils or oil additives. These base oils include, but are not limited to, C ₆ -C ₁₀ -(1-olefin) PAOs, mineral oils or synthetic esters.

The overall biodegradability of compositions containing the fluids of the present invention depends on the nature of the entire functional fluid or lubricant mixtures, including lubricating oil additives. In conclusion, the present invention relates to the use of the poly-alpha-olefin containing fluids of the present invention as a base fluid alone or in combination with other lubricating oils (e.g., Group I, Group II, Group III, Group III+ mineral oils , oils obtained using GZZh technology) in motor oils with viscosity grades SAE 0W-8, SAE 0W-12 and SAE 0W-16, or in lubricants for marine vessels.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

The present invention relates to a poly-alpha-olefin containing liquid that contains an oligomer obtained by oligomerizing one or more alpha-olefin components. In a preferred embodiment, the alpha-olefin component contains a first C ₁₄ alpha-olefin and from 0 to about 70 wt. % of a second olefin containing an even number of carbon atoms, equal to C ₁₂ to C ₂₀ . The structure of the second olefin is shown below, where R' is hydrogen (H) and R'' is C ₁₀ -C ₁₈ -hydrocarbyl, or where R' and R'' vary independently and both are hydrocarbyl, and where the sum of those contained in R' and R'' of carbon atoms is from C ₁₀ to C ₁₈ .

The liquid of the present invention is prepared by cationic oligomerization of the olefin or olefins described above using a boron trifluoride catalyst and a cocatalyst or "promoter" of an alcohol alkoxylate (R _a -O-CHR _b -CHR _c -O-) _n - H, thus obtaining a liquid which, after hydrogenation, has a kinematic viscosity at 100° C. of from about 2.5 to about 4.6 mm ² /s, and has biodegradability determined in accordance with the OECD (Organization for Economic Co-operation) test method and development) 301B, equal to at least 50%. The OECD Biodegradability Test Method 301B (Modified Sturm Test) is recommended by the OECD Biodegradability Expert Group for determining the biodegradability of organic chemicals in the aquatic environment. The test procedure is suitable for soluble and insoluble non-volatile organic compounds and measures the amount of O ₂ released, providing a determination of “total” biodegradability. The material to be tested is placed in a flask containing an inorganic substrate and a bacterial inoculum. After treatment with ultrasonic vibration, the contents of the flask are saturated with CO ₂ -free air. At the same time, a control sample is examined (for example, sodium benzoate, 20 (mg C)/l). The EPA (Environmental Protection Agency) recommends the use of aniline (freshly distilled) as a control substance. All released CO ₂ is absorbed in flasks containing a barium hydroxide solution, the concentration of which is periodically determined using hydrochloric acid. Biodegradability is expressed as a percentage of the total amount of CO ₂ released during the test (adjusted for the value for the control sample) in terms of the theoretical amount of CO ₂ that the test material can produce. Typically the trial is completed over a period of 28 days, although it can be completed earlier, i.e. immediately after the biodegradability relationship reaches a plateau for at least 3 measurements. On the other hand, the duration of the test may exceed 28 days if the dependence shows that biodegradation began within the first 28 days, but the dependence did not reach a plateau on day 28.

In an alcohol alkoxylate, (R _a -O-CHR _b -CHR _c -O-) _n -H, R _a denotes hydrocarbyl containing from 1 to 24 carbon atoms, including mixtures thereof, R _b and R _c independently denote hydrogen, methyl or ethyl, and n is in the range from 1 to 15. Preferred alcohol alkoxylate promoters are 2-methoxyethanol and 1-methoxy-2-propanol.

The present invention relates to a method for producing a poly-alpha-olefin-containing liquid from a first olefin comprising 1-tetradecene and 0-70 wt. % of a second olefin (R'R''C=CH ₂ described above), comprising introducing the olefin(s) into reaction with a catalyst comprising boron trifluoride and an alcohol alkoxylate (R _a -O-CHR _b -CHR _c -O- ) _n -H described above) thereby obtaining a reaction product - an oligomer, which contains at least about 70 wt. % dimer (or codimer) of said olefin monomer(s), and which has a dimer to trimer ratio of greater than about 1. In a preferred embodiment, the poly-alpha-olefin-containing mixture contains greater than 90% of the 1-tetradecene described in this embodiment.

