Alkyl-substituted hydroxyl aromatic compounds having highly structured alkyl branching

Abstract

The present invention provides compositions and methods related to alkyl-substituted hydroxyaromatic products having highly structured alkyl groups. [Solution] An alkylhydroxyaromatic compound having a structure represented by the following formula, wherein R is a hydroxyaromatic group, X is a hydrogen or methyl group, and n is 1 or more. TIFF2026108678000009.tif53165

Description

[Technical Field]

[0001] This disclosure relates to commercially available alkyl-substituted hydroxyaromatic products. More specifically, this disclosure describes alkyl-substituted hydroxyaromatic additives having highly structured alkyl groups and 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 prepare many commercial products, including detergents, emulsifiers, pesticides, fragrances, thermoplastic elastomers, antioxidants, and surfactants. For example, alkylphenols can be used to synthesize alkyl sulfide-substituted phenate compounds that are useful as detergents for lubricants. One concern is the potential toxicity of alkylphenols to the environment. Certain alkylphenols, such as tetrapropenylphenol (TPP), are now classified as reproductive toxic. The lubricant industry is concerned about the residue of TPP as an unsulfurized alkyl-substituted phenate byproduct during detergent synthesis.

[0003] Another problem specific to TPP relates to its synthesis, including the alkylation of phenols with propylene oligomers. In conventional synthesis, phenol molecules are alkylated with propylene oligomers rich in propylene tetramers (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 may be one of the main reasons why the alkylation reaction takes several days to proceed and results in a large excess of propylene tetramers.

[0004] In efforts to address these ongoing issues, alternative olefins have been identified as potential replacements for propylene tetramer. In particular, structurally isomerized linear alpha olefins have been used in the manufacture of commercial alkylphenol detergents. However, the isomerization step already raises the cost of the linear alpha olefins and reduces the activity of the internal olefins. Furthermore, alkylphenol products made from isomerized linear alpha olefins often have relatively poor functionality in laboratory tests, presumably due to insufficient methyl branching.

[0005] Other efforts have focused on utilizing polyisobutylene-based olefins as a source of alkylphenol detergents. A major drawback of using polyisobutylene (PIB) as an olefin feed is the need to modify the alkylation technology with special alkylation catalysis. SUMMARY OF THE INVENTION

[0006] In one aspect, a hydroxyaromatic product is provided that includes: an alkylhydroxyaromatic compound having the structure shown below

Chemical formula

[0007] In another aspect, there is provided an alkyl-substituted hydroxyaromatic compound formed by a process comprising: alkylating a hydroxyaromatic compound with an alkylating agent comprising a propylene oligomer rich in vinylidene and comprising a propylene oligomer terminated with a vinylidene double bond, wherein the propylene oligomer is prepared by oligomerization of a propylene-rich feedstock comprising olefins, wherein at least 50 mol% of the olefins in the feedstock are propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond.

[0008] In yet another aspect, there is provided a lubricating oil composition comprising: a base oil; and a detergent comprising a sulfurized alkylphenol, wherein the alkylphenol is produced by alkylation using an alkylating agent comprising a propylene oligomer rich in vinylidene and comprising a propylene oligomer terminated with a vinylidene double bond, the propylene oligomer being prepared by oligomerizing a propylene-rich feedstock comprising olefins, wherein at least 50 mol% of the olefins in the feedstock are propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond.

[0009] In yet another aspect, there is provided a method for alkylating a hydroxyaromatic compound, the method comprising: oligomerizing a propylene monomer in the presence of a single-site catalyst to form a propylene oligomer rich in vinylidene and comprising a propylene oligomer terminated with a vinylidene double bond, wherein the propylene oligomer is prepared by oligomerizing a propylene-rich feedstock comprising olefins, wherein at least 50 mol% of the olefins in the feedstock are propylene and at least 50 mol% of the propylene oligomer has a vinylidene double bond; and alkylating the hydroxyaromatic compound with the propylene oligomer rich in vinylidene. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] [Figure 1] It shows the graph described in the examples. [Modes for carrying out the invention]

[0011] The term "olefin" refers to hydrocarbons having at least one carbon-carbon double bond that is not part of an aromatic ring or cyclic system. Unless otherwise specified, 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 with only one, two, or three carbon-carbon double bonds may be identified by using terms such as "mono," "di," or "tri" in the name of the olefin. 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 either an "olefin oligomer" or an "olefin monomer."

[0012] An "olefin oligomer" is an oligomer produced by the oligomerization of an "olefin monomer." For example, a "propylene oligomer" is nominally produced by the oligomerization of a propylene monomer. Examples of propylene oligomers include propylene tetramers and propylene pentamers. A "propylene tetramer" is an olefin oligomer product nominally resulting from the oligomerization of four propylene monomers. These terms can also be commonly used to describe homooligomers, cooligomers, oligomer salts, oligomer derivatives, and so on.

