CN111344271A - Novel alcohol compounds, process for producing the same and use thereof - Google Patents
Novel alcohol compounds, process for producing the same and use thereof Download PDFInfo
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- CN111344271A CN111344271A CN201880073050.9A CN201880073050A CN111344271A CN 111344271 A CN111344271 A CN 111344271A CN 201880073050 A CN201880073050 A CN 201880073050A CN 111344271 A CN111344271 A CN 111344271A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/02—Monohydroxylic acyclic alcohols
- C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
Abstract
The present invention relates to novel alcohol compounds derivable from neo-acids, the use of such novel alcohol compounds and processes for preparing novel alcohol products.
Description
Priority requirement
The present application claims priority and benefit of US62/565,501 filed on 9/29 of 2017 and EP17208115.0 filed on 12/18 of 2017, the contents of both of which are incorporated herein by reference in their entirety.
Technical Field
The present invention relates to alcohol compounds, their use and processes for their preparation. In particular, the present invention relates to novel alcohol compounds, uses of the novel alcohol compounds, and methods of making the novel alcohol products.
Background
Branched primary aliphatic alcohols, particularly those having long carbon chains, have been used in a number of applications, such as surfactants, solvents, wetting agents, solubilizers, emulsifiers, or as intermediates in the preparation of derivatives such as esters and ethers that can be used as surfactants, solvents, wetting agents, solubilizers, emulsifiers, and lubricant base stocks or additives.
One particular type of branched aliphatic alcohol is the Guerbet alcohol, which is an β -branched primary alcohol having the general structure:
wherein R isaAnd RbGuerbet alcohols may be produced by a Guerbet reaction in which two primary alcohol molecules condense to produce β branched-branched primary alcohol molecules and water.
Has a general structure
(wherein R isa，RbAnd RcIndependently a hydrocarbyl group) may have properties and uses similar to Guerbet alcohols having similar molecular structures derivatives of the neoalcohols may have uses similar to similar derivatives of the Guerbet alcohols.
Thus, there is a need for new alcohol products and methods of making such new alcohol products.
The present invention meets this and other needs.
Summary of The Invention
It has been found that by reduction it has the general formula
The neo-acid can be conveniently prepared into a compound with the general formula
The novel alcohols of (1). The novel alcohols have interesting properties for use in surfactants and can be used as such and can be converted into useful derivatives.
The first aspect of the present invention relates to a compound having the following formula (F-I):
wherein R is1And R2Each independently a hydrocarbyl group (preferably a C2-C60 hydrocarbyl group) containing at least two (2) carbon atoms.
A second aspect of the invention relates to the use of a compound of the first aspect in at least one of: (i) as an additive component in a lubricating oil composition; (ii) as a surfactant in detergent compositions; (iii) as a surfactant and/or solvent in a pharmaceutical composition; (iv) as a surfactant and/or solvent in the pesticide; (v) as surfactants and/or solvents in herbicides; (vi) as a plasticizer in plastic materials.
A third aspect of the present invention relates to a process for preparing a novel alcohol product comprising a novel alcohol compound having the following formula (F-I):
wherein R is1And R2Each independently a hydrocarbyl group containing at least two (2) carbon atoms (preferably a C2-C60 hydrocarbyl group, more preferably a C2-C30 linear or branched alkyl group), comprising: (I) providing a neo-acid product comprising a neo-acid compound having the following formula (F-II):
(II) under reducing conditionsThe neo-acid product is contacted with a reducing agent.
Detailed Description
Definition of
In the present invention, the indefinite articles "a" or "an" mean at least one unless the context clearly dictates otherwise or indicates otherwise.
"alkyl" means a saturated hydrocarbon group consisting of carbon and hydrogen atoms. "Linear alkyl" means an acyclic alkyl group in which all of the carbon atoms are covalently bonded to no more than 2 carbon atoms. "branched alkyl" refers to an acyclic alkyl group in which at least one carbon atom is covalently attached to more than 2 carbon atoms. "cycloalkyl" refers to an alkyl group in which all of the carbon atoms form a ring structure.
"hydrocarbyl" refers to a group consisting solely of hydrogen and carbon atoms. The hydrocarbyl groups may be saturated or unsaturated, linear or branched, cyclic or acyclic, containing cyclic structures or no cyclic structures, and aromatic or non-aromatic. "substituted" hydrocarbyl groups are hydrocarbyl groups in which a hydrogen atom is replaced with another group. An "unsubstituted" hydrocarbyl group is a hydrocarbyl group.
