Alkyl-substituted hydroxyaromatic compounds having highly structured alkyl branches

Abstract

The present disclosure provides a hydroxyaromatic product. The alkyl hydroxyaromatic compound has a structure imparted by the formula (I), where R is a hydroxyaromatic group, X is hydrogen or a methyl group, and n is 1 or more.

Description

Technology Field

[0001] The present disclosure relates to commercial alkyl-substituted hydroxyaromatic products. More specifically, the present disclosure relates to alkyl-substituted hydroxyaromatic additives having highly structured alkyl groups, and to compositions and methods for preparing lubricating oil compositions containing the same. Background Technology

[0002] Alkyl-substituted hydroxyaromatic compounds (e.g., alkylphenols) can be used to manufacture a number of commercial products, including detergents, emulsifiers, pesticides, fragrances, thermoplastic elastomers, antioxidants, and surfactants. For example, alkylphenols can be used to synthesize sulfide alkyl-substituted phenate compounds useful as detergents in lubricating oils. One problem is the potential toxicity of alkylphenols to the environment. Certain alkylphenols, such as tetrapropenphenol (TPP), are now classified as reproductive toxins. In the lubricating oil industry, the persistence of TPP as a byproduct of unsulfide alkyl-substituted phenate during detergent synthesis is a problem.

[0003] Another problem specific to TPP relates to the synthesis involving the alkylation of phenol using propylene oligomers. In conventional synthesis, phenol molecules are alkylated into propylene oligomers rich in propylene tetramers, which have a highly chaotic nonlinear structure and highly substituted internal double bonds (e.g., trisubstituted and tetrasubstituted). The dense structure of propylene tetramers is likely one of the main reasons why the alkylation reaction requires several days and an excessive amount of propylene tetramers to proceed.

[0004] As part of efforts to address these ongoing problems, alternative olefins have been identified as potential substitutes for propylene tetramers. In particular, structurally isomerized linear alpha-olefins have been used in the production of commercial alkylphenol detergents. However, the isomerization step results in less active internal olefins, adding to the already high cost of linear alpha-olefins. Furthermore, alkylphenol products prepared from isomerized linear alpha-olefins often perform relatively poorly in laboratory tests, possibly due to inappropriate methyl branching.

[0005] Other efforts focus on utilizing polyisobutylene-based olefins as a source for alkylphenol detergents. A major drawback of using polyisobutylene (PIB) as an olefin feedstock is that it requires modifying the alkylation technology with special alkylation catalysts.

[0006] In one aspect, a hydroxyaromatic product comprising the following is provided:

[0007] Alkyl hydroxyaromatic compounds having a structure imparted by the following:

[0008]

[0009] Here, R is a hydroxyaromatic group, X is a hydrogen or methyl group, and n is 1 or more.

[0010] In another aspect, an alkyl-substituted hydroxyaromatic compound is provided, formed by a process comprising the step of alkylating a hydroxyaromatic compound with an alkylating agent containing a vinylidene-rich propylene oligomer comprising a vinylidene double-bonded propylene oligomer, wherein the propylene oligomer is prepared by oligomerizing a propylene-rich feedstock containing an olefin, wherein at least 50 mol% of the olefin in the feedstock is propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond.

[0011] In another aspect, a lubricating oil composition comprising a base oil; and a detergent derived from an alkylphenol sulfide, wherein the alkylphenol is prepared by alkylation using an alkylating agent containing a vinylidene-rich propylene oligomer comprising a propylene oligomer terminated by a vinylidene double bond, and the propylene oligomer is prepared by oligomerizing a propylene-rich feedstock containing an olefin, wherein at least 50 mol% of the olefin in the feedstock is propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond.

[0012] In another aspect, a method for alkylating a hydroxyaromatic compound is provided, wherein the method comprises the step of oligomerizing a propylene monomer in the presence of a single-site catalyst to form a vinylidene-rich propylene oligomer comprising a propylene oligomer terminated by a vinylidene double bond, wherein the propylene oligomer is prepared by oligomerizing a propylene-rich feedstock containing an olefin, wherein at least 50 mol% of the olefin in the feedstock is propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond; and the step of alkylating a hydroxyaromatic compound into a vinylidene-rich propylene oligomer. Brief explanation of the drawing

[0013] Figure 1 shows a graph described in the embodiment. Specific details for implementing the invention

[0014] The term “olefin” refers to a hydrocarbon having at least one carbon-carbon double bond that is not part of an aromatic ring or cyclic system. Unless otherwise specifically stated, the term “olefin” includes aliphatic and aromatic, cyclic and acyclic, and / or linear and branched compounds having at least one carbon-carbon double bond that is not part of an aromatic ring or cyclic system. Olefins having only one, only two, only three, etc., carbon-carbon double bonds may be identified by using terms such as “mono,” “die,” or “tri” within the olefin name. Olefins may be further identified by the position of the carbon-carbon double bond(s). Depending on the context, the term “olefin” may refer to an “olefin oligomer” or an “olefin monomer.”