In a preferred embodiment of the present invention, the second olefin comprises a dimer of a C ₈ alpha olefin, namely 2-n-hexyl-1-decene, which is prepared by reacting the C ₈ alpha olefin with an alkylaluminum catalyst such as triethylaluminum and etc., as described in US Pat. No. 8,455,416, the disclosure of which is incorporated herein by reference. Alternatively, the dimer is prepared by reacting a C ₈ alpha-olefin with a metallocene catalyst containing a Group IVB element of the Periodic Table activated with organoaluminum compounds, as described in US Pat. No. 6,548,723, the disclosure of which is incorporated herein by reference.

The poly-alpha-olefin-containing liquid of the present invention is prepared without obtaining any co-products and without the need for subsequent mixing or distillation of any component other than unreacted monomers.

The poly-alpha-olefin containing fluid of the present invention is suitable for use as a base fluid alone or in conjunction with other petroleum-derived mineral lubricating oils (i.e., Group I, Group II, Group III, Group III+ mineral oils ), synthetic oils produced from methane using a Fischer-Tropsch catalyst (i.e., for example, gas-to-liquids fluids or coal-to-liquids fluids), in motor oils with grades viscosities SAE 0W-8, SAE 0W-12 and SAE 0W-16, or in marine lubricants that meet the requirements of the Marine General Approval (GMA).

A preferred embodiment of the present invention is a hydrogenated composition having a viscosity at 100°C of about 4 cSt, a Noack volatility at 250°C corresponding to a weight reduction of less than 19%, and a Noack volatility at 200°C of less than 4% , a viscosity index greater than 125, a pour point less than -35 C, and a simulated cold start viscosity at -35 °C less than 1500 cP. A more preferred embodiment of the present invention is a hydrogenated composition having a viscosity at 100°C of about 4 cSt, a Noack volatility at 250°C corresponding to a weight reduction of 13.9%, a pour point of about -59°C, and a viscosity when simulating a cold start at -35°C equal to less than 1700 cP.

In another embodiment of the present invention, a hydrogenated composition having a viscosity at 100°C of about 3.4 cSt, a Noack volatility at 200°C corresponding to a 4% weight reduction, a pour point of about -50°C, and a viscosity according to Brookfield at -40°C, equal to less than 1750 cP.

The poly-alpha-olefins of the present invention have a combination of excellent low temperature performance and excellent high temperature stability while being substantially biodegradable. These polyalpha-olefins are suitable for use as a base fluid in a variety of environmentally friendly lubricants, either as a single base fluid or in combination with plant-derived or synthetic esters, other polyalpha-olefins (PAOs), mineral oils, liquids obtained using gas-to-liquid technology, additives, etc.

Environmentally friendly oils that can benefit from the fluid of the present invention include, but are not limited to:

oils for 2-stroke engines,

lubricants for pneumatic tools,

lubricants for chains and cables,

lubricants for forklifts,

liquids that ensure the adhesion of concrete and asphalt,

lubricants for rail tracks,

universal lubricants,

hydraulic fluids for fixed and moving equipment, machine oils,

liquids for releasing from a metal casting mold,

oils for drilling machines,

coolants for transformer and transmission shaft,

lubricants for sliding guides,

completely consumable lubricants,

lubricants for wire ropes,

stern tube lubricants,

oils for the forestry industry.

Oils that are not necessarily considered environmentally friendly, but which may also benefit from the fluid of the present invention include, but are not limited to: industrial gear lubricants, automotive gear lubricants, compressor oils, crankcase lubricants gasoline engine, lubricants for diesel engine crankcase, transmission oils, turbine oils.

In particular, the viscometric characteristics of the poly-alpha-olefins proposed in the present invention meet the requirements defined by the Society of Automotive Engineers (SAE) for substances intended for use as base fluids in 0W-8, 0W-12 and 0W- engine oils. 16.

In addition, the poly-alpha-olefins of the present invention can be used in any type of lubricant that uses plant-derived esters, estolides, or natural/synthetic esters. Marine stern tube lubricants, open gear oils, wire rope oils, forestry oils, and hydraulic fluids are cases that benefit from the addition of the poly-alpha-olefins of the present invention. Substantial biodegradability of oils in this category can be achieved by suitable selection of additives and thickeners.