A "Cn" group or compound refers to a group or compound having a total number of carbon atoms of n. Thus, a "Cm-Cn" or "Cm to Cn" group or compound refers to a group or compound whose total number of carbon atoms is m-n. Thus, C1-C50 alkyl represents alkyl groups having a total number of carbon atoms of 1-50.
"monoester" means a compound having one ester (-C (O) -O-) functionality therein.
"neo-acid" refers to a carboxylic acid having the general structure:
wherein R isa，RbAnd RcThe same or different, independently is a hydrocarbon group.
"New alcohol" refers to an alcohol having the general structure
Wherein，Ra，RbAnd RcThe same or different, independently is a hydrocarbon group.
"lubricating oil" means a substance that can be introduced between two or more surfaces and that reduces the level of friction between two adjacent surfaces moving relative to each other. Non-limiting examples of lubricating oils include those in liquid form during their normal use, such as engine oils and gearbox oils, and those in viscous liquid form during normal use, such as greases. Lubricating oil "basestocks" are materials that are typically fluids at various viscosity levels at the operating temperature of the lubricating oil, which are used to formulate lubricating oils by mixing with other components. Non-limiting examples of base stocks suitable for use in lubricating oils include API group I, group II, group III, group IV and group V base stocks. If one base stock is referred to as the main base stock in the lubricant, any additional base stock may be referred to as a co-base stock.
All kinematic viscosity values in the present invention are determined in accordance with ASTM D445. The 100 ℃ kinematic viscosity is reported herein as KV100, and the 40 ℃ kinematic viscosity is reported herein as KV 40. All KV100 and KV40 values herein are in units of cSt unless otherwise specified.
All viscosity index ("VI") values herein are determined in accordance with ASTM D2270.
All Noack volatility ("NV") values herein are determined in accordance with ASTM D5800, unless otherwise specified. All NV values are in wt% unless otherwise specified.
All percentages describing chemical compositions herein are by weight unless otherwise specified. "Wt%" means weight percent.
By "consisting essentially of … …" is meant being included at a weight concentration of at least 90 wt%, based on the total weight of the mixture in question. Thus, a lubricating oil base stock consisting essentially of a given ester compound comprises a weight concentration of the ester compound of at least 90 wt.%, based on the total weight of the lubricating oil base stock.
All numbers expressing values used in the specification and claims are to be modified by the word "about" or "approximately" taking into account experimental error and deviation as would be expected by one skilled in the art.
I. Novel alcohol compounds
One aspect of the present invention is a novel class of alcohol compounds having the following general formula (F-1):
wherein R is1And R2Each independently a hydrocarbyl group comprising at least two (2) carbon atoms (preferably a C2 to C60 hydrocarbyl group, more preferably a C2 to C60 alkyl group, still more preferably a C2 to C60 linear or branched alkyl group, still more preferably a C2 to C30 linear or branched alkyl group). The compound having the molecular structure of (F-1) is a type of novel alcohol, and is referred to herein as "novel alcohol of the present invention".
In the formula (F-I), R is preferred1And R2Each independently comprises c1 to c2 carbon atoms, wherein c1 and c2 can be independently any integer from 2 to 60, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, or 60, provided that c1<c2. C 1-2 and c 2-30 are preferred. More preferably c 1-2 and c 2-24. Even more preferably c 1-4 and c 2-16. Even more preferably c 1-4 and c 2-12. Preferably R1And R2Each independently containing an even number of carbon atoms.
R1And R2At least one (preferably R) of1And R2Each independently) may be a branched alkyl group, preferably a branched alkyl group having the following formula (F-IV):
wherein R isaAnd RbIndependently a hydrocarbyl group, preferably an alkyl group, more preferably a linear or branched alkyl group, even more preferably a linear alkyl group, m is a non-negative integer, preferably m.gtoreq.2, more preferably m.gtoreq.3, even more preferably m.gtoreq.4, even more preferably m.gtoreq.5, even more preferably m.gtoreq.6, even more preferably m.gtoreq.7. Preferably RaAnd RbIndependently contain c3 to c4 carbon atoms, where c3 and c4 can be independently any integer from 1 to 57, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 23, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, or 57, provided that c3<c4. More preferably c 3-1 and c 4-50. Even more preferably c 3-1 and c 4-40. Even more preferably c 3-1 and c 4-20. Even more preferably c 3-1 and c 4-16. Even more preferably c3 ═ 1 and c4 ═ 10. In one embodiment, m ═ 0 and R1And/or R2There may be groups that are branched at the 1 position, i.e., the carbon is directly attached to a quaternary carbon atom. For R1And R2Non-limiting examples of branched alkyl groups of (a) include: 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl and 3, 5-dimethyloctyl.