[0015] "Olefin oligomers" are oligomers prepared from oligomers of "olefin monomers." For example, "propylene oligomers" are prepared by the oligomerization of nominal propylene monomers. Examples of propylene oligomers include propylene tetramers and propylene pentamers. "Propylene tetramers" are olefin oligomer products produced from the oligomerization of nominal four propylene monomers. These terms may also be commonly used to describe homo-oligomers, co-oligomers, salts of oligomers, derivatives of oligomers, etc.

[0016] The unrefined product of the oligomerization process typically comprises a mixture of branched olefin oligomers having a carbon number distribution. The unrefined oligomer product generated from the oligomerization of monomers can be distilled to further isolate or purify the olefin oligomer product to a desired carbon range.

[0017] The term "alkyl" or related terms refer to a saturated hydrocarbon group, which may be linear, branched, cyclic, or a combination of cyclic, linear, and / or branched.

[0018] "Vinylidene-rich propylene oligomers" refer to propylene-based oligomers in which a vinylidene moiety is dominant. Olefin oligomers possessing a vinylidene moiety undergo cosite disubstitutement at the inner end of the terminal double bond. Conventionally produced propylene oligomers are typically rich in molecules with trisubstituted or tetrasubstituted inner double bonds.

[0019] As used in this specification, the term “substituted” means that the hydrogen group is replaced by an alkyl group, an aromatic group, a heteroatom, or a heteroatom-containing group.

[0020] Where combinations, subsets, groups, etc. of elements (e.g., combinations of components in a composition, or combinations of steps in a method) are disclosed, specific references to each of the various individual and collective combinations and permutations of these elements may not be explicitly disclosed, but each is understood to be specifically conceived and described herein.

[0021] The present invention provides a composition and a method related to an alkyl-substituted hydroxyaromatic product having a highly structured alkyl group. More specifically, the present invention describes the synthesis of a vinylidene-rich propylene oligomer that can be used to synthesize an alkyl-substituted hydroxyaromatic product useful for the production of a wide range of commercial products.

[0022] Vinylidene-rich propylene oligomers can be prepared using a single-site catalyst. This allows the high vinylidene content oligomers of the present invention to be more reactive in alkylation reactions and enables more efficient synthesis of alkylphenol products.

[0023] High vinylidene content can provide many advantages over conventional propylene tetramer oligomers. For example, alkylation of phenlo using vinylidene-rich propylene oligomers can be efficiently achieved with a reduced olefin-to-phenol ratio. Other advantages may include lower reaction temperature, lower batch cycle time, higher conversion rate, and higher para-alkylphenol content.

[0024] Vinylidene-rich propylene oligomer

[0025] The vinylidene-rich propylene oligomer of the present invention features a highly aligned structure characterized by a long linear backbone and chains having regularly spaced methyl groups.

[0026] The vinylidene-rich propylene oligomer of the present invention has an average number of carbon atoms in the range of about 9 to about 50. In some embodiments, the average number of carbon atoms is in the range of 9 to 42, 9 to 39, 9 to 36, or 12 to 32.

[0027] Vinylidene oligomers are long straight-chain terminal olefins that have branching on all other carbons of the chain, starting from geminal branching on the vinylidene olefin. When numbered from the terminal olefin carbon, the branching is on every even-numbered carbon in the chain (i.e., branching on carbons 2, 4, 6, etc.), except for the last three carbons, and the oligomer chain may be unbranched or otherwise deviate from the regular branching of the rest of the molecule. 2,4-dimethyl 1-heptene (trimer), 2,4,6-trimethyl 1-nonene (tetramer), and 2,4,6,8-tetramethyl 1-undecene (pentmer) are examples of vinylidene oligomers of the present invention.

[0028] In some embodiments, a vinylidene-rich propylene oligomer is a product of oligomerization in which at least 50 mol% of the oligomer has a vinylidene moiety. In some embodiments, at least 60 mol%, 70 mol%, 80 mol%, 90 mol%, or 95 mol% of the oligomer has a vinylidene moiety. The byproduct of oligomerization may include an oligomer that does not have a vinylidene moiety. These oligomers may have other moiety / coordinations at the double bond, such as trisubstitution, tetrasubstitution, vinyl, and dissubstitution (cis or trans). A vinylidene-rich propylene oligomer is prepared by oligomerizing a propylene-rich feedstock containing an olefin, wherein at least 50 mol% of the olefin in the feedstock is propylene and at least 50 mol% or at least 70 mol% of the propylene oligomer may have vinylidene double bonds.

[0029] Although propylene is the main olefin monomer in the oligomerization reaction, the source may have a mixture of olefins having different numbers of carbon atoms, or a mixture of olefins having mainly a single number of carbon atoms. The olefin may 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 propylene. The monomer may be additionally introduced into the oligomerization reaction as a mixture with one or more non-olefinic hydrocarbons, such as alkanes or aromatics.

[0030] In one embodiment, propylene monomer is supplied from a cracking operation and is used without separating propylene from propane prior to the oligomerization reaction. This cracking operation may be catalytic cracking, e.g., fluid catalytic cracking, or thermal cracking, e.g., steam cracking, or coking. In one embodiment, the cracking operation may involve propane dehydrogenation.

[0031] The synthesis of vinylidene-rich propylene oligomers can be carried out through any known oligomerization method. The synthesis of olefin oligomers or polyolefins is generally known in the relevant art. In particular, the synthesis of polyolefins using single-site catalysts is known to provide polymers having a highly defined microstructure, tacticity, stereoregularity, etc.

