Functionalized olefin oligomers

Abstract

To provide a method of treating a hydrocarbon-containing reservoir and a surfactant composition used for the treatment.SOLUTION: The method involves introducing a surfactant composition into a hydrocarbon-containing reservoir. The surfactant composition includes an alpha olefin sulfonate or an isomerized olefin sulfonate. The alpha olefin sulfonate or the isomerized olefin sulfonate is synthesized by i) oligomerizing a monomer comprising a C3 to C6 mono-olefin to form an oligomerization product and ii) sulfonating the oligomerization product.SELECTED DRAWING: None

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to commercial applications using functionalized olefin oligomers and compositions containing the functionalized olefin oligomers. [Background technology]

[0002] Olefin oligomers and their derivatives (e.g., hydrogenated olefin oligomers) are end products or intermediates in the manufacture of a wide variety of commercial products, including surfactants, lubricants, and additives. The specific olefin oligomer used for a given application is typically determined by the physical and / or mechanical properties of the olefin oligomer. These properties can be customized by the specific process used to produce the olefin oligomer and the reaction conditions under which the olefin oligomer is produced. Summary of the Invention

[0003] In one aspect, a method for treating a hydrocarbon-containing oil reservoir is provided, comprising introducing into the oil reservoir a surfactant composition comprising an alpha olefin sulfonate or an internal olefin sulfonate, wherein the alpha olefin sulfonate or the internal olefin sulfonate is synthesized by i) oligomerizing a monomer comprising a C3-C6 monoolefin to form an oligomer, and ii) sulfonating the oligomer.

[0004] In another aspect, there is provided a surfactant for enhanced oil recovery, the surfactant comprising an alpha olefin sulfonate or an internal olefin sulfonate, the alpha olefin sulfonate or the internal olefin sulfonate being synthesized by i) oligomerizing a monomer comprising a C3 to C6 monoolefin to form an oligomer, and ii) sulfonating the oligomer.

[0005] In yet another embodiment, there is provided a lubricating oil composition comprising a base oil and a succinimide dispersant synthesized by oligomerizing a monomer comprising a C3 to C6 monoolefin to form an oligomerizate, and ii) functionalizing the oligomerizate with an ethylenically saturated carboxylic acid group.

[0006] In yet another aspect, there is provided a dispersant composition comprising a succinimide dispersant synthesized by oligomerizing a monomer comprising a C3 to C6 monoolefin to form an oligomerizate, and ii) functionalizing the oligomerizate with an ethylenically saturated carboxylic acid group.

[0007] In yet another further aspect, there is provided a lubricating oil composition comprising a base oil and a detergent additive synthesized by i) oligomerizing a monomer comprising a C3 to C6 monoolefin to form an oligomerizate, and ii) alkylating a hydroxyaromatic compound with the oligomerizate.

[0008] In yet another additional aspect, there is provided a detergent composition comprising a detergent additive synthesized by: i) oligomerizing a monomer comprising a C3 to C6 monoolefin to form an oligomerized product; and ii) alkylating a hydroxyaromatic compound with the oligomerized product.

[0009] In yet another additional aspect, there is provided a surfactant composition comprising an alcohol ether sulfate or alcohol ether carboxylate synthesized by oligomerizing a monomer comprising a C3-C6 monoolefin to form an oligomer, and ii) converting the oligomer into an alcohol. [Brief explanation of the drawings]

[0010] [Figure 1] 1 shows an electrospray ionization (ESI) mass spectrum of the sodium sulfonate composition prepared in Example 6. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention provides functionalized olefin oligomers and their use in various commercial applications. Importantly, at least some of the functionalized olefin oligomers can be used as surfactants in chemical enhanced oil recovery (CEOR). CEOR typically employs anionic surfactants, including, but not limited to, alkyl aromatic sulfonates (AAS), alpha olefin sulfonates (AOS), internal olefin sulfonates (IOS), alcohol sulfates, alkyl ether or alcohol ether sulfates (AES), and alkyl ether or alcohol carboxylates (AEC). Some olefin oligomers can also be used as oil additives, lubricants, anti-fog or wetting agents, and adhesion promoters. Olefin oligomers can also be used as plasticizers, soaps, detergents, fabric softeners, anti-static agents, and many other applications.

[0012] monomer Functionalized olefin oligomers can be made by oligomerizing an olefin monomer to form an olefin oligomer and then functionalizing the oligomer.

[0013] A wide variety of monomers can be oligomerized, including, consisting essentially of, or consisting of C3-C6 monoolefins. Suitable monomers include internal olefins, alpha olefins, trisubstituted olefins, and mixtures of any of these. Furthermore, the alpha olefins can include or consist essentially of normal alpha olefins (sometimes referred to as "linear alpha olefins").

[0014] Generally, the monomers can comprise (or consist essentially of, or consist of) C3-C6 monoolefins, C3-C5 monoolefins, or C3-C4 monoolefins. In alternative embodiments, the monomers can comprise (or consist essentially of, or consist of) C3 olefins, or C4 monoolefins, or C5 monoolefins, or C6 monoolefins. Thus, mixtures of olefins with different numbers of carbon atoms can be used, or olefins with a majority of one carbon atom can be used as the monomer.

[0015] The monomer can comprise at least 50 wt.%, at least 55 wt.%, at least 60 wt.%, at least 65 wt.%, at least 70 wt.%, at least 75 wt.%, at least 80 wt.%, at least 85 wt.%, at least 90 wt.%, or at least 95 wt.% of any olefin described herein, or a combination of olefins described herein. Additionally or alternatively, the monomer can comprise up to 100 wt.%, 99 wt.%, 98 wt.%, 97 wt.%, or 96 wt.% of any olefin described herein, or a combination of olefins described herein. Generally, the weight percent can range from any minimum weight percent disclosed herein to any maximum weight percent disclosed herein. That is, non-limiting ranges of monomer weight percent can include 50-100 wt.%, 55-99 wt.%, 60-98 wt.%, 65-97 wt.%, 70-96 wt.%, 75-100 wt.%, 80-100 wt.%, or 80-98 wt.% of any olefin described herein or mixture of olefins described herein.