R1And R2At least one (preferably R) of1And R2Both independently) may be a linear alkyl group, for example: ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-octacosyl and n-triacontyl. Preferably, linear R1And R2The total number of carbon atoms in (a) is an even number. Preferably, the linear R of the combination1And/or R2Wherein a1 and a2 may be independently 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96 or 100, as long as a1<a2. Preferably, the linear R of the combination1And R2The total number of carbon atoms in (A) is 8 to 96, more preferably 8 to 80, still more preferably 8 to 64, still more preferably 8 to 48, still more preferably 8 to 40, still more preferably 8 to 32, still more preferably 8 to 28, still more preferably 8 to 26, still more preferably 8 to 24, still more preferably 8 to 40More preferably 8 to 22, and still more preferably 8 to 20.
Preferably, R is combined1And R2Wherein b1 and b2 may independently be 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96 or 100, provided that b1<b2. Preferably R1And R2The total number of carbon atoms is 8 to 96, more preferably 8 to 80, more preferably 8 to 64, still more preferably 8 to 48, still more preferably 8 to 40, still more preferably 8 to 32, still more preferably 8 to 28, still more preferably 8 to 26, still more preferably 8 to 24, still more preferably 8 to 22, and still more preferably 8 to 20.
Preferably R1And R2Are the same. In such a case, R is particularly preferred1And R2Containing an even number of carbon atoms. Also particularly preferred is R1And R2Are the same linear alkyl groups. In the formula (F-I) R1And R2In various cases, it is highly desirable that they differ in their molar masses by no more than 145 (or 130, 115, 100, 85, 70, 55, 45, 30 or even 15) grams/mole. Preferably, in such a case, R1And R2With no more than 10 (or 9, 8, 7, 6, 5, 4, 3, 2, or even 1) difference in the total number of carbon atoms contained therein.
In particular, desirable examples of the novel alcohols of the present invention are as follows: 2-ethyl-2-methylhexan-1-ol; 2-methyl-2-propylhept-1-ol; 2-butyl-2-methyloctan-1-ol; 2-hexyl-2-methyldecan-1-ol; 2-methyl-2-octyldodecan-1-ol; 2-decyl-2-methyltetradecan-1-ol; 2-dodecyl-2-methylhexadecyl-1-ol; 2-methyl-2-tetradecyl octadecan-1-ol; 2-hexadecyl-2-methyl eicosan-1-ol; 2-methyl-2-octadecyldiehandol-1-ol; 2-eicosyl-2-methyltetracosan-1-ol; 2-docosyl-2-methyl hexacosanol-1-ol; 2-methyl-2-tetracosanyl octacosan-1-ol; and 2-hexacosanyl-2-methyltranstriacontan-1-ol.
Among the above novel alcohol compounds, the following are even more preferred: 2-ethyl-2-methylhexan-1-ol; 2-butyl-2-methyloctan-1-ol; 2-hexyl-2-methyldecan-1-ol; 2-methyl-2-octyldodecan-1-ol; 2-decyl-2-methyltetradecan-1-ol; and 2-dodecyl-2-methylhexadecane-1-ol.
Use of novel alcohol compounds
Each molecule of the novel alcohols of the present invention is characterized by hydroxyl groups that impart polarity and hydrophilicity. The hydrocarbon chains in the molecule, particularly those relatively long chains having a carbon backbone containing at least 6 carbon atoms, impart hydrophobicity to the molecule at the end opposite the hydroxyl group. The amphiphilic nature of the novel alcohol molecules makes them suitable for use as surfactants, as detergents, wetting agents, emulsifiers, foaming agents and dispersing agents.
Thus, the novel alcohols of the present invention may have many applications. One contemplated application is a lubricating oil composition (e.g., an additive package for a lubricating oil formulation; or a lubricating oil formulation). Other examples of applications include: detergents, such as household laundry detergents and soaps; personal care products such as lotions, hair care products, and the like; pharmaceutical products, such as pharmaceutical syrups; industrial products, such as degreasers and industrial cleaners; a pesticide; herbicides, and the like. The novel alcohols of the invention can also be used as plasticizers in plastics. Furthermore, the novel alcohols of the present invention may be used as modifiers for formulations in mining operations; as compatibilizers in printed products such as ink formulations and toner formulations; and many solvents or diluents in chemical mixtures have been used. All of these different products comprising the novel alcohols of the present invention also constitute various aspects of the present invention.