[0032] The vinylidene-rich propylene oligomer of the present invention can be prepared by using a commercially available single-site catalyst(s) capable of controlling side chain length and / or branching. Single-site catalysts generally belong to two groups: metallocene catalysts and non-metallocene catalysts.

[0033] Metallocenes are well-known complex organometallic molecules typically containing zirconium, titanium, hafnium, IVA, VA and VIA group transition metals, lanthanide metals, etc. The metal is typically located at or near the center of the complex and coordinates to two cyclic alkyl anions, such as a cyclopentadienyl anion. A more detailed discussion of metallocenes can be found in US6511568, which is incorporated herein by reference. Other suitable metallocenes include ansa-metallocenes and metallocene and metallocene catalyst systems described in US8536391, which is incorporated herein by reference.

[0034] In one embodiment, the metallocene has the following chemical formula:

[0035] (RCp)2MX2

[0036] In the formula, Cp is a cyclopentadieneyl group, RCp is a substituted cyclopentadieneyl group, R is an alkyl group or hydrogen, M is Ti, Zr or Hf, and X is Cl, Br, I, H, Me or Et.

[0037] Non-metallocene single-site catalysts are typically transition metal catalysts. Transition metal catalysts are described in WO9827124, WO9830612, WO9623010, and EP0816387, which are incorporated herein by reference. Specific examples of non-metallocene single-site catalysts include Ni, Pd diimine catalyst systems, Fe pyridine-diimine catalyst systems, 8-quinolinol Ti catalyst systems, azetidine titanium catalyst systems, chelating diamine catalyst systems, etc.

[0038] The oligomer product is a propylene oligomer (i.e., the repeating units of the olefin oligomer may be substantially all propylene units). For example, the repeating units of the oligomer may contain at least about 90 mol%, at least 95 mol%, at least 98 mol%, or at least 99 mol% of propylene units.

[0039] The oligomer product may comprise dimers, trimers, and / or higher-order oligomers. In some embodiments, the oligomer product comprises (i) at least 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of dimers, trimers, tetramers, pentamers, hexamers, heptmers, octamers, gummymers, and / or demers; (ii) at least 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 85 wt%, or 90 wt% of trimers, tetramers, pentamers, hexamers, heptmers, octamers, gummymers, and / or demers; (iii) at least 75 wt%, 80 wt%, 85 wt%, 90 wt% or 95 wt% of dimers, trimers, tetramers, pentamers, hexamers and / or heptmers; (iv) at least 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 80 wt%, 85 wt% or 90 wt% of trimers, tetramers, pentamers, hexamers and / or heptmers; (v) at least 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt% or 60 wt% of dimers, trimers, tetramers and / or pentamers; (vi) at least 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt% or 50 wt% of trimers, tetramers and / or pentamers; (vii) 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) may comprise any combination thereof.

[0040] In additional or alternative embodiments, the oligomer product may comprise at least 35 wt%, 45 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or 65 wt% of trimers, tetramers, and pentamers in total; alternatively or additionally, a mixture of 100 wt%, 95 wt%, 90 wt%, or 85 wt% of trimers, tetramers, and pentamers in total. In some embodiments, the olefin oligomer 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% of trimers, tetramers, and pentamers in total.

[0041] The oligomer product may comprise 40 wt%, 30 wt%, 25 wt%, 20 wt%, 18 wt%, 16 wt%, 14 wt%, 12 wt%, or less than 10 wt% of dimers. Additionally or alternatively, the oligomer product may comprise an oligomer containing 7 or more monomer units, comprising 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%, 8 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, or less than 2 wt%.

[0042] In some aspects, the oligomer product is at least 50 wt%, 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of C 12 to C 70 (e.g., C 12 to C 40 , C 12 to C 30 , C 12 to C 20 , C 14 to C 70 , C 14 to C 40, C 14 to C 30 , C 14 to C20 , C 16 to C 70 , C 16 to C 40, C 16 to C 30 , C 16 to C 24 , C 20 to C 70 , C 20 to C 40 , C 20 to C 30 , or C 20 to C 24 ) may include oligomers. In some aspects, the oligomer product comprises 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%, 8 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, or less than 2 wt% >C 70 It may include oligomers. The weight percentage of the oligomer(s) disclosed herein is based on the total weight of the oligomer product.

[0043] The oligomer product has a number average molecular weight (M) in the range of 150 to 10,000 g / mol. n It can have ). For example, M of the oligomer product n It may be at least 150, 250, 325, 400, 500, 600, 650, 700, or 750 g / mol. Additionally or alternatively, up to M n It can be 10,000, 7,500, 6,000, 5,000, 4,000, 3,000, 2,500, or 2,000 g / mol. Generally, M of the oligomer product n Any minimum M disclosed in this specification n Any maximum M disclosed in this specification from n It can be within the range up to.