One preferred embodiment of the finished fluids as described above includes mixtures containing a) 1-97% poly-alpha-olefin-containing fluid of the present invention, and b) 0-60% fluids selected from the group consisting of synthetic complex esters, synthetic hydrocarbon fluids, mineral oils, natural esters or hydrocarbon oils derived from natural and petroleum-derived raw materials, and c) 0.1-30% additives such as dispersants, antioxidants, anti-wear additives, anti-foam additives , corrosion inhibitors, detergents, seal swellers, viscosity index improvers, and combinations thereof, the viscometric characteristics of the finished composition meeting SAE requirements for grades 0W-XX, where XX is 16 or less.

Another preferred embodiment of the specified functional fluid or lubricant composition includes a mixture containing a) 1-97% containing poly-alpha-olefin fluid proposed in the present invention, and b) 0-60% fluids selected from the group consisting of synthetic esters , synthetic hydrocarbon fluids, mineral oils, natural esters or hydrocarbon oils derived from natural and petroleum-derived raw materials, and c) from 0.1 to 70% additives such as dispersants, antioxidants, anti-wear additives, anti-foam additives , corrosion inhibitors, detergents, seal swell additives and viscosity index improvers, wherein the finished composition has a biodegradability as determined by CEC L-33 A94 test method (or equivalent procedure) of at least 50%, where Intentional or unintentional release of said composition into the environment may occur.

Another preferred embodiment is a functional fluid or lubricant composition, wherein the composition contains a mixture of a) 1-98% of a poly-alpha-olefin-containing fluid of the present invention, and b) 0-60% of one or more components selected from the group comprising natural or synthetic esters, natural or synthetic hydrocarbon liquids, or hydrocarbon oils derived from natural and petroleum-derived raw materials, and c) from 0.1 to 70% additives such as dispersants, antioxidants, anti-wear additives , anti-foam additives, corrosion inhibitors, detergent additives, seal swell additives and viscosity index improvers. This embodiment may be particularly preferred in applications involving the operation of a chain saw, outboard engine, agricultural equipment, earthmoving equipment, or in cases of marine and submersible fluids. In specific applications for marine vessels, the finished composition must satisfy the EPA requirements specified in the General Permit for Marine Vessels regulations.

Examples

Commercially available 1-tetradecene (C ₁₄ ) from INEOS Oligomers was used without treatment; it can be replaced by 1-tetradecene, sold by other suppliers. All stages of the method can be carried out in batch, semi-batch or continuous mode. The reaction can be carried out in a continuous mode using 2-5 continuous stirred tank reactors (CSCRs) arranged in series or parallel, or using a combination of these arrangements.

Comparative example 1

A 1-gallon Parr reactor equipped with a heating jacket and internal cooling system was charged with 1200 g of 1-tetradecene and 3.0 g of 1-butanol (1-BuOH) and heated to 50° C. with stirring. Boron trifluoride (BF ₃ ) was added as a gas and the pressure was maintained at ⁴⁰ psig. The reaction mixture was stirred for 90 minutes. The reaction was stopped with 400 ml of 8% NaOH solution and then the mixture was washed with distilled water. After removal of the residual amount of unreacted monomer in the form of an upper fraction at reduced pressure (220°C, 0.1 mm Hg), 837.1 g of the lower fraction, a clear liquid, was isolated, which was hydrogenated under standard hydrogenation conditions (at 170°C , at a hydrogen pressure of 400 lbf/in ² using Ni on diatomaceous earth as a catalyst), and obtained a synthetic base stock having the following characteristics:

Example 2 proposed in the present invention:

A 1-gallon Parr reactor equipped with a heating jacket and internal cooling system was charged with 1,400 g of 1-tetradecene and 4.2 g of 1-methoxy-2-propanol (1-MOP) and heated to 50° C. with stirring. Boron trifluoride (BF ₃ ) was added as a gas and the pressure was maintained at ²⁰ psig. The reaction mixture was stirred for 120 minutes. The reaction was stopped with 400 ml of 8% NaOH solution and then the mixture was washed with distilled water. After removing the residual amount of unreacted monomer from the upper fraction at reduced pressure (220°C, 0.1 mm Hg), 1063.1 g of the lower fraction was isolated - a clear liquid, which was hydrogenated under standard hydrogenation conditions (at 170°C , at a hydrogen pressure of 400 lbf/in ² using Ni on diatomaceous earth as a catalyst), and obtained a synthetic base stock having the following characteristics:

From the above table it can be seen that after removing the residual amount of unreacted monomer, the resulting PAO has the balance of viscometric characteristics specified in the present invention. This product is a straight distilled liquid with a homogeneous composition and a viscosity of 4 cSt, obtained without additional distillation. This product is also a liquid having a viscosity of 4 cSt, a high viscosity index, low Noack volatility and a significantly improved pour point compared to the characteristics of a conventional C14 oligomer prepared using a BF ₃ containing catalyst system and conventional alcohols such as 1-butanol (1-BuOH), as promoters:

According to GC (gas chromatography) data, the PAO-containing oligomeric composition proposed in the present invention, obtained in example 2, had the following composition:

C ₂₈ (dimer): area = 88.0%

With ₄₂₊ (trimer and higher): area = 12.0%

Example 3 according to the present invention:

The procedure described in example 2 was carried out on a semi-industrial scale. The product had the following characteristics:

Example 4 according to the present invention:

A 1-gallon Parr reactor equipped with a heating jacket and internal cooling system was charged with 1,200 g of 1-tetradecene and 3.1 g of 2-methoxyethanol (2-MOE) and heated to 50° C. with stirring. Boron trifluoride (BF ₃ ) was added as a gas and the pressure was maintained at ⁴⁰ psig. The reaction mixture was stirred for 90 minutes. The reaction was stopped with 400 ml of 8% NaOH solution and then the mixture was washed with distilled water. After removal of the residual amount of unreacted monomer in the form of an upper fraction under reduced pressure (220°C, 0.1 mm Hg), 737.3 g of the lower fraction, a clear liquid, was isolated, which was hydrogenated under standard hydrogenation conditions (at 170°C , at a hydrogen pressure of 400 lbf/in ² using Ni on diatomaceous earth as a catalyst), and obtained a synthetic base stock having the following characteristics:

Example 5 proposed in the present invention:

A 1-gallon Parr reactor equipped with a heating jacket and internal cooling system was charged with 476 g of 1-tetradecene, 924 g of 1-dodecene, and 4.2 g of 1-methoxy-2-propanol (1-MOP) and heated to 50°C. Boron trifluoride (BF ₃ ) was added as a gas and the pressure was maintained at ²⁰ psig. The reaction mixture was stirred for 120 minutes. The reaction was stopped with 400 ml of 8% NaOH solution and then the mixture was washed with distilled water. After removal of the residual amount of unreacted monomer in the form of an upper fraction at reduced pressure (220°C, 0.1 mm Hg), 993.9 g of the lower fraction, a clear liquid, was isolated, which was hydrogenated under standard hydrogenation conditions (at 170°C , at a hydrogen pressure of 400 lbf/in ² using Ni on diatomaceous earth as a catalyst), and obtained a synthetic base stock having the following characteristics:

Example 6 according to the present invention:

Example 4 was repeated using 2-methoxyethanol (2-MOE) as cocatalyst. The product had the characteristics shown in Table 6.

Example 7 according to the present invention:

A 1 gallon Parr reactor equipped with a heating mantle and internal cooling system was charged with 515.0 g of 1-tetradecene, 885.0 g of 2-n-hexyl-1-decene (a dimerization product of 1-octene, prepared as described). in US 8455416) and 1.4 g of 1-methoxy-2-propanol (1-MOP). The mixture was heated to 30°C while stirring. Boron trifluoride (BF ₃ ) was added as a gas and the pressure was maintained at ²⁰ psig. The reaction mixture was stirred for 90 minutes. The reaction was stopped with 400 ml of 8% NaOH solution and then the mixture was washed with distilled water. After removal of the residual amount of unreacted monomer in the form of an upper fraction at reduced pressure (220°C, 0.1 mm Hg), 1162.0 g of the lower fraction, a clear liquid, was isolated, which was hydrogenated under standard hydrogenation conditions (at 170°C , at a hydrogen pressure of 400 lbf/in ² using Ni on diatomaceous earth as a catalyst), and obtained a synthetic base stock having the following characteristics:

BIODEGRADABILITY OF POLY-ALPHA-OLEFINS PROVIDED IN THE PRESENT INVENTION

Substances are considered biodegradable if they are effectively broken down by microorganisms. There are a number of techniques that can be used and have been used to study biodegradability. One OECD approved test method that is well suited for paraffinic hydrocarbons is Test Method 301B Biodegradability (also known as the Modified Sturm Test).