[0013] The unpurified products of the oligomerization process typically consist of a mixture of branched olefin oligomers having a distribution of carbon atoms. The unpurified oligomer products resulting from monomer oligomerization may be further isolated or purified to a preferred carbon range by distillation.

[0014] "Alkyl" or related terms refer to saturated hydrocarbon groups that may be linear, branched, cyclic, or a combination of cyclic, linear, and / or branched.

[0015] A "vinylidene-rich propylene oligomer" refers to a propylene-based oligomer in which the vinylidene moiety is dominant. Olefin oligomers containing a vinylidene moiety have gem disubstituted at the internal end of the terminal double bond. Propylene oligomers prepared by conventional methods are usually rich in molecules with trisubstituted or tetrasubstituted internal double bonds.

[0016] As used herein, the term “substituted” means that a hydrogen group is replaced by an alkyl group, an aromatic group, a heteroatom, or a heteroatom-containing group.

[0017] When combinations, subsets, or groups of elements (for example, combinations of components in a composition or combinations of steps in a method) are disclosed, it is understood that each specific reference to various individual and collective combinations and arrangements of these elements is disclosed herein with specific intent, even if not explicitly disclosed.

[0018] The present invention provides compositions and methods relating to alkyl-substituted hydroxyaromatic products having highly structured alkyl groups. More specifically, the present invention describes the synthesis of vinylidene-rich propylene oligomers that can be used to synthesize alkyl-substituted hydroxyaromatic products, which are then useful in the production of a wide range of commercial products.

[0019] The vinylidene-rich propylene oligomers can be prepared using a single-site catalyst. This makes the high-vinylidene-content oligomers of the present invention more reactive in alkylation reactions, enabling more efficient synthesis of alkylphenol products.

[0020] A high vinylidene content can offer several advantages compared to conventional propylene tetramer oligomers. For example, alkylation of phenols using vinylidene-rich propylene oligomers can be efficiently achieved by reducing the ratio of olefin to phenol. Other advantages may include lower reaction temperatures, shorter batch cycle times, higher conversion rates, and higher para-alkylphenol content.

[0021] Vinylidene-rich propylene oligomers The vinylidene-rich propylene oligomer of the present invention is characterized by a highly ordered structure comprising a long linear skeleton and chains having regularly spaced methyl groups.

[0022] The vinylidene-rich propylene oligomers of the present invention have an average carbon number in the range of about 9 to about 50. In some embodiments, the average carbon number is in the range of 9 to 42, 9 to 39, 9 to 36, or 12 to 32.

[0023] Vinylidene oligomers are long, straight-terminal olefins that have branching at every other carbon in the chain, starting from the geminal branching of the vinylidene olefin. If the terminal olefin carbons are numbered, the branching is on every even carbon in the chain except for the last three carbons of the oligomer chain (which may be unbranched or otherwise deviate from the usual branching of the rest of the molecule). (i.e., branching at carbon 2, 4, 6, etc.) 2,4-dimethyl-1-heptene (trimer), 2,4,6-trimethyl-1-nonene (tetramer), and 2,4,6,8-tetramethyl-1-undecene (pentamer) are examples of vinylidene oligomers of the present invention.

[0024] In some embodiments, vinylidene-rich propylene oligomers are the products of oligomerization, with at least 50 mol% of the oligomer having 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. By-products of oligomerization may include oligomers that do not have a vinylidene moiety. These oligomers may have other moieties / configurations in the double bond, such as trisubstituted, tetrasubstituted, vinyl, and disubstituted (cis or trans).

[0025] Propylene is the primary olefin monomer in oligomerization reactions, but the source may have olefins with different numbers of carbon atoms, or a mixture of olefins mainly having a single number of carbon atoms. The olefin may contain at least 50% by weight, at least 55% by weight, at least 60% by weight, at least 65% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 95% by weight of propylene. The monomer may further be introduced into the oligomerization reaction in a mixture with one or more non-olefinic hydrocarbons, such as alkanes or aromatic compounds.

[0026] In one embodiment, the propylene monomer is supplied from a decomposition operation and used without separating propylene from propane before the oligomerization reaction. Such a decomposition operation may be catalytic decomposition such as fluid catalytic decomposition, or thermal decomposition such as vapor decomposition or coking. In one embodiment, the decomposition operation may include propane dehydrogenation.

[0027] The synthesis of vinylidene-rich propylene oligomers can proceed via any known oligomerization method. The synthesis of olefin oligomers or polyolefins is generally known in the relevant art. In particular, the synthesis of polyolefins via single-site catalysts is known to provide polymers with highly defined microstructures, stereoregularity, and stereoregularity.