[0044] Heteroatom-functionalized oligomers

[0045] Depending on the application, olefin oligomers can be functionalized by reacting heteroatom-containing groups with the olefin oligomer with or without a catalyst. These reactions include hydroxylation, hydrosylation, ozone decomposition, hydroformylation, hydroamide, sulfonation, halogenation, hydrohalogenation, hydroboration, epoxidation, Diels-Alder reaction with polar dienes, Friedel-Crafts reaction with polar aromatics (e.g., hydroxyaromatics), and maleation by activators such as free radical generators (e.g., peroxides).

[0046] Exemplary heteroatom-containing groups include alcohols, amines, aldehydes, hydroxyaromatic compounds, sulfonates, acids, and anhydrides.

[0047] The number of functional groups in the resulting heteroatom-functionalized oligomer may be in the range of 0.60 to 1.2 functional groups / chain (e.g., 0.75 to 1.1 functional groups / chain). The number of functional groups per chain may be determined by any conventional method (e.g., 1 It can be determined by H NMR spectroscopy.

[0048] Alkyl-substituted hydroxyaromatic compounds having highly structured alkyl groups

[0049] The olefin oligomers described herein can be used to alkylate hydroxyaromatic compounds to form alkyl-substituted hydroxyaromatic compounds. Alkyl-substituted hydroxyaromatic compounds are useful as precursors or final products in various commercial applications.

[0050] Alkyl hydroxyaromatic compounds may have the structures assigned below:

[0051]

[0052] Here, R is a hydroxyaromatic group, X is a hydrogen or methyl group, and n is 1 or more. In some embodiments, n is 20 or more. In some embodiments, n is 2 to 6.

[0053] Useful hydroxyaromatic compounds that can be alkylated include mononuclear monohydroxy and polyhydroxyaromatic hydrocarbons having 1 to 4, preferably 1 to 3, hydroxyl groups. Suitable hydroxyaromatic compounds (or groups) include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, naphthol, hydroxybenzoic acid, etc., mixtures thereof, and salts thereof (e.g., phenates).

[0054] Alkylation of hydroxyaromatic compounds using olefin oligomers is generally carried out in the presence of an alkylation catalyst. Useful alkylation catalysts include Lewis acids, solid acids, trifluoromethanesulfonic acids, 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-phosphate). Suitable solid acids include sulfonated acidic ion exchange resin catalysts, e.g., AMBERLYST®-36 (Dow Chemical Company), clay catalysts (e.g., CelaClear F-24X Engineered Clays Corp), or zeolite materials.

[0055] The reaction conditions for alkylation depend on the type of catalyst used, and any suitable set of reaction conditions that result in a high conversion rate to the alkyl hydroxyaromatic product may be used. Typically, the reaction temperature for the alkylation reaction will be in the range of 15°C to 200°C (e.g., 85°C to 135°C). The reaction pressure may generally be atmospheric pressure, but higher or lower pressures may be used. The alkylation process may be carried out in a batch, continuous, or semi-continuous manner. The molar ratio of the hydroxyaromatic compound to the olefin oligomer may be in the range of 10:1 to 0.5:1 (e.g., 5:1 to 3:1).

[0056] The alkylation reaction can be carried out either by itself or in the presence of a solvent that is inert to the reaction of a mixture of hydroxyaromatic compounds and olefins.

[0057] When the reaction is complete, the desired alkyl-substituted hydroxyaromatic compound can be isolated using conventional techniques.

[0058] In alkyl-substituted hydroxyaromatic compounds, the alkyl group is typically attached to the hydroxyaromatic compound mainly at the ortho or para position relative to the hydroxyl group. The alkyl-substituted hydroxyaromatic compound may contain 1 to 99% ortho isomers and 99 to 1% para isomers (e.g., 5 to 70% ortho isomers and 95 to 30% para isomers). Additionally, at least 50 mol% of the alkyl group in the alkyl hydroxyaromatic compound may have a ratio of methyl carbon to methylene carbon greater than about 0.85. In addition, at least 50 mol% of the alkyl groups in the alkyl hydroxy aromatic compound may have an NMR branching index of 45% or more, and at least 50 mol% of the alkyl groups in the alkyl hydroxy aromatic compound may have a ratio of methyl carbon to methylene carbon and methine carbon greater than about 0.29. At least 50 mol% of the alkyl hydroxy aromatic compound may have a ratio of methyl-branched methylene carbon resonance in the range of 44 to 49 ppm measured in chloroform to combined saturated aliphatic carbon resonance in the range of 10 to 50 ppm measured in chloroform greater than 0.15.

[0059] Metal salts of alkylphenols (i.e., phenates) are a useful class of detergents. These detergents can be prepared 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 alkylphenols sulfated. When non-sulfated alkylphenols are used, the sulfation product can be obtained by methods well known in the art. These methods involve heating a mixture of alkylphenols and a sulfating agent (e.g., elemental sulfur, sulfur halides, e.g., sulfur dichloride, etc.) and then reacting the alkylphenol sulfated with an alkaline earth metal base.

[0060] Metal salts of alkyl-substituted hydroxyaromatic carboxylic acids are also useful as detergents. Alkyl-substituted hydroxyaromatic carboxylic acids are typically produced by the carboxylation of alkyl-substituted phenoxides, for example, by the Kolbe-Schmitt process.

[0061] Non-limiting examples of suitable metals include alkali metals, alkaline earth metals, and transition metals. Examples include Li, Na, K, Mg, Ca, Zn, Co, Mn, Zr, Ba, and B.