Example 8:

In OECD Test Procedure 301B, the test sample is treated with activated sewage sludge and culture medium in sealed tubes maintained at 21°C. The degree of decomposition of the test material is determined by determining the amount of carbon dioxide formed over 28 days. Control solutions containing wastewater microorganisms and standard materials are also tested.

According to this test, the poly-alpha olefin of Example 7 was 100% degraded after 28 days and 60% degraded after 10 days.

In contrast, PAO with the same viscosity, formed from 1-decene, decomposes only 28% after 28 days. The characteristics of other comparison samples are shown in Table 8 below:

1. The OECD Test Method 301B, also known as the modified Sturm test, determines the amount of CO ₂ released from a test tube during biological decomposition. The theoretical amount of CO ₂ is calculated based on the fact that all the carbon contained in the compound under study is converted into CO ₂ . The test is carried out for 28 days

2. An indicator of “biodegradability” is the formation of at least 60% of CO ₂ of the amount that could theoretically be formed within 10 days, with a biodegradation threshold of 10%. Since microorganisms use some carbon to grow new microorganisms, not the full theoretical amount of CO ₂ is produced

*DN - no data

Example 9

According to the OECD 301B biodegradability test, the product of Example 3 of the present invention, a poly-alpha-olefin formed entirely from 1-tetradecene, degraded 54% after 28 days.

Example 10

According to the OECD 301B biodegradability test, the product of Example 5 of the present invention, a poly-alpha-olefin formed from 1-tetradecene and 1-dodecene, was 87.3% degraded after 28 days.

FINISHED OILS CONTAINING THE PRODUCTS OFFERED IN THE PRESENT INVENTION

The fluids of the present invention can be used in finished lubricant products that are not typically formulated to be substantially biodegradable, such as crankcase lubricants, industrial and automotive gear oils, gear oils, etc. .p., but which may be accidentally released into the environment.

Because of their unique balance of biodegradability, low temperature performance and thermal stability and oxidation resistance, the fluids of the present invention are particularly well suited for use in lubricants that may be accidentally released into the environment (e.g., marine lubricants). ) or intentional (for example, lubricants for the forest industry). For these classes of lubricants, the significant biodegradability of the fluids of the present invention is an advantage.

In lubricant products formulated in such a way that they are substantially biodegradable, such as hydraulic oils, chain saw lubricants, outboard engine lubricants, turbine oils, compressor oils, greases, etc., liquids, those proposed in the present invention can be used as a single base fluid or in combination with other base fluids. Ideally, these other liquids should themselves have good intrinsic biodegradability. Illustrative examples of fluids that can be used with the fluids of the present invention include vegetable oils (e.g., canola oil, canola oil, etc.), vegetable oil derivatives (e.g., estolid esters), or even synthetic dicarboxylic acid esters, which have good biodegradability and good viscometric characteristics.

In cases where good overall biodegradability is not required, the product of the present invention can be used in conjunction with conventional poly-alpha-olefins (i.e., hydrogenated liquid 1-alkene oligomers), mineral oils, or conversion fluids gas in liquid, if they are used in the finished composition as a component contained in a small amount.

To improve specific performance characteristics of finished oils, additives are often needed and can be included in the fluids of the present invention. These additives may themselves be biodegradable or non-biodegradable and include anti-wear additives, detergent additives, viscosity index improvers, tribomodifiers, fuel economy additives, antioxidants or heat stabilizers, dispersants, ultra-high pressure agents, additives tackifiers, corrosion inhibitors, additives that change the pour point of paraffin oils, antifoam additives, copper passivators, sulfur absorbers, seal swelling additives, color stabilizers and similar materials.

The fluids of the present invention can be used in conjunction with additives that are themselves designed to be biodegradable.

If possible, the additive should be selected so that it at least does not impair the biodegradability of the final composition.