[0016] The olefins can be cyclic or acyclic, and / or linear or branched. For example, the monomers can comprise, consist essentially of, or consist of acyclic olefins, and additionally or alternatively, the monomers can comprise, consist essentially of, or consist of linear olefins.

[0017] The monomers can comprise (or consist essentially of, or consist of) propylene, 1-butene, isobutylene, 1-pentene, 2-methyl-1-butene, 2-methyl-2-butene, or any combination thereof, or propylene, or 1-butene, or isobutylene. Thus, mixtures of olefins with different numbers of carbon atoms can be used, or olefins with a majority of one carbon atom can be used as the monomer.

[0018] The oligomerization reaction of the present invention generally involves introducing a monomer containing a C3-C6 monoolefin and a catalyst into a reaction section, where the monomer is oligomerized to form an olefin oligomer. Generally, any suitable catalyst can be used. Suitable catalysts include, but are not limited to, ionic liquid catalysts, phosphoric acid, zeolites, mesoporous aluminosilicates, or Ziegler-Natta catalysts. Additional catalysts may be used. A more detailed discussion of ionic liquid catalysts can be found in U.S. Pat. No. 9,938,473, which is incorporated herein by reference. A more detailed discussion of phosphoric acid catalysts can be found in U.S. Pat. No. 2,592,428, U.S. Pat. No. 2,814,655, U.S. Pat. No. 3,887,634, and U.S. Pat. No. 8,183,192, which are incorporated herein by reference. A more detailed discussion of zeolite catalysts can be found in U.S. Pat. No. 4,547,612, which is incorporated herein by reference. A more detailed discussion of mesoporous aluminosilicate catalysts can be found in WO 201120968, which is incorporated herein by reference. A more detailed discussion of Ziegler-Natta catalysts can be found in EP 638593, which is incorporated herein by reference. Various methods for oligomerizing olefins are described in Skupinska, J. Chem. Rev. 1991, 91, 613-648, which is incorporated herein by reference.

[0019] Olefin Oligomer Products The olefin oligomers of the present invention can comprise dimers, trimers, and / or tetramers or higher oligomers. In some embodiments, the olefin oligomers comprise (i) at least 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% dimers, trimers, tetramers, pentamers, hexamers, heptamers, octamers, nonamers, and / or decamers, (ii) at least 50 wt% trimers, tetramers, pentamers, hexamers, heptamers, octamers, nonamers, and / or decamers. %, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 85 wt%, or 90 wt%, (iii) at least 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of dimers, trimers, tetramers, pentamers, hexamers, and / or heptamers, (iv) at least 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 85 wt%, or 90 wt% of trimers, trimers, tetramers, pentamers, hexamers, and / or heptamers. t%, 65wt%, 70wt%, 80wt%, 85wt%, or 90wt%, (v) at least 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, or 60wt% of dimers, trimers, tetramers, and / or pentamers, (vi) at least 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, or 50wt% of trimers, tetramers, and / or pentamers, (v ii) at least 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, or 60 wt% of dimers, trimers, and / or tetramers; (viii) at least 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, or 50 wt% of trimers and / or tetramers; or (ix) any combination thereof.

[0020] In additional or alternative embodiments, the olefin oligomers may comprise at least 35 wt%, 45 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or 65 wt% trimers, tetramers, and pentamers combined, or alternatively or additionally, may comprise up to 100 wt%, 95 wt%, 90 wt%, or 85 wt% trimers, tetramers, and pentamers combined. In some embodiments, the olefin oligomers may comprise 35 wt% to 100 wt%, 40 wt% to 95 wt%, 45 wt% to 90 wt%, 40 wt% to 85 wt%, 50 wt% to 90 wt%, or 50 wt% to 85 wt% trimers, tetramers, and pentamers combined.

[0021] The olefin oligomer may contain less than 40 wt%, less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 18 wt%, less than 16 wt%, less than 14 wt%, less than 12 wt%, or less than 10 wt% dimers. Additionally or alternatively, the olefin oligomer may contain less than 30 wt%, less than 25 wt%, less than 20 wt%, less than 15 wt%, less than 10 wt%, less than 8 wt%, less than 6 wt%, less than 5 wt%, less than 4 wt%, less than 3 wt%, or less than 2 wt% oligomers containing seven or more monomer units.

[0022] In some embodiments, the olefin oligomer is C 12 ~C 70 (For example, C 12 ~C 40 , C 12 ~C 30 , C 12 ~C 20 , C 14 ~C 70 , C 14 ~C 40、 C 14 ~C 30 , C 14 ~C 20 , C 16 ~C 70 , C 16 ~C 40、 C 16 ~C 30 , C16 ~C 24 , C 20 ~C 70 , C 20 ~C 40 , C 20 ~C 30 or C 20 ~C 24 In some embodiments, the olefin oligomer may comprise at least 50 wt%, 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of C) oligomers. 70 The wt% of oligomer(s) disclosed herein may be based on the total weight of the olefin oligomers.

[0023] The olefin oligomer can be a propylene oligomer (i.e., the repeating units of the olefin oligomer can be substantially all propylene units). For example, the repeating units of the oligomer can comprise at least about 90 mol%, at least 95 mol%, at least 98 mol%, or at least 99 mol% propylene units.

[0024] The olefin oligomer can be an isobutylene oligomer (i.e., the repeat units of the olefin oligomer can be substantially all isobutylene units). For example, the repeat units of the oligomer can include at least 75 mol%, at least 90 mol%, at least 95 mol%, at least 98 mol%, or at least 99 mol% isobutylene units.