The novel alcohols of the present invention can be readily converted into a number of useful derivatives, such as esters, ethers, and the like. Such derivatives may be conveniently used in a number of applications.
Lubricating oil compositions comprising novel alcohols
In the present invention, a lubricating oil formulation means a lubricating oil product intended for its intended use. Thus, examples of lubricating oil formulations include: preparing engine oil disposed in a crankcase of an internal combustion engine; preparing gear oil for distribution into a gearbox; preparing the grease for application to a device in need of the grease; and so on. In the present invention, the lubricating oil composition may be any part or whole of a lubricating oil formulation. Thus, the lubricating oil composition may be: (i) a base stock; (ii) an additive package comprising one or more additives; (iii) a mixture of two or more base stocks, in the absence of any additives; (iv) a mixture of one or more base stocks and one or more additives, but not the entirety of a lubricating oil formulation; and (iv) a lubricating oil formulation as a whole.
The novel alcohols of the present invention may be used as additive components in formulating lubricating oil compositions. To prepare the final lubricating oil formulation as a product, additional components such as other base stocks, additional amounts of materials already present in the lubricating oil composition, additive components, and the like may be added to the lubricating oil composition. However, one particularly preferred embodiment of the lubricating oil composition of the present invention is a lubricating oil formulation.
For example, the neoalcohol may be present as an additive component in the lubricating oil formulation in an amount of about c1 to c2 wt%, wherein c1 and c2 may independently be 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, or 5, based on the total weight of the oil composition, as long as c1< c 2.
Due to the polarity of the new alcohols generated by hydroxyl groups in their molecular structure, they have the ability to enhance sludge solvency and dispersancy and solvency compared to other lubricating oil compositions that do not contain alcohols.
IIa.1 base stocks useful in the lubricating oil compositions
A wide range of lubricating oil base stocks known in the art may be used in combination with the novel alcohols in the lubricating oil compositions of the present invention as either the main base stock or the co-base stock. Such base stocks may be derived from natural sources or synthetic, including unrefined, refined or rerefined oils. Unrefined oil basestocks include shale oil obtained directly from retorting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from natural sources (e.g., plant matter and animal tissue) or directly from chemical esterification processes. Refined oil base stocks are those unrefined base stocks that have been further subjected to one or more purification steps such as solvent extraction, secondary distillation, acid extraction, base extraction, filtration, and percolation to improve at least one lubricating oil property. Rerefined oil base stocks are obtained by processes similar to refined oils but using oils that have been previously used as feed stocks.
API groups I, II, III, IV, and V are broad classifications of base stocks established and defined by the U.S. Petroleum organization (API Publication 1509; www.API.org) to generate guidelines for lubricating oil base stocks group I base stocks typically have viscosity indices of about 80-120 and contain greater than about 0.03% sulfur and less than about 90% saturates group II base stocks typically have viscosity indices of about 80-120 and contain less than or equal to about 0.03% sulfur and greater than or equal to about 90% saturates group III base stocks typically have viscosity indices greater than about 120 and contain less than or equal to about 0.03% sulfur and greater than about 90% saturates group IV includes poly α -olefins (PAO) group V base stocks include base stocks not included in groups I-IV.
Natural oils include animal oils (e.g., lard oil), vegetable oils (e.g., castor oil), and mineral oils. Animal and vegetable oils with advantageous thermo-oxidative stability can be used. Among natural oils, mineral oils are preferred. Mineral oils are different in terms of their oil source, for example in terms of whether they are paraffinic, naphthenic or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present invention. Natural oils also differ with respect to the methods used for their production and purification, such as their distillation range and whether they are straight run or cracked, hydrofinished or solvent extracted.
Group II and/or group III base stocks are typically hydrotreated or hydrocracked base stocks derived from crude oil refining processes.
Synthetic base stocks include polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene- α olefin copolymers).
Synthetic poly α -olefin ("PAO") base stocks fall into group IV advantageous group IV base stocks are those prepared from one or more of the C6, C8, C10, C12 and C14 linear α -olefins ("LAO") these base stocks are commercially available at a wide range of viscosities, e.g., KV100 is 1.0-1000cStTMAnd SpectraSyn EliteTMSeries, available from ExxonMobil Chemical Company, USA, with the address 4500Bayway Drive, Baytown, Texas 77520.