Example 11:

Example of a tractor fluid containing the fluid of the present invention having a viscosity of 3.9 cSt

1. A commercially available tractor hydraulic fluid additive composition available from Afton; Hitec 8703

2. The liquid proposed in the present invention, corresponding to example 7

3. Commercially available shear viscosity stability improver from Evonik; Viscoplex 8-219

4. This test procedure is a procedure for comparing the biodegradability of 2-stroke outboard engine lubricants or other oils with the biodegradability of standard calibration materials

Example 12:

An example of an environmentally friendly chain oil containing the fluid of the present invention having a viscosity of 3.9 cSt

1. Commercially available additive composition; Esp Afton Hitec 2211

2. The liquid proposed in the present invention, corresponding to example 7

3. Commercially available canola oil from Archer Daniels Midland

Example 13:

Example of a 2-stroke marine engine oil containing the fluid of the present invention

1. A commercially available additive composition that meets the requirements of NAMI (National Marine Manufacturers Association) TC W3; Esp Lubrizol 424

2. The liquid proposed in the present invention, corresponding to example 7

3. Commercially available synthetic saturated linear acid ester complex; Esp.Nycobase 8306

4. A commercially available synthetic ester complex of a partially unsaturated linear acid; Esp.Nycobase 4045

5. This test procedure is a procedure for comparing the biodegradability of 2-stroke outboard engine lubricants or other oils with the biodegradability of standard calibration materials

Example 14:

Example of Biodegradable Multi-Purpose Marine Gear Oil/Stern Tube Oil

1. A commercially available biodegradable gear additive composition available from Functional Products; GA-502

2. Commercially available bio-based ester thickener; viscosity at 100°C=293 cSt, viscosity at 40°C=3113 cSt, produced by Inolex, bio-based component content=67%; Lexolube CG-3000.

3. Commercially available canola oil from Cargill, viscosity at 100°C=8.53 cSt, viscosity at 40°C=38.71 cSt

4. The liquid proposed in the present invention, corresponding to example 2

5. 75W oil must have a minimum viscosity value at 100°C of 24 to 41 mm ² /s

Conventional lubricants

It is believed that the synthetic fluids of the present invention can be used in any application where hydrogenated 1-decene oligomers having similar viscosity are used. Applications include, but are not limited to, automotive engine oils, heavy-duty diesel vehicle oils, automatic transmission oils, continuously variable transmission oils, and industrial and automotive gear oils, compressor/ turbine oils, and particularly in applications that benefit from the energy-reducing characteristics of low-viscosity fluids such as 0W-XX ultra-low and low viscosity motor oils where X is 16 or less. To illustrate the applicability of the fluids of the present invention to a number of 0W-X oil compositions, several illustrative compositions have been prepared.

Motor oils for passenger cars

The synthetic fluids produced by the present invention are ideally suited for use as components of fully synthetic and/or semi-synthetic lubricating oils used in internal combustion engines. The fluids of the present invention can be used as a complete base lubricant or they can be blended with other lubricating oils, including Group I, II or III mineral oils, gas-to-liquids (GTL) oils, synthetic ester oils (for example, di-2-ethylhexyl adipate, trimethylolpropane tripelargonate, etc.), alkylnaphthalene oils (for example, di-dodecylnaphthalene, di-tetradecylnaphthalene, etc.), etc. Lubricating oils used for internal combustion engines are typically formulated to contain conventional lubricating oil additives such as calcium arylsulfonates, alkaline calcium sulfonates, calcium or barium phenolates, alkaline magnesium alkylbenzenesulfonates, zinc dialkyldithiophosphates, VI improvers (e.g. , copolymers of ethylene with propylene, polyalkyl methacrylates, etc.), ashless dispersants (for example, polyisobutylene succinimides formed from tetraethylenepentamine, products of the condensation reaction of polyisobutylenephenol, formaldehyde and tetraethylenepentamine according to Mannich, etc.), additives that lower the pour point, tribo-modifiers, corrosion inhibitors, demulsifiers, oil-soluble antioxidants (for example, hindered phenols or alkylated diphenylamines), various sulfonated components and foam inhibitors (anti-foam additives).

When used in the present invention, a synthetic oil or base stock is a lubricant formed from chemical compounds that are artificially produced. Synthetic lubricants can be made using chemically modified petroleum components such as ethylene, the precursor from which alpha-olefins are made, or they can be synthesized from other non-petroleum precursors. Synthetic base oils, produced artificially, typically have a defined molecular structure and predictable characteristics, unlike mineral base oils, which are a complex mixture of naturally occurring hydrocarbons.

Mineral oils or oils derived from petroleum refining are defined as components of API (American Petroleum Institute) Groups I, II, II+, III and III+ base oils.

API Group III base oils are sometimes considered fully synthetic, however, when used in the present invention, Group III/Group III+ base oils are classified as mineral base oils.