[0025] The olefin oligomer has a number average molecular weight (M n ) can be in the range of 150 to 10,000 g / mol. For example, the M nmay be at least 150 g / mol, 250 g / mol, 325 g / mol, 400 g / mol, 500 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, or 750 g / mol. Additionally or alternatively, a maximum M n can be 10,000 g / mol, 7500 g / mol, 6000 g / mol, 5000 g / mol, 4000 g / mol, 3000 g / mol, 2500 g / mol or 2000 g / mol. Generally, the M of the olefin oligomer n is any minimum M n to any maximum M n The range can be:

[0026] The olefin oligomer can have a viscosity index (ASTM D2270) of at least 80. For example, the viscosity index of the olefin oligomer can be at least 85, 90, 95, 100, or 110. Additionally or alternatively, the maximum viscosity index can be 200, 175, 150, 140, 135, 130, 125, or 120. Generally, the viscosity index of the olefin oligomer can range from any minimum viscosity index disclosed herein to any maximum viscosity index disclosed herein.

[0027] The olefin oligomer has a kinematic viscosity (ASTM D445) at 100°C of any suitable value, for example, 1.5 to 50 mm 2 For example, the olefin oligomer or hydrogenated olefin oligomer may have a kinematic viscosity at 100°C of at least 2 mm / s. 2 / s, 3mm 2 / s, 4mm 2 / s or 6mm 2 Additionally or alternatively, the oligomer may have a maximum kinematic viscosity at 100°C of 50 mm / s. 2 / s, 20mm 2 / s, 14mm 2 / s, 12mm 2 / s, 10mm 2 / s or 8mm 2 Generally, the kinematic viscosity at 100° C. of the olefin oligomer can range from any minimum kinematic viscosity disclosed herein to any maximum kinematic viscosity disclosed herein.

[0028] The pour point (ASTM D97) of the olefin oligomer can be within the range of −5° C. to −60° C. For example, the minimum pour point of the olefin oligomer can be −60° C., −50° C., −45° C., −40° C., or −35° C. Additionally or alternatively, the maximum pour point can be −5° C., −8° C., −10° C., −15° C., or −20° C. In general, the pour point of the olefin oligomer can range from any minimum pour point temperature disclosed herein to any maximum pour point temperature disclosed herein.

[0029] Functionalized Olefin Oligomers Heteroatom-functionalized oligomers The olefin oligomers of the present invention may be functionalized by reacting them with heteroatom-containing groups, with or without a catalyst, including hydroxylation, hydrosilylation, ozonolysis, hydroformylation, hydroamination, sulfonation, halogenation, hydrohalogenation, hydroboration, epoxidation, Diels-Alder reactions with polar dienes, Friedel-Crafts reactions with polar aromatic compounds (e.g., hydroxyaromatic compounds), and maleation with activators such as free-radical generators (e.g., peroxides).

[0030] Exemplary groups containing heteroatoms include alcohols, amines, aldehydes, hydroxy aromatic compounds, sulfonates, acids, and anhydrides.

[0031] The number of functional groups in the resulting heteroatom-functionalized oligomer can range from 0.60 to 1.2 functional groups per chain (e.g., 0.75 to 1.1 functional groups per chain). The number of functional groups per chain can be determined by any conventional method, e.g., 1 H NMR spectroscopy).

[0032] Cleaning alcohol The olefin oligomers of the present invention can be functionalized to prepare detergent alcohols such as alkyl ether sulfates (or alcohol ether sulfates) (AES), alkyl ether carboxylates (or alcohol ether carboxylates) (AEC), and alkyl sulfates (AS). Detergent alcohols and their derivatives are widely used as raw materials in the manufacture of surfactants for laundry and dish detergents, as well as other household cleaners and shampoos. These oligomers are also widely used in the cosmetics and hygiene industries.

[0033] Alcohols can be prepared from olefin oligomers and used as feedstocks for preparing high molecular weight polyethers. The polyethers can then be converted to AES and AEC. These compositions can be used as surfactants for chemical EOR applications. A detailed description of these compounds can be found in C. Negin et al. (Petroleum 2017, 3, 197-211) and U.S. Patent No. 9,745,259, the relevant portions of which are incorporated herein by reference.

[0034] In conventional processes, olefin oligomers can be converted to primary alcohols via oxo synthesis. For example, the alcohols can be reacted with ethylene oxide to form various nonionic ethoxylates, which themselves can function as surfactants or can be further derivatized. Sulfation of the ethoxylates can lead to alcohol ether sulfates. Alternatively, the alcohols can be directly sulfated to produce alkyl sulfates (AS).

[0035] Olefin sulfonate Olefin sulfonate surfactants (e.g., alpha olefin sulfonates and internal olefin sulfonates) have favorable detergency, high compatibility with hard water, and good wetting and foaming properties. Commercial applications include shampoos, light-duty liquid detergents, bubble baths, heavy-duty liquid detergents, heavy-duty powder detergents, and emulsion polymerization. In particular, C 14 ~C 16 Alpha olefin sulfonate (AOS) blends are often used in liquid hand soaps. Olefin sulfonates can be used as surfactants in chemical EOR applications and household cleaners due to their good detergency, foaming, and wetting properties.

[0036] Olefin oligomers can be precursors in the production of AOS surfactants. They can be functionalized by reaction of the oligomer with a sulfonating reagent to provide an olefin sulfonic acid intermediate, which can then be neutralized to provide an olefin sulfonate salt.

[0037] In internal olefin sulfonates (IOS), the sulfonation reaction can occur at any position along the chain because the double bonds are randomly distributed. IOS can be prepared by sulfonation of internal olefins.

[0038] Sulfonation of the olefin oligomer may be carried out by any known method, for example, the olefin oligomer can first be sulfonated in a continuous thin film reactor to produce a mixture of alkene sulfonic acids and sultones (cyclic sulfonate esters).

[0039] Sulfonation can also be carried out by using chlorosulfonic acid, sulfamic acid and sulfuric / oleum.