[0062] Many detergent compositions containing a large amount of metal base, achieved by reacting an excess amount of metal compound (e.g., metal carbonate, hydroxide, or oxide) with an acidic gas (e.g., carbon dioxide), are superbased. Useful detergents can be neutral, slightly superbased, or highly superbased. The superbasing process is known to those skilled in the art.

[0063] The basicity of a detergent can be expressed as the total base number (TBN). The total base number is the amount of acid required to neutralize all the basicity of a superbasicized substance. TBN can be measured using ASTM D2896 or an equivalent procedure. Detergents may have a low TBN (i.e., TBN less than 50 mg KOH / g), a medium TBN (i.e., TBN between 50 and 150 mg KOH / g), or a high TBN (i.e., TBN greater than 150 mg KOH / g, e.g., TBN between 150 and 500 mg KOH / g).

[0064] Functionalized oligomers and / or derivatized oligomers have uses as lubricant additives that can act as dispersants, viscosity index improvers, or multifunctional viscosity index improvers.

[0065] The olefin oligomers and products thereof described in this specification may be combined with other additives (e.g., detergents, dispersants, oxidation inhibitors, wear inhibitors, friction modifiers, rust inhibitors, viscosity modifiers, pour point depressants, foam inhibitors, etc.) to form compositions for many uses, including lubricant additive packages, lubricants, etc.

[0066] Compositions containing these additives are typically blended into the base oil in an amount effective to provide their normal accompanying functions. Typical amounts of these additives are shown in Table 1 below. The weights in the table below, as well as other amounts mentioned herein, relate to the amount of the active ingredient (the undiluted portion of the ingredient). The weight percentages (weight%) shown below are based on the total weight of the lubricating oil composition.

[0067]

[0068] lubricant

[0069] The olefin oligomers of the present disclosure may be useful as additives in lubricating oils (e.g., as dispersants, detergents, etc.) to prevent or reduce undesirable ignition events in combustion engines. When used in this manner, the additive is typically present in the lubricating oil composition at a concentration ranging from 0.001 to 10 weight percent (including, but not limited to, 0.01 to 5 weight percent, 0.2 to 4 weight percent, 0.5 to 3 weight percent, 1 to 2 weight percent, etc.) based on the total weight of the lubricating oil composition. If other hydride donors are present in the lubricating oil composition, a smaller amount of the additive may be used.

[0070] The oil used as the base oil will be selected or blended according to the intended end use and additives in the final oil to provide a lubricant composition having a Society of Automotive Engineers: SAE viscosity grade of the desired grade of engine oil, e.g., 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.

[0071] An oil of lubricating viscosity (sometimes referred to as "base stock" or "base oil") is the main liquid component of a lubricant, to which additives and possibly other oils are blended to produce, for example, a final lubricant (or lubricant composition). Base oils useful for the preparation of concentrates as well as for the preparation of lubricant compositions derived therefrom may be selected from natural (vegetable, animal, or mineral) and synthetic lubricants and mixtures thereof.

[0072] The definitions of base stock and base oil in this disclosure are the same as those found in Appendix E of API (American Petroleum Institute) Publication 1509 ("API Base Oil Interchangeability Guidelines for Passenger Car Motor Oils and Diesel Engine Oils," December 2016). Group I base stock contains less than 90% saturation and / or more than 0.03% sulfur and has a viscosity index of 80 or greater and less than 120 using the test method specified in Table E-1. Group II base stock contains 90% or more saturation and less than 0.03% sulfur and has a viscosity index of 80 or greater and less than 120 using the test method specified in Table E-1. Group III base stock contains 90% or more saturation and less than 0.03% sulfur and has a viscosity index of 120 or greater using the test method specified in Table E-1. Group IV base stock is polyalphaolefin (PAO). Group V base stock includes all other base stocks not included in Groups I, II, III, or IV.

[0073] Natural oils include animal oils, vegetable oils (e.g., castor oil and lard oil), and mineral oils. Animal and vegetable oils possessing good thermal oxidation stability may be used. Among natural oils, mineral oil is preferred. Mineral oils vary greatly regarding the crude oil source, for example, whether they are paraffinic, naphthenic, or a mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils also vary depending on the methods used for their production and refining, such as the extent of their distillation and whether they are straight-line or cracked, hydrogenated, or solvent-based.

[0074] Synthetic oils include hydrocarbon oils. Hydrocarbon oils include oils such as polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene isobutylene copolymer, ethylene-olefin copolymer, and ethylene-alphaolefin copolymer). Polyalphaolefin (PAO) oil-based stocks are commonly used synthetic hydrocarbon oils. For example, C8 to C 14 Olefins, e.g., C8, C 10 , C 12 , C 14 PAO derived from olefins or mixtures thereof may be used.

[0075] Other useful fluids for use as base oils include non-conventional or unconventional base stocks that are treated, preferably catalytically treated, or synthesized to provide high-performance characteristics.