Lubricants that contain synthetic lubricants and do not contain API Group I, II, II+, III and III+ mineral base components are considered fully synthetic. Lubricants containing synthetic lubricants and API Group I, II, II+, III and III+ base ingredients are considered "semi-synthetic" or "partly synthetic".

For both partially synthetic and full synthetic oils, the base stocks are combined with additive formulations, performance additives and esters (usually API Group V) or other solubility aids.

Proprietary combinations of these additives, called additive combinations, are designed for specific base oils and applications and are sold by a variety of companies, including Lubrizol, Infineum and Afton Corporations. Viscosity Index (VI) improvers are available from these and other suppliers.

The liquid proposed in the present invention can be used to prepare motor oils for passenger cars with a viscosity grade of 0W-XX, which are preferred due to their energy-saving characteristics.

Example 15:

Example of oil for a passenger car

The following fully and partially synthetic motor oils for passenger cars (MMLA) were prepared containing the liquids proposed in the present invention.

1. Commercially available dispersant/inhibitor composition, Infineum P5707, API SN, ILSAC GF5/GF6B

2. The liquid proposed in the present invention, corresponding to example 7

3. The liquid proposed in the present invention, corresponding to example 3

4. The liquid proposed in the present invention, corresponding to example 5

5. A commercially available hydrogenated poly-alpha-olefin derived from 1-dodecene, available from INEOS; viscosity at 100°C=5.1 cSt

6. A commercially available hydrogenated poly-alpha-olefin derived from 1-decene, available from INEOS; viscosity at 100°C=3.93 cSt

7. Commercially available Group II mineral oil; Puralub 75, viscosity at 100°C=3.1 cSt, IV=102, pour point = -15°C

8. Commercially available 15% w/w. a solution of hydrogenated styrene-polyisoprene polymer in PAO, manufactured by Shell; SV261

9. Ester, produced by Croda; P3970, viscosity at 100°C=4.9 cSt, IV=213

*HTVS - high temperature and high shear rate

**IH3 - cold start simulation

Example 16:

If a Group III mineral oil having a viscosity of 4 cSt is replaced by the fluid of the present invention having a viscosity of 4 cSt, mixed with a Group III oil having a viscosity of 6 cSt and a pour point depressant, then the resulting mixture has a lower pour point, lower viscosity when simulating a cold start at -30°C and -35°C, and a higher flash point.

1. The liquid proposed in the present invention, corresponding to example 3

2. Group III mineral oil, viscosity=4 cSt; S-Oil Ultra S4, viscosity at 100°C = 4.2 cSt, IV = 125, pour point = -21°C. Noack volatility=14.2%

3. Group III mineral oil, viscosity=6 cSt; S-Oil Ultra S6, viscosity at 100°C=5.9 cSt, IV=127, pour point=-15°C. Noack volatility=8.2%

4. Additive that lowers the pour point; Afton Hitec 623

Example 17:

Partially synthetic MMLA 0W-16

1. Commercially available dispersant/inhibitor composition, Infineum P5707, API SN, ILSAC GF5/GF6B

2. Mineral oil of group III+; Yubase 4+, viscosity=4.1 cSt, IV=134

3. The liquid proposed in the present invention, corresponding to example 7

4. Commercially available 15% w/w. a solution of hydrogenated polymer styrene-polyisoprene in PAO6, manufactured by Shell; SV261

5. Ester, produced by Croda; P3970, viscosity at 100°C=4.9 cSt, IV=213

*RMV - rotational mini viscometer

Claims (28)