[0040] Neutralization of olefin sulfonic acid to produce olefin sulfonate salts may be carried out in a continuous or batch process by any method known to those skilled in the art. Typically, the olefin sulfonic acid is neutralized with a source of monovalent cation (e.g., sodium or an alkali metal such as ammonium or substituted ammonium ion) and then hydrolyzed at elevated temperatures to convert the remaining sultone to alkene sulfonate and hydroxy sulfonate salts. This provides an aqueous solution of olefin sulfonate salts. If a solid, anhydrous product is desired, the product can be obtained by neutralizing and hydrolyzing a solution of the product in isopropanol instead of water. Optionally, the neutralized olefin sulfonate salts may be further hydrolyzed with additional base or caustic.

[0041] The surfactant composition may also contain aqueous bases such as carbonates, hydroxides, bicarbonates of alkali metal ions, ammonium ions, and amine compounds.

[0042] Depending on the type of oil layer, an alkali may be included with the surfactant composition. In one embodiment, the alkali used is a basic salt of an alkali metal of Group IA metal of the periodic table (such as an alkali metal hydroxide, borate, carbonate, or bicarbonate). For example, the alkali may include sodium carbonate, sodium bicarbonate, sodium silicate, tetrasodium EDTA, sodium metaborate, sodium citrate, or sodium tetraborate. The use of an alkali maintains the surfactant in a high pH environment, thereby extending the stability of the surfactant or minimizing its adsorption. The alkali can also protect the surfactant from hardness.

[0043] The surfactant composition may also contain additional additives such as co-surfactants, polymers, chelators, co-solvents, reducing agents / scavengers, and biocides. This combined composition is often referred to as a slug.

[0044] Suitable co-solvents may be selected from lower carbon chain alcohols such as isopropyl alcohol, ethanol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, n-amyl alcohol, sec-amyl alcohol, n-hexyl alcohol, sec-hexyl alcohol, etc., alcohol ethers, polyalkylene alcohol ethers, polyalkylene glycols, poly(oxyalkylene) glycols, poly(oxyalkylene) glycol ethers or any other common organic co-solvent, or a combination of any two or more co-solvents. In some cases, the co-solvent may be water.

[0045] In particular, polymers may be used to control the fluidity of slugs when they are injected into oil reservoirs for enhanced oil recovery. Suitable polymers include, but are not limited to, biopolymers such as xanthan gum and scleroglucan, and synthetic polymers such as unhydrolyzed or partially hydrolyzed water-soluble polyacrylamide (HPAM or PHPA) and hydrophobically modified related polymers. Also included are copolymers of polyacrylamide (PAM) with one or both of 2-acrylamido-2-methylpropanesulfonic acid (more commonly known as acrylamido tertiary butyl sulfonic acid, or ATBS) (and / or its sodium salt), sold under the trademark AMPS, and N-vinylpyrrolidone (NVP).

[0046] A chelating agent may be added to form a complex with multivalent cations to soften the water in the surfactant composition. Examples of chelating agents include ethylenediaminetetraacetic acid (EDTA) and methylglycine diacetic acid (MGDA), which can also be used as alkalis. The chelating agent may be used to treat hard brine. The amount of chelating agent may be selected based on the amount of divalent ions in the surfactant solution.

[0047] A reducing agent / deoxidizer such as sodium dithionite is added to remove any oxygen in the mixture and reduce any free iron to Fe 2+The iron ions can be used to protect synthetic polymers from reactions that can cleave the polymer molecules and reduce or eliminate their viscosifying ability. The reducing environment can also reduce surfactant adsorption.

[0048] Biocides can be added to prevent the growth of organic matter (algae) within the facility, inhibit the growth of sulfate-reducing bacteria (SRB) that "spoil" the reservoir by producing dangerous and deadly H2S, and also to protect the biopolymer from organisms that feed on its sugar-like structures, thereby causing it to flow uncontrollably. Biocides include aldehydes and quaternary ammonium compounds.

[0049] Alkyl-substituted hydroxyaromatic compounds The olefin oligomers described herein may be functionalized by alkylating a hydroxyaromatic compound with the olefin oligomer to form an alkyl-substituted hydroxyaromatic compound. The alkyl-substituted hydroxyaromatic compounds and their salts are useful as lubricating oil additives.

[0050] Alkyl-substituted hydroxyaromatic compounds are prepared by alkylation methods well known in the art. Useful hydroxyaromatic compounds that may be alkylated include monocyclic monohydroxyaromatic hydrocarbons and polyhydroxyaromatic hydrocarbons having 1 to 4, preferably 1 to 3, hydroxyl groups. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like, and mixtures thereof.

[0051] The alkylation of the hydroxyaromatic compound with the olefin oligomer is generally carried out in the presence of an alkylation catalyst. Useful alkylation catalysts include Lewis acids, solid acids, trifluoromethanesulfonic acid, and acidic molecular sieve catalysts. Suitable Lewis acids include aluminum trichloride, boron trifluoride, and boron trifluoride complexes (e.g., boron trifluoride etherate, boron trifluoride-phenol, and boron trifluoride-phosphoric acid). Suitable solid acids include sulfonated acidic ion exchange resin-type catalysts (e.g., AMBERLYST®-36 (Dow Chemical Company)), clay catalysts (e.g., CelaClear F-24X, Engineered Clays Corp.), or zeolite materials.

[0052] The reaction conditions for the moderation depend on the type of catalyst used, and any suitable set of reaction conditions can be employed that result in a high degree of conversion to alkyl hydroxyaromatic products. Typically, the reaction temperature for the alkylation reaction ranges from 15°C to 200°C (e.g., 85°C to 135°C). The reaction pressure is generally atmospheric, although higher or lower pressures may be used. The alkylation process can be carried out in a batch, continuous, or semi-continuous mode. The molar ratio of hydroxyaromatic compound to olefin oligomer can range from 10:1 to 0.5:1 (e.g., 5:1 to 3:1).

[0053] The alkylation reaction may be carried out neat or in the presence of a solvent that is inert to the reaction of the hydroxyaromatic compound with the olefin mixture.

[0054] Once the reaction is complete, the desired alkyl-substituted hydroxyaromatic compound can be isolated using conventional techniques.