[0028] The vinylidene-rich propylene oligomers of the present invention may also be prepared by using a suitable single-site catalyst(s) capable of controlling the length and / or branching of the side chains. Single-site catalysts are generally classified into two groups: metallocene catalysts and non-metallocene catalysts.

[0029] Metallocenes are well-known complex organometallic molecules, typically including zirconium, titanium, hafnium, transition metals of groups IVA, VA, and VIA, and lanthanide metals. The metal is usually located at or near the center of the complex and coordinates to two cyclic alkyl anions, such as the cyclopentadienyl anion. A more detailed discussion of metallocenes can be found in U.S. Patent No. 6,511,568, which is incorporated herein by reference. Other suitable metallocenes include ANSA-metallocenes and metallocene and metallocene catalyst systems described in U.S. Patent No. 8,536,391, which is incorporated herein by reference.

[0030] In one embodiment, metallocene is formula (RCp)2MX2 has, In the formula, Cp is a cyclopentadienyl group, RCp is a substituted cyclopentadienyl group, R is an alkyl group or hydrogen, M is Ti, Zr or Hf, and X is Cl, Br, I, H, Me or Et.

[0031] Non-metallocene single-site catalysts are typically transition metal catalysts. Transition metal catalysts are described in WO9827124, WO9830612, WO9623010 and European Patent No. 0816387, 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, and chelated diamine catalyst systems.

[0032] The oligomeric product is 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 may contain at least about 90 mol%, at least 95 mol%, at least 98 mol%, or at least 99 mol% of propylene units.

[0033] The oligomeric product may include dimers, trimers, and / or higher-order oligomers. In some embodiments, the oligomeric product may include (i) at least 75% by weight, 80% by weight, 85% by weight, 90% by weight, or 95% by weight of dimers, trimers, tetramers, pentamers, hexamers, heptamers, octamers, nocumerers, and / or decapers; (ii) at least 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 80% by weight, 85% by weight, or 90% by weight of trimers. (iii) Tetramers, pentamers, hexamers, heptamers, octamers, notermers, and / or decapers; (iii) Dimers, trimers, tetramers, pentamers, hexamers, and / or heptamers in amounts of at least 75% by weight, 80% by weight, 85% by weight, 90% by weight, or 95% by weight; (iv) Trimers in amounts of at least 50% by weight, 55% by weight, 60% by weight, 65% by weight, 70% by weight, 80% by weight, 85% by weight, or 90% by weight (v) dimers, trimers, tetramers, hexamers, and / or heptamers in amounts of at least 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, or 60% by weight; (vi) trimers, tetramers, and / or pentamers in amounts of at least 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, or 50% by weight; (vii) small (viii) at least 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, 55% by weight, or 60% by weight of dimers, trimers, and / or tetramers; (ix) may include any combination thereof.

[0034] In additional or alternative embodiments, the oligomer product comprises at least 35 wt%, 45 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, or 65 wt% in total of trimers, tetramers and pentamers; alternatively or additionally, it may comprise up to 100 wt%, 95 wt%, 90 wt%, or 85 wt% in total of trimers, tetramers, and pentamers. In some embodiments, the olefin oligomer may comprise 35 wt% - 100 wt%, 40 wt% - 95 wt%, 45 wt% - 90 wt%, 40 wt% - 85 wt%, 50 wt% - 90 wt%, or 50 wt% - 85 wt% in total of trimers, tetramers and pentamers.

[0035] The oligomer product may comprise less than 40 wt%, 30 wt%, 25 wt%, 20 wt%, 18 wt%, 16 wt%, 14 wt%, 12 wt%, or 10 wt% of dimers. Alternatively or additionally, the oligomer product may comprise less than 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%, 8 wt%, 6 wt%, 5 wt%, 4 wt%, 3 wt%, or 2 wt% of oligomers (comprising 7 or more monomer units).

[0036] In some embodiments, the oligomer product comprises at least 50 wt%, 60 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt% of C 70 , 20 , 20 , 30 , 30 , 40 , 40 , 70 , 24 , 70 , , 30 , , 40、 , 14 , 12 , 16 , 12 , 16 , 12 , 20 ,<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​70 , C 20 ~C 40 , C 20 ~C 30 , or C 20 ~C 24 ) may contain oligomers. In some embodiments, the oligomer product may contain less than 30% by weight, 25% by weight, 20% by weight, 15% by weight, 10% by weight, 8% by weight, 6% by weight, 5% by weight, 4% by weight, 3% by weight, or 2% by weight of >C 70 The product may contain oligomers. The weight percentages of oligomers(s) disclosed herein are based on the total weight of the oligomer product.