[0076] Unusual or unusual base stocks / base oils comprise mixtures of base stock(s) derived from one or more gas-to-liquid (GTL) substances, as well as mineral and / or non-mineral waxy raw materials such as natural waxes or waxy feeds, slack wax, natural waxes, and waxy raw materials such as non-petroleum derived waxy materials such as light oil, waxy fuel hydrocracker sub-materials, waxy raffinates, hydrocrackers, thermal cracks, or other waxy materials obtained from minerals, mineral oils, or even coal liquefaction or shale oil, and mixtures of such base stocks.

[0077] The base oil for use in the lubricating oil composition of the present disclosure is any of the 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, more preferably any of the Group III to Group V base oils, due to their excellent volatility, stability, viscosity, and cleanliness characteristics.

[0078] Typically, the base oil is 2.5 to 20 mm 2 / s(e.g., 3 to 12 mm 2 / s, 4 to 10 mm 2 / s, or 4.5 to 8 mm 2 It will have a kinematic viscosity (ASTM D445) at 100°C in the range of / s.

[0079] The lubricating oil composition of the present invention may also contain conventional lubricating additives to provide auxiliary functions, which are dispersed or dissolved to provide a finished lubricating oil composition. For example, the lubricating oil composition may be combined with antioxidants, ashless dispersants, anti-wear agents, detergents, e.g., metal detergents, rust inhibitors, dehazing agents, anti-emulsifying agents, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, defoaming agents, co-solvents, package compatibilizers, corrosion inhibitors, dyes, extreme pressure agents, etc., and mixtures thereof. Various additives are known and commercially available. These additives, or compounds similar to them, may be used in the preparation of the lubricating oil composition of the present invention by a useful compounding procedure.

[0080] Each of the aforementioned additives is used in a functionally effective amount to provide desirable properties to the lubricant when used. Thus, for example, if the additive is an ashless dispersant, the functionally effective amount of this ashless dispersant will be sufficient to impart the desired dispersion properties to the lubricant. Generally, the concentration of each of these additives, when used, may be in the range of about 0.001 to about 20 weight%, e.g., about 0.01 to about 10 weight%, unless otherwise specified.

[0081] Examples

[0082] FIGS. 1 and 2 summarize the characteristics of the propylene oligomers used in the embodiments described herein. The propylene oligomers include five distillation products of a conventional propylene tetramer and a vinylidene-rich propylene oligomer. The distillation products vary in boiling temperature (Fig. 1) and number of carbon atoms (Fig. 2).

[0083] Propylene oligomers were tested and analyzed according to the methods described in US 2008 / 0171672A1, which is incorporated herein by reference. 1 H NMR-based methods characterized the samples and calculated the average number of branches per molecule, as well as the number of aliphatic and olefin branches per chain.

[0084] Figure 1 shows that the distillation product has a high vinylidene content and very low trisubstituted and tetrasubstituted olefins. Figure 2 shows that the distillation product has a desirable level of branching while maintaining a high vinylidene content.

[0085] Alkylphenol Sample

[0086] The branching levels of alkylphenol compositions alkylated with various propylene tetramer samples were investigated using NMR spectroscopy. Alkylphenol NMR data are summarized in Table 2 (Proton NMR Integration) below. All NMR data were obtained using chloroform as the solvent.

[0087] Comparative Example A is an alkylphenol alkylated to a propylene tetramer oligomerized by a conventional method. Comparative Example B is an alkylphenol alkylated to an isomerized alpha-olefin. Example 1 is an alkylphenol alkylated to a vinylidene-rich propylene oligomer of the present invention. Such vinylidene-rich propylene oligomers are prepared by oligomerizing a propylene-rich feedstock containing an olefin, wherein at least 50 mol% of the olefin in the feedstock is propylene and at least 50 mol% or at least 70 mol% of the propylene oligomer has vinylidene double bonds.

[0088] The main characteristics of the alkylphenol prepared by the alkylation of phenol using the propylene oligomer of the present invention are the regularity and high concentration of methyl branching in the alkyl side chains. Except for the terminals of the alkyl chains and the carbons to which aromatic units are attached, the alkyl groups consist of alternating -CH2- and -CH(R)- groups, wherein R is methyl when the alkylating agent is a propylene oligomer. This structure of the alkyl group, which is likely responsible for some of the desirable characteristics of the alkylphenol product, is as follows: 1 H and 13 It provides product characteristics that allow it to be distinguished from other alkylphenol products through a combination of C NMR spectroscopy.

[0089] Alternating CH2 and CH(Me) groups impart a higher concentration of methyl groups to the alkyl side chains of the alkylphenol according to the present invention, as exemplified by a higher NMR branching index defined as the ratio of the integral of methyl hydrogen resonance to the integral of all aliphatic hydrogen resonances of the molecule, which is found in the side chains of other alkylphenols. The alkylphenol according to the present invention has an NMR branching index exceeding 45%. That is, the integral of methyl resonance constitutes more than 45% of the integral of all resonances for protons of the alkyl side chain. More specifically, the NMR branching index of the product according to the present invention is in the range of 45 to 60%. In addition, at least 50 mol% of the alkyl groups in the alkyl hydroxy aromatic compound included in the product according to the present invention have an NMR branching index of 45% or more, and at least 50 mol% of the alkyl groups in the alkyl hydroxy aromatic compound have a ratio of methyl carbon to methylene carbon and methine carbon greater than about 0.29. In addition, at least 50 mol% of the alkyl hydroxy aromatic compound included in the product according to the present invention has a ratio of methyl-branched methylene carbon resonance in the range of 44 to 49 ppm measured in chloroform to combined saturated aliphatic carbon resonance in the range of 10 to 50 ppm measured in chloroform greater than 0.15.