[0055] The alkyl groups of the alkyl-substituted hydroxyaromatic compound are typically attached to the hydroxyaromatic compound primarily at the ortho and para positions relative to the hydroxyl group, and the alkyl-substituted hydroxyaromatic compound may contain 1 to 99% ortho isomer and 99 to 1% para isomer (e.g., 5 to 70% ortho isomer and 95 to 30% para isomer).

[0056] Metal salts of alkylphenols (i.e., phenates) are a useful class of detergents. These detergents can be made by reacting alkaline earth metal hydroxides or oxides (e.g., CaO, Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2) with alkylphenols or sulfurized alkylphenols. When non-sulfurized alkylphenols are used, the sulfurized product may be obtained by methods well known in the art. These methods include heating a mixture of alkylphenol and sulfurizing agent (e.g., elemental sulfur, sulfur halides such as sulfur dichloride, etc.) and then reacting the sulfurized alkylphenol with an alkaline earth metal base.

[0057] Metal salts of alkyl-substituted hydroxyaromatic carboxylic acids are also useful as detergents. Alkyl-substituted hydroxyaromatic carboxylic acids are typically prepared by the carboxylation of alkyl-substituted phenoxides, for example, by the Kolbe-Schmitt process.

[0058] Non-limiting examples of suitable metals include alkali metals, alkaline earth metals, and transition metals, including Li, Na, K, Mg, Ca, Zn, Co, Mn, Zr, Ba, and B.

[0059] Many detergent compositions are overbased, containing large amounts of metal base obtained by reacting an excess of a metal compound (e.g., a metal carbonate, hydroxide, or oxide) with an acid gas (e.g., carbon dioxide). Useful detergents can be neutral, moderately overbased, or highly overbased. Overbasing processes are known to those skilled in the art.

[0060] The basicity of a detergent may be expressed as a total base number (TBN). The total base number is the amount of acid required to neutralize all of the bases in the overbased material. TBN may be measured using ASTM D2896 or an equivalent procedure. The detergents of the present invention may have a low TBN (i.e., a TBN less than 50 mg KOH / g), a medium TBN (i.e., a TBN between 50 and 150 mg KOH / g), or a high TBN (i.e., a TBN greater than 150 mg KOH / g, such as between 150 and 500 mg KOH / g or greater).

[0061] Olefin oligomers grafted with ethylenically unsaturated carboxylic acid materials The olefin oligomers described herein may be functionalized by reacting the oligomer with an ethylenically unsaturated carboxylic acid or derivative thereof.

[0062] The ethylenically unsaturated carboxylic acid or derivative thereof may be an acid, anhydride, or derivative thereof, which may be fully esterified, partially esterified, or a mixture thereof. If partially esterified, the other functional group may include an acid, a salt, or a mixture thereof. Suitable salts include alkali metal, alkaline earth metal, or a mixture thereof.

[0063] Suitable examples of ethylenically unsaturated carboxylic acids or derivatives thereof include (meth)acrylic acid, methyl acrylate, maleic acid or anhydride, fumaric acid, itaconic acid or anhydride, mixtures thereof, or substituted equivalents thereof.

[0064] The olefin oligomer can be functionalized with an ethylenically unsaturated carboxylic acid or derivative thereof by any suitable method, for example, the ethylenically unsaturated carboxylic acid or derivative thereof may be grafted onto the olefin oligomer by a process involving the use of chlorine, or by a thermal "ene" process or a free radical process.

[0065] Upon reaction with the oligomer, the double bond of the ethylenically unsaturated carboxylic acid or derivative becomes saturated. Thus, for example, maleic anhydride reacted with the olefin oligomer becomes an alkyl-substituted succinic anhydride.

[0066] The alkyl-substituted succinic anhydride can then be used as a feedstock to make succinimide dispersants. Succinimide dispersants help keep critical engine parts clean, extending engine life, maintaining proper emissions, and good fuel economy. Succinimides as additives can also provide protection against soot-promoting abrasive engine wear in diesel engine oil formulations. Succinimides can provide excellent soot dispersancy and also function as viscosity index improvers for oils.

[0067] In turn, functionalized olefin oligomers can be derivatized with a derivatizing compound. The derivatizing compound can react with the functional groups of the functionalized oligomer by means such as nucleophilic substitution, Mannich base condensation, etc. Exemplary derivatizing compounds include amines, hydroxyl-containing compounds, metal salts, anhydride-containing compounds, and acetyl halide-containing compounds. The derivatizing compound can contain one or more nucleophilic groups. Derivatized oligomers can be made by contacting a functionalized oligomer (i.e., a carboxylic acid / anhydride- or ester-substituted oligomer) with a nucleophile (i.e., an amine, an alcohol (including polyols, aminoalcohols), a reactive metal compound, etc.).

[0068] Amine compounds useful as nucleophiles for reacting with the functionalized oligomer include monoamines and polyamines having a total of about 2 to 60 (e.g., 3 to 20) carbon atoms and about 1 to 12 (e.g., 3 to 9) nitrogen atoms. Suitable polyamines include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, aliphatic polyamines containing ether groups, and polyoxyalkylene polyamines, such as those available under the trade name JEFFAMINE® (from Huntsman International LLC, USA).

[0069] An exemplary polyamine is HN-(R'NH) x -H, where R' is a straight or branched chain alkylene group having 2 or 3 carbon atoms, and x is 1 to 9 (e.g., ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, and heavy polyamines such as Heavy Polyamine X available from Dow Chemical Company).

[0070] The functionalized and / or derivatized oligomers find use as lubricating oil additives which can function as dispersants, viscosity index improvers or multifunctional viscosity index improvers.

[0071] Functionalized and / or derivatized oligomers that find use as dispersants typically have a number average molecular weight (M n ) is 10,000 g / mol or less, and can typically be in the range of 500 to 10,000 g / mol, 750 to 5000 g / mol, or 1000 to 3000 g / mol.

[0072] The functionalized and / or derivatized oligomers described herein may be combined with other additives (e.g., detergents, dispersants, antioxidants, antiwear agents, friction modifiers, rust inhibitors, viscosity modifiers, pour point depressants, antifoam agents, etc.) to form compositions for many applications, including lubricating oil additive packages, lubricating oils, etc.