All other synthetic base stocks (including but not limited to alkylaromatics and synthetic esters) are in group V.
Additional esters not in the neo-acid derived ester class may be used in minor amounts in the lubricating oil compositions of the present invention. By using esters such as esters of dibasic acids with monoalkanols and polyol esters of monocarboxylic acids, additive solvency and seal compatibility characteristics can be imparted. The former type of esters include, for example, esters of dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acids, alkenylmalonic acids, etc., with various alcohols such as butanol, hexanol, dodecanol, 2-ethylhexanol, etc. Specific examples of these types of esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, and the like. Useful ester type group V basestocks include Esterx, commercially available from ExxonMobil Chemical CompanyTMAnd (4) series.
One or more of the following may also be used as base stocks in the lubricating oil of the present invention: (1) one or more Gas To Liquid (GTL) materials; and (2) hydrodewaxed, hydroisomerized, solvent dewaxed or catalytically dewaxed base stocks derived from synthetic waxes, natural waxes, waxy feeds, slack waxes, gas oils, waxy fuels, hydrocracker bottoms, waxy raffinates, hydrocrackers, thermal cracked products, foots, and waxy materials derived from coal liquefaction or shale oils. Such waxy feeds may be derived from mineral or non-mineral oil processing or may be synthetic (e.g., Fischer-Tropsch feed stocks). Such base stocks preferably comprise C20 or higher, more preferably C30 or higher linear or branched hydrocarbyl compounds.
In addition to the neoalcohols, the lubricating oil compositions of the present invention may also contain one or more group I, II, III, IV or V basestocks. Preferably, if a high quality lube is desired, the group I base stock (if any) is present in a relatively low concentration. Group I base stocks may be introduced in small amounts as diluents for the additive package. Group II and III basestocks may be included in the lubricating oil compositions of the present invention, but are preferably only those of high quality, such as those having a VI of 100-120. Group IV and V basestocks, preferably those of high quality, are desirably included in the lubricating oil compositions of the present invention.
IIa.2 lubricating oil additive
The novel alcohols of the present invention can be advantageously used as additive components in lubricating oil compositions. The lubricating oil compositions of the present invention containing the neo-acids may additionally comprise one or more of other conventional lubricating oil performance additives, including, but not limited to, dispersants, detergents, viscosity modifiers, antiwear additives, corrosion inhibitors, rust inhibitors, metal deactivators, extreme pressure additives, anti-seize agents, wax modifiers, viscosity modifiers, fluid loss additives, seal compatibilisers, lubricants, anti-staining agents, colourants, anti-foaming agents, demulsifiers, densifiers, wetting agents, gelling agents, tackifiers, colorants and others. For a review of many commonly used additives and amounts, see: (i) klamann, Lubricants and Related Products, VerlaggChemie, Deerfield Beach, FL; ISBN 0-89573-177-0; (ii) "Lunbrict Additives", M.W. Ranney, published by the Noyes Data Corporation of Parkridge, NJ (1973); (iii) "Synthesis, Mineral Oils, and Bio-Based Lubricants", edited by L.R. Rudnick, CRCTaylor and Francis, 2006, ISBN 1-57444-; (iv) "contamination Fundamentals", J.G.Wills, Marcel Dekker Inc. (New York, 1980); (v) synthetic Lubricants and High-Performance Functional Fluids, 2 nd edition, Rudnick and shunkin, Marcel Dekker inc. (new york, 1999); and (vi) "Polyalpha-oleosins", L.R. Rudnick, Chemical Industries (BocaRaton, FL, USA) (2006), 111 (Synthesis, Mineral Oils, and Bio-base Lubricants), 3-36. Reference may also be made to: (a) U.S. patent nos. 7704930B2; (b) U.S. patent No.9458403B2, column 18, line 46 to column 39, line 68; (c) U.S. patent No.9422497B2, column 34, line 4 to column 40, line 55; and (d) U.S. patent No.8048833B2, column 17, line 48 to column 27, line 12, the disclosure of which is incorporated herein by reference in its entirety. Prior to incorporation into the formulated oil, the additives, including the novel alcohol(s) of the present invention and other additives, are typically delivered with various amounts of diluent oil, which can range from 5 wt% to 50 wt%, based on the total weight of the additive package. The additives useful in the present invention need not be soluble in the lubricating oil composition. Additives that are insoluble in oil may be dispersed in the lubricating oil composition of the present invention. One or more of these other types of additive components can be combined with the novel alcohol(s) of the present invention to form a mixture and delivered as an additive package. The additive package may be conveniently combined with other lubricant components (e.g., a main base stock, one or more co-base stocks, and other additive packages) in desired amounts to prepare a lubricant formulation (e.g., an engine oil) that may be used directly for its intended use (e.g., the crankcase of an internal combustion engine). As discussed above, the additive package for a lubricating oil composition is a specific type of lubricating oil composition. It should be noted that many additive packages are shipped from additive manufacturers as concentrates (containing one or more additives along with a certain amount of base oil diluent). The novel alcohol(s) of the present invention, as a lubricity additive and as an additive containing the novel alcohol(s) of the present invention, may also be shipped as a concentrate containing an amount of base oil diluent.