[0090] While a high concentration of methyl groups among the alkyl groups is a distinguishing feature, another equally important difference is the methyl substituent -CH(Me)- CH It is a high concentration of -CH2- groups (methylene groups) located between two carbons each possessing 2-CH(Me)-. 13 In the 1C NMR spectrum, the resonances for these methylene resonances are in the range of 44 to 49 ppm, which is different for aliphatic carbons 13It is more downfield than C resonance. In the case of the alkylphenol according to the present invention, resonances in the range of 44 to 49 ppm constitute more than 10% or 15% of all resonances in the aliphatic carbon range of 10 to 50 ppm.

[0091]

[0092] The NMR branching index can be calculated from NMR data. Table 3 summarizes branching and carbon number information. N 지방족 H is N CH3 , N CH2 and N CH It is the sum of. As shown, Example 1 has the highest NMR branch index.

[0093]

[0094] Carbon NMR results comparing alkylphenols having different alkyl groups (Table 4) were obtained. NMR samples included alkylphenols having a conventional tetramer, an isomerized oligomer, and a vinylidene-rich propylene oligomer. Data were collected using a 400 MHz instrument (100.6 MHz 13C frequency) with a 2-second recirculation delay using Cr(acac)3 relaxant, which is chromium acetylacetonate, at a concentration of 0.05 M.

[0095]

[0096] All documents described herein, including any priority documents and / or test procedures to the extent that they do not contradict this text, are incorporated by reference herein. As is evident from the foregoing general description and specific embodiments, forms of the invention have been illustrated and described, but various modifications may be made without departing from the spirit and scope of the present disclosure. Accordingly, the present disclosure is not intended to be limited by these modifications.

[0097] For the sake of brevity, only specific ranges are explicitly disclosed in this specification. However, a range of lower values ​​may be combined with any upper value to refer to a range not explicitly mentioned, as well as combined with any other lower value to refer to a range from any lower value and a range not explicitly mentioned, and in the same way, a range from any upper value may be combined with any other upper value to refer to a range not explicitly mentioned. Furthermore, all points or individual values ​​between endpoints are included within the range, even if not explicitly mentioned. Thus, any point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit to refer to a range not explicitly mentioned.

[0098] Likewise, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a composition, element, or group of elements precedes the transitional phrase "comprising," it is understood that the same composition or group of elements is posited by the transitional phrases "essentially composed of," "composed of," "selected from a group composed of," or "is" before the citation of the composition, element, or elements, or vice versa.

[0099] Terms of singular expression as used in this specification are understood to include not only the singular but also the plural.

[0100] Various terms have been defined above. Unless a term used in the claims is defined above, the broadest definition given by persons in the relevant art as reflected in at least one printed publication or published patent shall be applied. Furthermore, all patents, test procedures, and other literature cited in this application are fully referenced by reference to the extent that such disclosures do not contradict the present invention and to all rights where such reference is permitted.

[0101] The foregoing description of the present disclosure illustrates and explains the present disclosure. Furthermore, while the present disclosure merely illustrates and describes preferred embodiments, as mentioned above, the present disclosure may be used in various other combinations, variations, and environments, and it should be understood that changes or modifications may be made in accordance with the skills or knowledge of the teachings and / or related technologies within the scope of the concepts as expressed herein. Although the foregoing describes embodiments of the present disclosure, other additional embodiments of the present disclosure may be devised without departing from the basic scope of the present disclosure, the scope of which is determined by the following claims.

[0102] The embodiments described above are also intended to describe the best mode known to be practiced and to enable those skilled in the art to utilize the present disclosure in such or other embodiments and with various modifications required by a particular application or use. Accordingly, the above description is not intended to limit it to the form disclosed herein. Furthermore, the appended claims are intended to be interpreted as including alternative embodiments.

Claims

Claim 1 A hydroxyaromatic composition comprising a mixture of highly structured alkyl-substituted hydroxyaromatic compounds having a structure imparted by the following: Here, R is a hydroxyaromatic group, X is hydrogen or a methyl group, and n A hydroxyaromatic composition in which 1 or more is present, and at least 50 mol% of the alkyl group of the alkyl-substituted hydroxyaromatic compound constituting the mixture of the alkyl-substituted hydroxyaromatic compounds is such that the ratio of methyl carbon to methylene carbon is greater than 0.

85. Claim 2 A hydroxyaromatic composition according to claim 1, wherein R is a phenol group, a catechol group, a resorcinol group, a hydroquinone group, a pyrogallol group, a cresol group, a naphthol group, a hydroxybenzoic acid group, or a salt thereof. Claim 3 A hydroxyaromatic composition according to claim 1, wherein n is 20 or less. Claim 4 A hydroxyaromatic composition according to claim 1, wherein n is 2 to 6. Claim 5 A hydroxyaromatic composition according to claim 1, wherein at least 50 mol% of the alkyl group of the alkyl-substituted hydroxyaromatic compound constituting the mixture of the alkyl-substituted hydroxyaromatic compounds has an NMR branching index of 45% or more. Claim 6 delete Claim 7 A hydroxyaromatic composition according to claim 1, wherein at least 50 mol% of the alkyl group of the alkyl-substituted hydroxyaromatic compound constituting the mixture of the alkyl-substituted hydroxyaromatic compounds is such that the ratio of the methyl carbon to the methylene carbon and the methine carbon is greater than 0.