[0073] Compositions containing these additives are typically blended into base oils in amounts effective to provide their usual attendant functions. Typical amounts of such additives are shown in Table 1 below. The weight amounts in the table below, and other amounts referred to herein, are based on the amount of active ingredient (which is the non-diluent portion of that ingredient). The weight percent (wt.%) shown below is based on the total weight of the lubricating oil composition.

[0074] Lubricating oil The olefin oligomers of the present disclosure may be useful as additives in lubricating oils to prevent or reduce undesirable light-off phenomena in combustion engines (e.g., dispersants, detergents, etc.). When used in this manner, the additives are typically present in the lubricating oil composition at a concentration ranging from 0.001 to 10 wt. % (including, but not limited to, 0.01 to 5 wt. %, 0.2 to 4 wt. %, 0.5 to 3 wt. %, 1 to 2 wt. %, etc.) based on the total weight of the lubricating oil composition. Lesser amounts of the additive may be used when other hydride donors are present in the lubricating oil composition.

[0075] Oils used as base oils are selected or blended depending on the desired end use and additives in the finished oil to produce a lubricating oil composition having a desired grade of engine oil, for example, a Society of Automotive Engineers (SAE) Viscosity Grade of 0W, 0W-8, 0W-16, 0W-20, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, or 15W-40.

[0076] An oil of lubricating viscosity (sometimes referred to as a "base stock" or "base oil") is the primary liquid component of a lubricating oil into which additives and, optionally, other oils are blended to make, for example, the final lubricating oil (or lubricating oil composition). Base oils useful for making concentrates and lubricating oil compositions therefrom may be selected from natural lubricating oils (vegetable, animal, or mineral) and synthetic lubricating oils, and mixtures thereof.

[0077] The definitions of base stocks and base oils in this disclosure are the same as those found in American Petroleum Institute (API) Publication 1509 Annex E (“API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils,” December 2016). Group I base stocks have less than 90% saturates and / or greater than 0.03% sulfur, and a viscosity index greater than or equal to 80 and less than 120, using the test methods defined in Table E-1. Group II base stocks have greater than or equal to 90% saturates, less than or equal to 0.03% sulfur, and a viscosity index greater than or equal to 80 and less than 120, using the test methods defined in Table E-1. Group III base stocks have greater than or equal to 90% saturates, less than or equal to 0.03% sulfur, and a viscosity index greater than or equal to 120, using the test methods defined in Table E-1. Group IV base stocks are polyalphaolefins (PAOs). Group V substrates include all other substrates not included in Groups I, II, III, or IV.

[0078] Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), and mineral oils. Animal oils and vegetable oils with favorable thermal oxidative stability can be used. Among natural oils, mineral oils are preferred. Mineral oils vary greatly in their crude oil source, for example, whether the crude oil is paraffinic, naphthenic, or a mixture of paraffinic and naphthenic. Oils derived from coal or shale are also useful. Natural oils also vary in the methods used to produce and refine them, for example, their distillation range and whether they are straight run, cracked, hydrotreated, or solvent extracted.

[0079] Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized olefins and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alphaolefin copolymers). The base material for polyalphaolefin (PAO) oil is a commonly used synthetic hydrocarbon oil. Examples include C8 to C 14 Olefins, such as C8 olefins, C 10 Olefin, C 12 Olefin, C 14 PAOs derived from olefins or mixtures thereof may be used.

[0080] Other fluids useful for use as base oils include non-traditional or unconventional base stocks that are preferably catalytically treated or synthesized to provide high performance characteristics.

[0081] Non-conventional or unconventional base stocks / base oils include one or more of a blend of base stock(s) derived from one or more gas-to-liquids (GTL) materials, isomerized / hydrodewaxed base stock(s) derived from natural wax or waxy feeds, mineral oil and non-mineral waxy feeds (such as slack wax, natural waxes), and waxy feeds (such as gas oil, waxy fuel hydrocracked bottoms, waxy raffinates, hydrocrackates, thermal crackers), or waxy materials derived from other minerals, mineral oils, or non-petroleum oils (such as waxy materials obtained from coal liquids or shale oil), and blends of such base stocks.

[0082] The base oil used in the lubricating oil composition of the present disclosure may be any of various oils corresponding to API Group I, Group II, Group III, Group IV, and Group V oils, and mixtures thereof, preferably API Group II, Group III, Group IV, and Group V oils, and mixtures thereof, and more preferably Group III to Group V base oils because of their excellent volatility, stability, viscosity, and detergency characteristics.

[0083] Typically, the base oil has a kinematic viscosity (ASTM D445) at 100°C of 2.5 to 20 mm 2 / s (e.g., 3 to 12 mm 2 / s, 4~10mm 2 / s or 4.5 to 8 mm 2 / s).

[0084] The lubricating oil composition of the present invention may also contain conventional lubricating oil additives to provide auxiliary functions, resulting in a finished lubricating oil composition in which these additives are dispersed or dissolved. For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, antiwear agents, detergents (such as metal-based detergents), rust inhibitors, dehaze removers, demulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, antifoam agents, cosolvents, package compatibilizers, corrosion inhibitors, colorants, extreme pressure agents, and the like, and mixtures thereof. A variety of additives are known and commercially available. These additives or their analogous compounds can be used in preparing the lubricating oil composition of the present invention by conventional blending procedures.

[0085] Each of the above additives, when used, is used in a functionally effective amount to impart the desired characteristics to the lubricating oil. That is, for example, if the additive is an ashless dispersant, a functionally effective amount of the ashless dispersant would be an amount sufficient to impart the desired dispersant characteristics to the lubricating oil. Generally, the concentration of each of these additives, when used, can range from about 0.001 to about 20 wt. %, such as from about 0.01 to about 10 wt. %, unless otherwise specified. [Table 1] [Example]

[0086] The following illustrative examples are intended to be non-limiting.