When the lubricating oil composition comprises one or more of the above-described additives, the additive(s) are blended into the oil composition in an amount sufficient for it to perform its intended function.
Other uses of the novel alcohols of the invention
The novel alcohols of the present invention exhibit amphiphilic properties due to the presence of hydroxyl groups and one or more hydrocarbon chains in their molecules and are therefore useful as surfactants in detergent compositions, pharmaceutical compositions, pesticidal compositions and herbicidal compositions, to name a few. It may also be used as a solvent in these compositions. The novel alcohols of the present invention are conveniently converted to various derivatives, which may also be used as surfactants in the above compositions.
Plasticizers are incorporated into resins (typically plastics or elastomers) to increase the flexibility, processability or malleability of the resin. The largest use of plasticizers is in the production of "plasticized" or flexible polyvinyl chloride (PVC) products. Common uses for plasticized PVC include films, sheets, tubing, coated fabrics, wire and cable insulation and jacketing, toys, flooring materials such as vinyl sheet flooring or vinyl floor tile, adhesives, sealants, inks, and medical products such as blood bags and tubing, and the like. Other polymer systems that use small amounts of plasticizer include polyvinyl butyral, acrylic polymers, nylon, polyolefins, polyurethanes, and fluoroplastics. Plasticizers may also be used with the rubber (although these materials generally fall within the definition of rubber extender rather than plasticizer). "plastisizers," A.D.Godwin, Applied Polymer Science 21st centre, C.D.Craver and C.E.Carraher eds, Elsevier (2000); the primary plasticizers and their compatibility with different polymer systems are listed on pages 157-175.
There is an increasing interest in developing new plasticizers with good plasticizer performance characteristics (e.g., melt or chemical and thermal stability, pour point, glass transition, increased compatibility, good performance and low temperature properties) and that are economically competitive.
The novel alcohols of the present invention can be advantageously used as the above-mentioned plasticizers.
The novel alcohols of the present invention can be advantageously used as intermediates for the preparation of various chemical derivatives thereof. Such derivatives may include, but are not limited to, esters, ethers, polyether (polyethylene oxide, polypropylene oxide, etc.) polyurethanes, sulfates, and the like.
Process for preparing novel alcohol products
One aspect of the present invention relates to a process for preparing a novel alcohol product comprising a novel alcohol compound having the following formula (F-1):
wherein R is1And R2Each independently a hydrocarbyl group comprising at least two (2) carbon atoms (preferably C2 to C60 hydrocarbyl groups, more preferably C2 to C60 alkyl groups, still more preferably C2 to C60 linear or branched alkyl groups, and still more preferably C2 to C30 linear or branched alkyl groups), the process comprising: (I) providing a neo-acid product comprising a neo-acid compound having the formula (F-II):
and (II) contacting the neo-acid product with a reducing agent under reducing conditions.
It is highly desirable that the neo-acid product used in the process consists essentially of a single mono-neo-acid, which will result in a neo-alcohol product consisting essentially of a single neo-alcohol compound, although mixtures of multiple neo-acids having different formulas (F-II) can also be used, which will result in a neo-alcohol product comprising multiple corresponding neo-alcohol compounds. Different but similar neo-acid mixtures can then be purchased at a lower cost than the high purity neo-acid compounds, and the latter can be economically more advantageous where a neo-alcohol mixture derivable from such a neo-acid mixture is acceptable for its intended use.
In the formula (F-II), preferably, R1And R2Each independently comprising c1 to c2 carbon atoms, whereinc1 and c2 may independently be any integer from 2 to 60, such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, or 60, provided that c1<c2. C 1-2 and c 2-30 are preferred. More preferably c 1-2 and c 2-24. Even more preferably c 1-4 and c 2-16. Preferably R1And R2Each independently containing an even number of carbon atoms.