[0037] The oligomeric products have a number-average molecular weight (M) in the range of 150 to 10,000 g / mol. n ) may have. For example, the M of the oligomer product n This can be at least 150, 250, 325, 400, 500, 600, 650, 700, or 750 g / mol. Additionally or alternatively, up to M n This can be 10,000, 7,500, 6,000, 5,000, 4,000, 3,000, 2,500, or 2,000 g / mol. Generally, the M of the oligomeric product... n This is any minimum M disclosed herein. n Any maximum M disclosed herein n It could be within that range.

[0038] Heteroatom-functionalized oligomers Depending on the application, olefin oligomers may be functionalized by reacting them with heteroatom-containing groups, with or without a catalyst. These reactions include hydroxylation, hydrosylation, ozonolysis, hydroformylation, hydroamidation, sulfonation, halogenation, hydrohalogenation, hydroboration, epoxidation, Diels-Alder reaction with polar dienes, Friedel-Crafts reaction with polar aromatic compounds (e.g., hydroxyaromatic compounds), and maleic acid treatment with activators such as free radical generators (e.g., peroxides).

[0039] Examples of heteroatom-containing groups include alcohols, amines, aldehydes, hydroxyaromatic compounds, sulfonates, acids, and anhydrides.

[0040] 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 This can be determined by 1H NMR spectroscopy.

[0041] Alkyl-substituted hydroxyl aromatic compounds having highly structured alkyl branching The olefin oligomers described herein may be used to alkylate hydroxyaromatic compounds to form alkyl-substituted hydroxyaromatic compounds. Alkyl-substituted hydroxyaromatic compounds are useful as precursors or final products for a variety of commercial applications.

[0042] Alkylhydroxyaromatic compounds are as follows: [ka] The structure may be represented by the formula, where R is a hydroxyaromatic group, X is a hydrogen or methyl group, and n is 1 or greater. In some embodiments, n is 20 or less. In some embodiments, n is between 2 and 6.

[0043] 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, as well as mixtures thereof and salts thereof (e.g., phenates).

[0044] Alkylation of hydroxyaromatic compounds with olefin oligomers 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-phosphate). Suitable solid acids include sulfonated acid 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.

[0045] The reaction conditions for alkylation depend on the type of catalyst used, and any suitable set of reaction conditions that yield a high conversion to alkylhydroxyaromatic products may be used. Typically, the reaction temperature for alkylation reactions is in the range of 15°C to 200°C (e.g., 85°C to 135°C). The reaction pressure is generally atmospheric pressure, but higher or lower pressures may be used. The alkylation process can be carried out in 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).

[0046] 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.

[0047] Once the reaction is complete, the desired alkyl-substituted hydroxyaromatic compound may be isolated using conventional techniques.

[0048] The alkyl group in alkyl-substituted hydroxyaromatic compounds is typically bonded to the hydroxyl group primarily at the ortho and para positions. Alkyl-substituted hydroxyaromatic compounds may contain 1-99% ortho isomers and 99-1% para isomers (e.g., 5-70% ortho isomers and 95-30% para isomers).

[0049] Metal salts of alkylphenols (i.e., phenates) are a useful class of cleaning agents. These cleaning agents may be produced by reacting an alkaline earth metal hydroxide or oxide (e.g., CaO, Ca(OH)2, BaO, Ba(OH)2, MgO, Mg(OH)2) with an alkylphenol or an alkylphenol sulfide. When non-alkylphenol sulfides are used, the sulfide product may be obtained by methods well known in the art. These methods involve heating a mixture of alkylphenol and a sulfurizing agent (e.g., elemental sulfur, sulfur halides such as sulfur dichloride), and then reacting the alkylphenol sulfide with an alkaline earth metal base.

[0050] Metal salts of alkyl-substituted hydroxyaromatic carboxylic acids are also useful as detergents. Alkyl-substituted hydroxyaromatic carboxylic acids are typically prepared, for example, by carboxylation of alkyl-substituted phenoxides using the Kolbe-Schmidt process.

[0051] 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.

[0052] Many detergent compositions are overbasic and contain a large amount of metallic base, achieved by reacting an excess of metal compounds (e.g., metal carbonates, hydroxides, or oxides) with an acidic gas (e.g., carbon dioxide). Useful detergents may be neutral, slightly overbasic, or highly overbasic. The process of overbasing is known to those skilled in the art.

[0053] The basicity of a detergent may be expressed as total bases (TBN). Total bases is the amount of acid required to neutralize all the basicity of the over-basicated material. TBN can be measured using ASTM D2896 or an equivalent procedure. Detergents may have low TBN (i.e., TBN less than 50 mg KOH / g), moderate TBN (i.e., TBN between 50 and 150 mg KOH / g), or high TBN (i.e., TBN greater than 150 mg KOH / g, e.g., TBN between 150 and 500 mg KOH / g).