1. A method for producing a liquid containing poly-alpha-olefin having predetermined characteristics, including: a. the reaction of an alpha-olefin component comprising at least one alpha-olefin containing from 30 to 100 wt.%. 1-tetradecene (C ₁₄ ), in the presence of a catalytic system containing BF ₃ and a promoter - alcohol alkoxylate to obtain a reacted bottom product and a residual amount of unreacted monomers; b. removing the residual amount of unreacted monomers in the form of an upper fraction by distillation; And c. hydrogenating at least a portion of said bottoms product to produce a hydrogenated liquid having a kinematic viscosity at 100°C, determined according to ASTM D-445, of 2.5 to 4.6 cSt, and in which the content of C ₂₈ dimer in the poly-alpha-olefin-containing liquid is more than 70 wt.%. 2. The method according to claim 1, in which the alpha-olefin component contains more than 90% wt. C ₁₄ alpha olefin. 3. The method according to claim 1, wherein the poly-alpha-olefin-containing hydrogenated liquid has a biodegradability, determined in accordance with the OECD (Organization for Economic Co-operation and Development) test method 301B, of at least 50%. 4. The method of claim 1, wherein the alpha olefin component comprises a first alpha olefin and a second alpha olefin, and wherein the first alpha olefin is a C ₁₄ alpha olefin and the second olefin is a C ₁₂ alpha olefin . 5. The method of claim 1, wherein the alpha olefin component comprises a first alpha olefin and a second alpha olefin, and wherein the first alpha olefin is a C ₁₄ alpha olefin and the second olefin is a C ₈ alpha dimer. olefin. 6. The method according to claim 1, wherein the alcohol alkoxylate promoter used in step (a) is 2-methoxyethanol. 7. The method according to claim 1, wherein the alcohol alkoxylate promoter used in step (a) is 1-methoxy-2-propanol. 8. A lubricating composition comprising a poly-alpha-olefin-containing hydrogenated liquid obtained by the method according to any one of claims. 1-7, and either a. having a kinematic viscosity at 100°C equal to 4 cSt, a Noack volatility at 250°C corresponding to a mass reduction of less than 19%, and a Noack volatility at 200°C corresponding to a mass reduction of less than 4%, a viscosity index of more than 125, a pour point less than -35°C and a simulated cold start viscosity at -35°C less than 1500 cP, or b. having a kinematic viscosity at 100°C equal to 3.4 cSt, a Noack volatility at 200°C corresponding to a weight reduction of 4%, a pour point equal to -50°C, and a Brookfield viscosity at -40°C equal to less than 1750 cP, or c. having a kinematic viscosity at 100°C of 4 cSt, a Noack volatility at 250°C corresponding to a 13.9% weight reduction, a pour point of -59°C and a simulated cold start viscosity of -35°C , equal to less than 1700 cP. 9. A finished fully or partially synthetic lubricating oil containing a hydrogenated liquid having a kinematic viscosity at 100°C equal to from 2.5 to 4.6 cSt, wherein the hydrogenated liquid is a liquid containing poly-alpha-olefin, obtained by any method from paragraphs. 1-7. 10. Finished lubricating oil according to claim 9, containing a mixture of: a. from 1 to 97% wt. said hydrogenated liquid having a kinematic viscosity at 100°C of 2.5 to 4.6 cSt; And b. from 0 to 60% wt. fluids selected from the group consisting of synthetic esters, synthetic hydrocarbon fluids, mineral oils, natural esters or hydrocarbon oils derived from natural raw materials and raw materials derived from petroleum, and combinations thereof; And c. from 0.1 to 30% wt. additives selected from the group consisting of dispersants, antioxidants, anti-wear additives, anti-foam additives, corrosion inhibitors, detergent additives, seal swell additives, viscosity index improvers, and combinations thereof. 11. Finished lubricating oil according to claim 9, containing a mixture of: a. from 1 to 97% wt. said hydrogenated liquid having a kinematic viscosity at 100°C of 2.5 to 4.6 cSt; And b. from 0 to 60% wt. a component selected from the group consisting of natural or synthetic esters, natural or synthetic hydrocarbon fluids, or hydrocarbon oils derived from natural raw materials and raw materials derived from petroleum, and combinations thereof; And c. from 0.1 to 70% wt. additives selected from the group consisting of dispersants, antioxidants, anti-wear additives, anti-foam additives, corrosion inhibitors, detergent additives, seal swell additives, viscosity index improvers, and combinations thereof. 12. Finished lubricating oil according to claim 9, containing a mixture of: a. from 1 to 98% wt. said hydrogenated liquid having a kinematic viscosity at 100°C of 2.5 to 4.6 cSt; And b. from 0 to 60% wt. a component selected from the group consisting of natural or synthetic esters, natural or synthetic hydrocarbon fluids, or hydrocarbon oils derived from natural raw materials and raw materials derived from petroleum, and combinations thereof; And c. from 0.1 to 70% wt. additives selected from the group consisting of dispersants, antioxidants, anti-wear additives, anti-foam additives, corrosion inhibitors, detergent additives, seal swell additives, viscosity index improvers, and combinations thereof.