R1And R2At least one (preferably R) of1And R2Each independently) may be a branched alkyl group, preferably a branched alkyl group having the following formula (F-IV):
wherein R isaAnd RbIndependently a hydrocarbyl group, preferably an alkyl group, even more preferably a linear or branched alkyl group, even more preferably a linear alkyl group, m is a non-negative integer, preferably m.gtoreq.2, more preferably m.gtoreq.3, even more preferably m.gtoreq.4, even more preferably m.gtoreq.5, even more preferably m.gtoreq.6, even more preferably m.gtoreq.7. Preferably RaAnd RbIndependently contain c3 to c4 carbon atoms, where c3 and c4 can be independently any integer from 1 to 57, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, 23, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, or 57, provided that c3<c4. More preferably c 3-1 and c 4-50. Even more preferably c 3-1 and c 4-40. Even more preferably c 3-1 and c 4-20. Even more preferably c 3-1 and c 4-16. Even more preferably c3 ═ 1 and c4 ═ 10. In a specific embodiment, m ═ 0 and R1And/or R2There may be groups that are branched in the 1 position, i.e., the carbon is directly attached to a quaternary carbon atom. For R1And R2Non-limiting examples of branched alkyl groups of (a) include: 2-ethylhexyl, 2-propylheptyl, 2-butyloctyl and 3, 5-dimethyloctyl.
R1And R2At least one (preferably R) of1And R2Both independently) may be a linear alkyl group such as: ethyl, n-propylN-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-octacosyl and n-triacontyl. Preferably linear R1And R2The total number of carbon atoms in (a) is an even number. Preferably combined linear R1And/or R2Wherein a1 and a2 may be independently 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96 or 100, as long as a1<a2. Preferably combined linear R1And R2The total number of carbon atoms in (A) is 8 to 96, more preferably 8 to 80, still more preferably 8 to 64, still more preferably 8 to 48, still more preferably 8 to 40, still more preferably 8 to 32, still more preferably 8 to 28, still more preferably 8 to 26, still more preferably 8 to 24, still more preferably 8 to 22, and still more preferably 8 to 20.
Preferably, R is combined1And R2Wherein b1 and b2 may independently be 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 52, 56, 60, 64, 80, 96 or 100, provided that b1<b2. Preferably, R1And R2The total number of carbon atoms in (A) is 8 to 96, more preferably 8 to 80, still more preferably 8 to 64, still more preferably 8 to 48, still more preferably 8 to 40, still more preferably 8 to 32, still more preferably 8 to 28, still more preferably 8 to 26, still more preferably 8 to 24, still more preferably 8 to 22, and still more preferably 8 to 20.
Preferably, R1And R2Are the same. In such a case, R is particularly preferred1And R2Containing an even number of carbon atoms. Also particularly preferred is R1And R2Are the same linear alkyl groups. At R1And R2In various cases, it is highly desirable that they differ in their molar masses by no more than 145 (or 130, 115, 100, 85)70, 55, 45, 30 or even 15) grams/mole. Preferably, in such a case, R1And R2With no more than 10 (or 9, 8, 7, 6, 5, 4, 3, 2, or even 1) difference in the total number of carbon atoms contained therein.
The neo-acid products useful in the process for making the neo-alcohols of the present invention can be made by a process comprising the steps of: (Ia) providing a vinylidene olefin feed comprising a vinylidene olefin having the following formula (F-III):
wherein R is1And R2Corresponding to R in the formula (F-I)1And R2(ii) a (Ib) contacting the vinylidene olefin with carbon monoxide in a reactor in the presence of an acid catalyst, preferably at a carbon monoxide partial pressure of at least 1.0MPa, more preferably at least 3.5MPa, even more preferably at least 5.0MPa, to obtain a reaction mixture; (Ic) contacting the reaction mixture with water to obtain an acid product mixture; and (Id) obtaining at least a portion of the neo-acid product from the crude acid mixture.