[0054] Functionalized oligomers and / or derivatized oligomers have applications as lubricant additives that can act as dispersants, viscosity index improvers, or multifunctional viscosity index improvers.

[0055] The olefin oligomers and their products described herein may be combined with other additives (e.g., cleaning agents, dispersants, antioxidants, anti-wear agents, friction modifiers, rust inhibitors, viscosity modifiers, pour point depressants, anti-foaming agents, etc.) to form compositions for many applications, including lubricant additive packages and lubricants.

[0056] Compositions containing these additives are typically blended with a base oil in amounts effective to provide their usual ancillary functions. Typical amounts of such additives are shown in Table 1 below. The weights in the following table, and other amounts described herein, refer to the amount of the active ingredient (i.e., the undiluted portion of the ingredient). The weight percentages (W%) shown below are based on the total weight of the lubricating oil composition. [Table 1]

[0057] lubricating oil The olefin oligomers of this 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% by weight (including, but not limited to, 0.01 to 5%, 0.2 to 4%, 0.5 to 3%, 1 to 2% by weight, etc.) based on the total weight of the lubricating oil composition. If other hydroxide donors are present in the lubricating oil composition, the additive may be used in smaller amounts.

[0058] The oil used as the base oil is selected or blended according to the desired end use and additives in the finished oil to obtain a lubricating oil composition having an engine oil of the desired grade, for example, an engine oil with a 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.

[0059] Lubricating viscosity oil (sometimes called "base stock" or "base oil") is the primary liquid component of a lubricant, to which additives and possibly other oils are blended to produce, for example, the final lubricant (or lubricant composition). Base oils useful for producing concentrates and from which lubricating oil compositions may be selected from natural (vegetable, animal, or mineral) and synthetic lubricants, as well as mixtures thereof.

[0060] The definitions of base stock and base oil 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 contain less than 90% saturated sulfur and / or more than 0.03% sulfur, and have a viscosity index of 80 or more and less than 120, using the test method specified in Table E-1. Group II base stocks contain 90% or more saturated sulfur and 0.03% or less sulfur, and have a viscosity index of 80 or more and less than 120, using the test method specified in Table E-1. Group III base stocks contain 90% or more saturated sulfur and 0.03% or less sulfur, and have a viscosity index of 120 or more, using the test method specified in Table E-1. Group IV base stocks are polyalphaolefins (PAOs). Group V base stocks include all other base stocks not included in Group I, Group II, Group III, or Group IV.

[0061] Examples of natural oils include animal oils, vegetable oils (e.g., castor oil and lard), and mineral oils. Animal and vegetable oils with desirable thermal oxidative stability may be used. Of the natural oils, mineral oils are preferred. Mineral oils differ considerably in terms of their crude oil source, for example, whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful. Natural oils also differ in the methods used for their production and refining, for example, their distillation range, and whether they are straight-run, cracked, hydrogenated, or extracted solvents.

[0062] Examples of synthetic oils include hydrocarbon oils. Examples of hydrocarbon oils include oils of polymerized and crosspolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymer, ethylene-olefin copolymer, and ethylene-alphaolefin copolymer). Polyalphaolefin (PAO) oil base stocks are commonly used for synthetic hydrocarbon oils. Examples include C8-C 14 Olefins, for example, C8, C 10 , C 12 , C 14 PAO derived from olefins or mixtures thereof may be used.

[0063] Other useful fluids for use as base oils include, preferably, catalytically treated or synthesized unconventional or non-conventional base stocks that provide high-performance properties.

[0064] Non-conventional or non-conventional base stocks / base oils include mixtures of base stocks derived from one or more gas-to-liquid (GTL) materials, as well as isomerized / iso-dewaxed base stocks derived from natural waxes or waxy feedstocks, mineral and / or non-mineral oil waxy feedstocks, e.g., slack wax, natural wax, as well as waxy stocks, e.g., gas oil, waxy fuel hydrocracker bottom, waxy raffinate, hydrocracking products, pyrolysis products (crackate), or other mineral, mineral oil, and even non-petroleum-derived waxy materials, e.g., waxy materials received from coal liquefaction or shale oil, as well as mixtures of such base stocks.

[0065] The base oils for use in the lubricating oil compositions of this disclosure are 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 various oils corresponding to Group III to Group V base oils due to their outstanding volatility, stability, viscosity measurement, and cleanliness characteristics.

[0066] Typically, the base oil is 2.5-20 mm 2 / second (for example, 3-12mm) 2 / sec, 4~10mm 2 / second, or 4.5-8mm 2 It has a kinetic viscosity (ASTM D445) at 100°C in the range of ( / second).