[0087] Example 1 Distillation of crude propylene oligomers Propylene oligomerization was carried out in an autoclave reactor for a time sufficient to produce 10 gallons of product. After washing and drying, the hydrocarbon phase containing the product and n-heptane was vacuum distilled to remove the n-heptane and obtain a stripped oligomer product. The stripped oligomer product was then vacuum distilled (approximately 1.5 torr) using a distillation column (36" x 2") packed with convex packing, and 10 fractions of distilled product were collected. The carbon number distribution of each fraction was analyzed by GC and FIMS. 1 The isomerization level was analyzed by H NMR, and the results are summarized in Table 2. The branching index can be defined as the ratio (%) of the integer value of the protons of the methyl group (CH3) to the sum of the protons of the methylene group (-CH2-), the methynyl group (-CH-), and the methyl group (-CH3). [Table 2]

[0088] Example 2 Preparation of alkylphenols from propylene oligomers. Three different alkylphenols were prepared separately from the combined distillation fractions of Example 1: (1) Alkylphenol 1 derived from fractions 1 and 2 (2) Alkylphenol 2 derived from fractions 4 to 6 (3) Alkylphenol 3 derived from fractions 6 to 8

[0089] Each of the three alkylphenols was prepared using the following general procedure: A 3 L, 3-neck round bottom flask equipped with a mechanical stirrer and thermocouple was charged with the following propylene oligomer fractions: (1) Alkylphenol 1: Approximately 335 g each of fractions 1 and 2 (total approximately 2.5 mol) (2) Alkylphenol 2: Approximately 250 g each of fractions 4, 5, and 6 (total approximately 2.0 mol) (3) Alkylphenol 3: Fractions 6, 7, and 8, each about 250 g (total about 1.7 mol)

[0090] After the oligomer fraction was added, the stirrer was turned on and 1 kg of phenol was added to the flask. The reaction mixture was heated to 60°C, and then 200–250 g of AMBERLYST®-36 ion exchange resin (acid form, dried at 116–120°C for 48–72 hours) was added. The flask was fitted with an air condenser and maintained under a nitrogen purging. The reaction was monitored by GLPC and considered complete when no further reduction of propylene oligomers was observed (approximately 6 days for alkylphenol 1, approximately 3 days for alkylphenol 2, and approximately 4 days for alkylphenol 3). The reaction mixture was allowed to cool and vacuum filtered to remove the catalyst. Excess phenol was removed by vacuum distillation. The properties of the alkylphenols are summarized in Table 3. [Table 3]

[0091] Distortion-free signal enhancement by polarization transfer (DEPT) NMR was performed to determine the total number of CH2 carbon atoms adjacent to the benzylic carbon atom attached to the hydroxyaromatic ring of alkylphenols 1-3. The CH2 carbon atom adjacent to the benzylic carbon atom attached to the hydroxyaromatic ring is 13 The C NMR spectrum is interpreted as appearing at approximately 49-51 ppm. This chemical shift is unique among the CH carbon atoms of propylene oligomeric alkylphenols. This interpretation was determined using a CHEMDRAW® Ultra (Perkin Elmer). The results are summarized in Table 4. [Table 4]

[0092] The results show that more than 99% of the CH2 carbon atoms in alkylphenols 1-3 are not adjacent to a benzylic carbon atom attached to a hydroxy aromatic ring.

[0093] Example 3 Synthesis of alkylphenol carboxylic acids A 4 L, three-necked round-bottom flask equipped with a Dean-Stark tube was charged with alkylphenol 2 (1411 g) from Example 8, xylene (706 g), 45% aqueous KOH (365 g), and antifoam agent (0.2 g). The mixture was heated at 135°C under reduced pressure (450 mm Hg) for 6 hours, during which time xylene and water were continuously distilled back into the mixture via the Dean-Stark tube. The mixture was allowed to cool to ambient temperature under nitrogen. The mixture was then placed in a pressure vessel, heated to 140°C, and the reactor was pressurized with CO (3 bar). After 4 hours, the reactor was depressurized, and the reaction mixture was allowed to cool to ambient temperature.

[0094] The potassium carboxylic acid salt (1100 g) prepared above was added to a round-bottom flask, followed by xylene (602 g), and the mixture was heated to 80°C. A 10% aqueous solution of H2SO4 (887 g) was slowly added to the mixture, and the mixture was maintained at 70°C for 30 minutes. The mixture was transferred to a separatory funnel and allowed to stand for 2 hours. After separation, the upper layer containing the carboxylic acid in xylene was collected.

[0095] The carboxylic acid acidity was determined to be 14.4 mg KOH / g by potentiometry, and the xylene content was 60.2 wt%.

[0096] Example 4 Preparation of overbased carboxylate detergents A reactor was charged with slaked lime (60.3 g), methanol (72.3 g), and xylene (125 g). The carboxylic acid from Example 3 (2200 g) was added to the reactor, and the temperature was maintained at 40° C. Subsequently, a 50 / 50 mixture of acetic acid and formic acid (5.7 g) was added. After cooling to 30° C., CO2 (12.8 g) was slowly introduced into the reactor while the temperature was increased from 30 to 40° C. The temperature was then increased to 128° C., during which time methanol, water, and some of the xylene were distilled off. After adding base oil (175.3 g), the resulting mixture was centrifuged to remove unreacted lime and other solids. The mixture was then heated under vacuum at 170° C. to remove the xylene and yield the overbased carboxylate detergent.

[0097] The properties of the overbased carboxylate detergent are 2.88% Ca, TBN=81 mg KOH / g, and kinematic viscosity at 100°C=20.6 mm 2 / s.