29. Claim 8 A hydroxyaromatic composition according to claim 1, wherein at least 50 mol% of the alkyl group of the alkyl-substituted hydroxyaromatic compound constituting the mixture of the alkyl-substituted hydroxyaromatic compounds has a ratio of a methyl-branched methylene carbon resonance in the range of 44 to 49 ppm measured in chloroform to a combined saturated aliphatic carbon resonance in the range of 10 to 50 ppm measured in chloroform greater than 0.

15. Claim 9 A lubricating oil composition comprising a base oil; and a hydroxyaromatic composition of claim 1. Claim 10 A mixture of highly structured alkyl-substituted hydroxyaromatic compounds, wherein at least 50 mol% of the alkyl groups of the alkyl-substituted hydroxyaromatic compounds constituting the mixture of alkyl-substituted hydroxyaromatic compounds are formed by a process comprising the step of alkylating the hydroxyaromatic compounds with an alkylating agent containing a vinylidene-rich propylene oligomer terminated by a vinylidene double bond, wherein the ratio of methyl carbon to methylene carbon is greater than 0.85, the propylene oligomer is prepared by oligomerizing a propylene-rich feedstock containing an olefin, wherein at least 50 mol% of the olefin in the feedstock is propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond. Claim 11 In claim 10, the hydroxyaromatic compound is a mixture of alkyl-substituted hydroxyaromatic compounds, wherein the hydroxyaromatic compound is phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, naphthol, or hydroxybenzoic acid. Claim 12 A mixture of alkyl-substituted hydroxyaromatic compounds according to claim 10, wherein at least 70 mol% of the olefin in the above feedstock is propylene. Claim 13 In paragraph 10, the propylene-rich feedstock is a mixture of alkyl-substituted hydroxyaromatic compounds produced by fluid catalytic cracking and oligomerized without prior separation of propane and propylene. Claim 14 In claim 10, a mixture of alkyl-substituted hydroxyaromatic compounds, wherein at least 70 mol% of the propylene oligomer has a vinylidene double bond. Claim 15 delete Claim 16 In claim 10, the propylene oligomer is a mixture of alkyl-substituted hydroxyaromatic compounds having an average number of carbon atoms in the range of 9 to 50. Claim 17 delete Claim 18 delete Claim 19 delete Claim 20 A mixture of alkyl-substituted hydroxyaromatic compounds according to claim 10, wherein at least 50 mol% of the alkyl group of the alkyl-substituted hydroxyaromatic compound constituting the mixture of the alkyl-substituted hydroxyaromatic compounds is an alkyl group having at least 5 carbons. Claim 21 delete Claim 22 A lubricating oil composition comprising: a base oil; and a detergent derived from a mixture of highly structured alkyl-substituted hydroxyaromatic compounds of claim 10, wherein the alkyl-substituted hydroxyaromatic compounds are sulfurized. Claim 23 A lubricating oil composition according to claim 22, wherein at least 70 mol% of the olefin among the above feedstocks is propylene. Claim 24 In claim 22, the propylene-rich feedstock is a lubricating oil composition in which the olefin-to-alkane molar ratio is in the range of 10 / 1 to 1 / 10. Claim 25 In paragraph 22, the propylene-rich feedstock is a lubricating oil composition isolated from a catalytic or thermal cracking process at a propylene-to-propane ratio of 5% or less, as produced in a catalytic cracking process without separation of propane and propylene. Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 delete Claim 30 A method for alkylating a hydroxyaromatic compound to form a mixture of highly structured alkyl-substituted hydroxyaromatic compounds, wherein at least 50 mol% of the alkyl groups of the alkyl-substituted hydroxyaromatic compound constituting the mixture of alkyl-substituted hydroxyaromatic compounds have a ratio of methyl carbon to methylene carbon greater than 0.85, and a step of forming a vinylidene-rich propylene oligomer comprising a propylene oligomer terminated by a vinylidene double bond by oligomerizing a propylene-rich feedstock containing an olefin, wherein at least 50 mol% of the olefin in the feedstock is propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond; A method comprising the step of alkylating the hydroxyaromatic compound into the vinylidene-rich propylene oligomer. Claim 31 In paragraph 30, the above single-site catalyst is a metallocene, method. Claim 32 The method of claim 31, wherein the metallocene has the general formula (RCp)2MX2, wherein Cp is a cyclopentadieneyl group, RCp is a substituted cyclopentadieneyl group, R is an alkyl group, M is Ti, Zr or Hf, and X is Cl, Br, I, H, Me or Et. Claim 33 delete Claim 34 delete Claim 35 In claim 30, the hydroxyaromatic compound is phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, hydroxybenzoic acid, or a salt thereof.

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