[0067] The lubricating oil composition of the present invention may also contain conventional lubricant additives to impart auxiliary functions, and a finished lubricating oil composition may be obtained in which these additives are dispersed or dissolved. For example, the lubricating oil composition may be blended with antioxidants, ashless dispersants, anti-wear agents, cleaning agents such as metal cleaners, rust inhibitors, deodorizers, deemulsifiers, friction modifiers, metal deactivators, pour point depressants, viscosity modifiers, defoaming agents, cosolvents, package conforming agents, corrosion inhibitors, dyes, extreme pressure agents, and mixtures thereof. Various additives are known and commercially available. These additives, or compounds similar thereto, may be used in the preparation of the lubricating oil composition of the present invention by conventional blending procedures.

[0068] Each of the aforementioned additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricant. Therefore, for example, if the additive is an ashless dispersant, the functionally effective amount of this ashless dispersant is sufficient to impart the desired dispersion characteristics to the lubricant. Generally, the concentration of each of these additives, when used, may range from about 0.001 to about 20% by weight, for example, from about 0.01 to about 10% by weight, unless otherwise specified. [Examples]

[0069] Figures 1 and 2 summarize the characteristics of the propylene oligomers used in the examples described herein. The propylene oligomers include five distillation products of conventional propylene tetramers and vinylidene-rich propylene oligomers. The distillation products differ in their boiling temperature (Figure 1) and carbon number (Figure 2).

[0070] The propylene oligomer was tested and analyzed in accordance with the method described in U.S. Patent Application Publication No. 2008 / 0171672A1, which is incorporated herein by reference. 1 Using 1H NMR-based methods, we characterized the samples and calculated the average number of branches per molecule and the number of aliphatic and olefinic branches per chain.

[0071] 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.

[0072] Alkylphenol sample The branching levels of alkylphenol compositions alkylated with various propylene tetramer samples were investigated using NMR spectroscopy. The alkylphenol NMR data are summarized in Table 2 (proton NMR integrals). All NMR data were obtained using chloroform as the solvent.

[0073] Comparative Example A is an alkylphenol alkylated with a propylene tetramer oligomerized by a conventional method. Comparative Example B is an alkylphenol alkylated with an isomerized alpha-olefin. Example 1 is an alkylphenol alkylated with a vinylidene-rich propylene oligomer according to the present invention.

[0074] Key characteristics of alkylphenols prepared by alkylation of phenols with the propylene oligomer of the present invention are the regularity of the alkyl side chain and the high concentration of methyl branching. Apart from the terminals of the alkyl chain and the carbons to which aromatic units are attached, the alkyl groups are alternating -CH 2- It consists of a group and a -CH(R)- group, where R is methyl when the alkylating agent is a propylene oligomer. This structure of the alkyl group, which is likely to be involved in some of the desirable properties of alkylphenol products, 1 H and 13 The combination of 13C NMR spectroscopy provides product characteristics that allow for differentiation from other alkylphenol products.

[0075] The alternating CH2 and CH(Me) groups give the alkyl side chain of the alkylphenol according to the present invention a higher concentration of methyl groups than is found in the side chains of other alkylphenols, as indicated by a higher NMR branching index, which is defined as the ratio of the integral of methyl hydrogen resonance to the integral of all aliphatic hydrogen resonances in the molecule. The alkylphenol according to the present invention has an NMR branching index of over 45%. In other words, the integral of methyl resonance constitutes more than 45% of the integral of all proton resonances in the alkyl side chain. More specifically, the NMR branching index of the product according to the present invention is in the range of 45-60%.

[0076] While the high concentration of methyl groups in the alkyl group is a distinctive feature, another equally important difference is the high concentration of -CH2- groups (methylene groups) positioned between two carbon atoms, each possessing a methyl substituent -CH(Me)-CH2-CH(Me)-. 13 In the 13C NMR spectrum, the resonances of these methylene resonances are in the range of 44–49 ppm, and the other 13 aliphatic carbons C This is even more downfield than resonance. In the case of alkylphenols according to the present invention, the resonances in the 44-49 ppm range constitute 10% or 15% or more of all the resonances in the 10-50 ppm range of aliphatic carbons. [Table 2]

[0077] The NMR branching index can be calculated from the NMR data. Table 3 summarizes the branching and carbon number information. 脂肪族H is, N CH3 , N CH2 , and N CH This is the sum. As shown, Example 1 has the best NMR branching index. [Table 3]

[0078] Carbon NMR results (Table 4) were obtained to compare alkylphenols with different alkyl groups. NMR samples included alkylphenols containing conventional tetramers, isomerized oligomers, and vinylidene-rich propylene oligomers. Data were collected using a 400 MHz instrument (100.6 MHz 13C frequency) with a 2-second recycle delay, using a 0.05 M concentration of acetylacetonate chromium, Cr(acac)3, as a relaxant. [Table 4]

[0079] All documents described herein, including any priority documents and / or test procedures, are incorporated herein by reference to the extent that they do not conflict with this text. While the forms of this disclosure are illustrative and described as evident from the general description and specific embodiments above, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, this disclosure is not intended to be limited thereto.