[0098] Example 5 Preparation of overbased phenate detergents A 4-L, three-necked round-bottom flask was charged with alkylphenol 1 from Example 8 (881.6 g), 130N base oil (357.9 g), alkylarylsulfonic acid (39.7 g), and antifoam agent (0.2 g). The mixture was heated to 110°C over 25 minutes, and slaked lime (304 g) was added while warming. Sulfur (90.2 g) was then added, and the reaction temperature was increased to 150°C over 20 minutes. After the sulfur addition, the reactor pressure was reduced to 680 mm Hg. Hydrogen sulfide gas produced during sulfurization was collected using two caustic soda bubblers. Ethylene glycol (46.6 g) was then added over 45 minutes, and the mixture was heated to 170°C. 2-Ethylhexanol (393.6 g) was added over a 30-minute period, and the reaction was cooled to 162°C. The mixture was heated to 170°C, and additional ethylene glycol (76.4 g) was added over 1 hour. After the ethylene glycol addition, the pressure was increased to 720 mm Hg, and the reaction conditions were maintained for 20 minutes. While maintaining the temperature at 170°C, the pressure was increased to 760 mm Hg. CO2 (9 g) was then added over 30 minutes. Ethylene glycol (63.4 g) was then added, and the CO2 rate was increased to 0.8 g / min. Carbonation was stopped once approximately 96 g of CO2 had been added. The solvent was then distilled at 215°C and 30 mm Hg for 1 hour. The temperature was increased to 220°C over 1 hour with a N2 purge at 80 mm Hg. The product was vacuum filtered through CELITE® diatomaceous earth at 165°C, and the filtered overbased phenate was degassed under air for 4 hours at 150°C with 5 L / h / kg of product.

[0099] The properties of the overbased phenate detergent were 10.5 wt% Ca, 3.15 wt% S, TBN=293 mg KOH / g, kinematic viscosity at 100°C=574 mm2 / s.

[0100] Example 6 Preparation of olefin sulfonates Propylene oligomer distillation fraction 3 from Example 1 was sulfonated using SO3 / air in a stainless steel water-jacketed falling film tubular reactor (approximately 0.19" ID x approximately 60" length) under the following conditions: Propylene oligomer feed temperature = 30°C Reactor temperature = 40 °C Air flow rate = 200 L / hour Make-up air flow rate = 11 L / hour SO2 flow rate=16L / hour Conversion rate of SO2 to SO3 = 87% Propylene oligomer feed rate = 2.9 g / min

[0101] The resulting sulfonic acid had properties of 4.28 wt% H2SO4 and 35.18 wt% sulfonic acid (cyclohexylamine titration). The sulfonic acid was digested at 65°C for 30 minutes to give a digested sulfonic acid with properties of 3.99 wt% H2SO4 and 30.03 wt% sulfonic acid.

[0102] The digested sulfonic acid (222.3 g) was neutralized by adding 50 wt. % aqueous NaOH (33.2 g) in portions over 30 minutes at 25°C to 51°C with stirring. The resulting sodium sulfonate was found by hyamine titration to be 27.35 wt. % active and pH = 10.4 (approximately 1 wt. % in aqueous solution). ESI mass spectrometry indicated that the m / z charge ratio of the major component in the sodium sulfonate composition was 373 (see Figure 1).

Claims

1. 1. A method for treating a hydrocarbon-containing reservoir, comprising: introducing a surfactant composition into the oil phase; The surfactant composition comprises an alpha olefin sulfonate or an internal olefin sulfonate, and the alpha olefin sulfonate or the internal olefin sulfonate comprises i) C ３ ~C ６ ii) oligomerizing a monoolefin-containing monomer to form an oligomer; and ii) sulfonating the oligomer; The method as defined above, wherein the step i) of oligomerizing produces oligomers having at least 50 wt % C 12 -C 70 oligomers.

2. By the step i) of oligomerizing, C １６ ~C ４０ 10. The method of claim 1, wherein an oligomer having at least 50 wt% oligomer is produced.

3. The method of claim 1 , wherein the monomer comprises one or more of propylene and isobutylene.

4. The surfactant is Co-surfactants, co-solvents, bases, enhanced oil recovery fluids or well remediation fluids The method of claim 1 further comprising:

5. 5. The method of claim 4, wherein the co-surfactant comprises secondary alkane sulfonates, internal olefin sulfonates, alkoxylated alcohol sulfates, alkoxylated alcohol carboxylates and glycerol sulfonates, linear alkyl benzene sulfonates, heavy alkyl benzene sulfonates, sulfosuccinates, alkyl aromatic sulfonates, nonionic alkoxylated alcohol or alkylaryl disulfonates, and mixtures thereof.

6. The method of claim 4 , wherein the co-solvent is water, an alcohol, or a glycol.

7. 5. The method of claim 4, wherein the base is a carbonate, hydroxide, bicarbonate, ammonium, or an amine.

8. 1. A surfactant for enhanced oil recovery, said surfactant comprising: The alpha olefin sulfonate or the internal olefin sulfonate, wherein the alpha olefin sulfonate or the isomerized olefin sulfonate comprises: i) C ３ ~C ６ ii) oligomerizing a monoolefin-containing monomer to form an oligomer; and ii) sulfonating the oligomer; i) the oligomerization step produces oligomers having at least 50 wt% C 12 -C 70 oligomers; The surfactant.

9. By the step i) of oligomerizing, C １６ ~C ４０ 9. The surfactant of claim 8, wherein an oligomer is produced having at least 50 wt% oligomer.

10. 9. The surfactant of claim 8, wherein the monomer comprises one or more of propylene and isobutylene.

11. Co-surfactants, co-solvents, bases, enhanced oil recovery fluids or well remediation fluids The surfactant of claim 8 further comprising:

12. 12. The surfactant of claim 11, wherein the co-surfactant comprises secondary alkane sulfonates, internal olefin sulfonates, alkoxylated alcohol sulfates, alkoxylated alcohol carboxylates and glycerol sulfonates, linear alkyl benzene sulfonates, heavy alkyl benzene sulfonates, sulfosuccinates, alkyl aromatic sulfonates, nonionic alkoxylated alcohol or alkylaryl disulfonates, and mixtures thereof.

13. 12. The surfactant of claim 11, wherein the co-solvent is water, an alcohol, or a glycol.

14. 12. The surfactant of claim 11, wherein the base is a carbonate, hydroxide, bicarbonate, ammonium, or amine.

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