[0080] For the sake of brevity, only specific ranges are expressly disclosed herein. However, ranges not expressly disclosed may be enumerated by combining any lower bound with any upper bound, similarly, ranges not expressly disclosed may be enumerated by combining any lower bound with any other lower bound, and similarly, ranges not expressly disclosed may be enumerated by combining any upper bound with any other upper bound. Furthermore, ranges include all points or individual values ​​between endpoints, even if not expressly disclosed. Thus, any point or individual value may function as its own lower or upper bound in combination with any other point or individual value or any other lower or upper bound to enumerate ranges not expressly disclosed.

[0081] Similarly, the term “contains” is considered synonymous with the term “contains.” Likewise, whenever the transition phrase “contains” precedes a component, element, or group of elements, it is assumed that the same component or group of elements has the transition phrase “essentially consists of,” “consists of,” “selected from a group consisting of,” or “is” preceding the component, element, or reference to an element, and vice versa.

[0082] As used herein, the terms “a” (indefinite article) and “the” (definite article) are understood to include both singular and plural forms.

[0083] Various terms are defined above. Unless a term used in a claim is defined above, a person skilled in the art should be given the broadest possible definition of that term, taking it into consideration, so as reflected in at least one printed document or issued patent. Furthermore, all patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent that such disclosures do not conflict with this application and to all rights for which such incorporation is permitted.

[0084] The foregoing description of this disclosure illustrates and illustrates the disclosure. Furthermore, while this disclosure shows and describes only preferred embodiments, as stated above, this disclosure can be used in a variety of other combinations, modifications, and environments, and may be changed or modified within the scope of the concepts expressed herein, to be understood in accordance with the teachings and / or skills or knowledge of the relevant art. Although the foregoing is directed toward embodiments of this disclosure, other and further embodiments of this disclosure may be devised without departing from its basic scope, which is determined by the following claims.

[0085] The embodiments described above in this specification further describe the best known mode of implementation and are intended to enable other persons skilled in the art to utilize this disclosure with various modifications required by specific uses or applications in such or other embodiments. Therefore, this description is not intended to limit the scope to the forms disclosed herein. Furthermore, the appended claims are intended to be construed as including alternative embodiments.

Claims

1. It is a hydroxyaromatic product: Alkylhydroxyaromatic compounds having the structure shown below 【Chemistry 1】 The hydroxyaromatic product comprising the formula, wherein R is a hydroxyaromatic group, X is a hydrogen or methyl group, and n is 1 or more.

2. The hydroxyaromatic product according to claim 1, wherein R is a phenol group, a hydroxybenzyl 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.

3. The hydroxyaromatic product according to claim 1, wherein n is 20 or less.

4. The hydroxyaromatic product according to claim 1, wherein n is between 2 and 6.

5. The hydroxyaromatic product according to claim 1, wherein at least 50 mol% of the alkylhydroxyaromatic compound has an alkyl group having an NMR branching index of 45% or more.

6. The hydroxyaromatic product according to claim 1, wherein at least 50 mol% of the alkyl group of the alkylhydroxyaromatic compound has an alkyl group in which the ratio of methyl carbon to methylene carbon is greater than about 0.

85.

7. The hydroxyaromatic product according to claim 1, wherein at least 50 mol% of the alkylhydroxyaromatic compound has an alkyl group in which the ratio of methyl carbon to methylene carbon and methine carbon is about 0.

29.

8. The hydroxyaromatic product according to claim 1, wherein at least 50 mol% of the alkylhydroxyaromatic compound has an alkyl group having a ratio of methyl-branched permethylene carbon resonance in the range of 44 to 49 ppm when measured in chloroform to a composite saturated aliphatic carbon resonance in the range of 10 to 50 ppm when measured in chloroform of 0.15 ppm.

9. A lubricating oil composition, Base oil; and The lubricating oil composition comprising the hydroxyaromatic product described in claim 1.

10. Alkyl-substituted hydroxyaromatic compounds, the following: The alkyl-substituted hydroxyaromatic compound is formed by a process comprising alkylating a hydroxyaromatic compound with an alkylating agent containing a vinylidene-rich propylene oligomer containing a propylene oligomer terminated by a vinylidene double bond, wherein the propylene oligomer is prepared by oligomerizing a propylene-rich raw material containing an olefin in which at least 50 mol% of the olefin in the raw material is propylene, and at least 50 mol% of the propylene oligomer has the vinylidene double bond.

11. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein the hydroxyaromatic compound is phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, naphthol, or hydroxybenzoic acid.

12. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 80 mol% of the olefin in the raw material is propylene.

13. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein the propylene-rich raw material is prepared by fluid catalytic cracking and oligomerized without prior separation of propane and propylene.

14. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 70 mol% of the propylene oligomer has a vinylidene double bond.

15. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 80 mol% of the propylene oligomer has a vinylidene double bond.

16. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein the propylene oligomer has an average number of carbon atoms in the range of about 9 to about 50.

17. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 50 mol% of the alkyl group of the alkylhydroxyaromatic compound has an NMR branching index of 45% or more.

18. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 50 mol% of the alkyl group of the alkylhydroxyaromatic compound has a methyl carbon to methylene carbon ratio greater than about 0.

85.

19. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 50 mol% of the alkyl group of the alkylhydroxyaromatic compound has a methyl carbon to methylene carbon and methine carbon ratio of about 0.29 or more.

20. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 50 mol% of the composition has an alkyl group having at least 5 carbon atoms.

21. The alkyl-substituted hydroxyaromatic composition according to claim 10, wherein at least 50 mol% of the alkyl group of the alkylhydroxyaromatic compound has a ratio of methyl-branched permethylene carbon resonance in the 44-49 PPM range when measured with chloroform to composite saturated aliphatic carbon resonance in the 10-50 ppm range when measured with chloroform greater than 0.

15.

22. A lubricating oil composition, Base oil; and A cleaning agent derived from alkylphenol sulfide, wherein the alkylphenol is produced by alkylation using an alkylating agent containing a vinylidene-rich propylene oligomer containing a propylene oligomer terminated by a vinylidene double bond, the propylene oligomer is prepared by oligomerizing a propylene-rich raw material containing an olefin, wherein at least 50 mol% of the olefin in the raw material is propylene, and at least 50 mol% of the propylene oligomer has a vinylidene double bond, the cleaning agent comprising the cleaning agent and the lubricating oil composition.

23. The lubricating oil composition according to claim 22, wherein at least 70 mol% of the olefin in the raw material is propylene.

24. The lubricating oil composition according to claim 22, wherein the propylene-rich raw material has an olefin-to-alkane molar ratio in the range of about 1 / 10 to about 1 / 10.

25. The lubricating oil composition according to claim 22, wherein the propylene-rich raw material is produced in a catalytic cracking process without separating propane and propylene, and is separated from a catalytic cracking or thermal cracking process with a propylene-to-propane ratio of 5% or less.

26. The lubricating oil composition according to claim 22, wherein at least 80 mol% of the olefin in the propylene-rich raw material is propylene.

27. The lubricating oil composition according to claim 22, wherein at least 70 mol% of the propylene oligomer has a vinylidene double bond.

28. The lubricating oil composition according to claim 22, wherein at least 80 mol% of the propylene oligomer has vinylidene double bonds.

29. The lubricating oil composition according to claim 22, wherein the propylene oligomer has an average number of carbon atoms in the range of about 9 to about 50.

30. A method for alkylating a hydroxyaromatic compound: The method involves oligomerizing a propylene monomer in the presence of a single-site catalyst to form a vinylidene-rich propylene oligomer containing a propylene oligomer terminated by a vinylidene double bond, wherein the propylene oligomer is prepared by oligomerizing a propylene-rich raw material containing an olefin, wherein at least 50 mol% of the olefin in the raw material is propylene, and at least 50 mol% of the propylene oligomer has the vinylidene double bond; The method comprising alkylating the hydroxyaromatic compound with the vinylidene-rich propylene oligomer.

31. The method according to claim 30, wherein the single-site catalyst is a metallocene.

32. The aforementioned metallocene is given by the general formula (RCp) ２ MX ２ The method according to claim 30, wherein Cp is a cyclopentadienyl group, RCp is a substituted cyclopentadienyl group, R is an alkyl group or hydrogen, M is Ti, Zr or Hf, and X is Cl, Br, I, H, Me or Et.

33. The method according to claim 30, wherein the propylene oligomer is prepared by oligomerizing a propylene-rich raw material containing an olefin, wherein at least 80 mol% of the olefin in the raw material is propylene.

34. The method according to claim 30, wherein at least 80 mol% of the propylene oligomer has the vinylidene double bond.

35. The method according to claim 30, wherein the hydroxyaromatic compound is phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, hydroxybenzoic acid, or a salt thereof.

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