The vinylidene olefin feed useful in step (Ia) above may advantageously be prepared from a terminal olefin monomer feed in a process comprising the steps of: (Ia.1) providing a monomer feed comprising a terminal olefin having the following formula (F-IV) and a terminal olefin having the following formula (F-V): r1-CH＝CH2(F-IV)；R2-CH＝CH2(F-V); wherein R is1And R2Corresponding to R in the formulae (F-III), (F-II) and (F-I)1And R2(ii) a (ia.2) oligomerizing the monomer feed in an oligomerization reactor in the presence of a catalyst system comprising a metallocene compound to obtain an oligomerization product mixture; and (ia.3) obtaining at least a portion of the vinylidene olefin feed from the oligomerization product mixture. In this process, R in the formula (F-I) of the novel alcohol1And R2In the same case, a single terminal olefin of formula (F-IV) is used for the monomer feed. In the formula (F-I) of the novel alcohols R1And R2In different cases, at least two terminal olefins having different formula (F-IV) are used for the monomer feed. Use of two different terminal olefins for monomersIn the case of a feed, the oligomerization product mixture that can be obtained from step (ia.2) can comprise up to four vinylidene olefins as dimers of two terminal olefins, which can be separated in step (ia.3) to obtain the desired vinylidene olefin feed comprising 1, 2, 3 or all 4 vinylidene olefins, as the case may be. Nine vinylidene olefin dimers can be produced from the three terminal olefins in the monomer feed. These different vinylidene olefins, if included in the vinylidene olefin feed in step (Ia) of the above-described process for making neo-acids, can be converted to the corresponding neo-acids in the neo-acid product, which in turn can be converted to the corresponding neo-alcohol compounds in the neo-alcohol product.
The above process for preparing the neo-acid product via the vinylidene olefin intermediate starting from a terminal olefin monomer can be as shown in scheme-I below:
only one vinylidene olefin dimer is illustrated in scheme-I above. The method is described in further detail below. Specific examples of scheme-I are provided in section A of the embodiments of the present invention.
Vinylidene olefin feed and process for preparing same
The vinylidene olefins useful in the process of the present invention for making the neo-acid product have the following formula (F-III):
wherein R is1And R2R in the formula (F-II) corresponding to neo-acids respectively1And R2 radicals which in turn correspond respectively to R in the formula (F-I) of the novel alcohols1And R2A group.
Preferably, in the formula (F-III) of the vinylidene olefin, R1And R2Are the same. Thus, examples of preferred vinylidene olefins having the formula (F-III) useful in the process of the present invention are: 3-methylene heptane; 4-methyleneAn alkyl nonane; 5-methyleneundecane; 7-methyleneheptadecane; 9-methylenenonadecane; 11-methylene eicosatriane; 13-methyleneheptacosane; and 15-methylenehentriacontane and mixtures thereof.
When R in the formula (F-III)1And R2In contrast, it is highly desirable that they differ in their regral masses by no more than 145 (or 130, 115, 100, 85, 70, 55, 45, 30, or even 15) grams/mole. In this case, preferably, R1And R2Not more than 10 (or 9, 8, 7, 6, 5, 4, 3, 2, or even 1) in total number of carbon atoms contained therein.
The vinylidene olefin having the formula (F-III) can be advantageously prepared by dimerizing a monomer feed comprising a terminal olefin having the formula (F-III) below and a terminal olefin having the formula (F-IV) below: r1-CH＝CH2(F-III)；R2-CH＝CH2(F-IV) wherein R1And R2Corresponding to R in (F-III), (F-II) and (F-I)1And R2. It is highly desirable that the monomer feed consists essentially of a single terminal olefin having the formula (F-III). In this case, the compound of formula (F-III) (wherein R is1And R2Identical) single vinylidene olefin which may be used as the vinylidene olefin feed in step (I) of the process of the invention for preparing the neo-acid product. It is contemplated that the monomer feed may comprise a plurality of terminal olefins having different formulas (F-III). In this case, as discussed below, a plurality of vinylidene olefins having different formulas (F-III) can be produced in the dimerization reaction, which can be used together as a vinylidene olefin feed to produce a neo-acid product comprising a plurality of neo-acid compounds. When the monomer feed comprises a plurality of terminal olefins, it is highly desirable that they differ in their molecular weight by no more than 145 (or 130, 115, 100, 85, 70, 55, 45, 30, or even 15) grams/mole. In this case, preferably, the terminal olefins contained in the monomer feed differ by no more than 10 (or 9, 8, 7, 6, 5, 4, 3, 2, or even 1) in the total number of carbon atoms contained therein.
Such dimerization can advantageously be carried out in the presence of a catalyst system comprising a metallocene compound. U.S. patent No.4658078, the contents of which are incorporated herein by reference in their entirety, discloses a process for preparing vinylidene olefin dimers from terminal olefin monomers. The batch process disclosed in U.S. patent No.4658078 results in various levels of trimers and higher oligomers being produced along with the target dimer, which can be removed, for example, by distillation to obtain a substantially pure dimer product. The dimer product produced by the batch process of U.S. patent No.4658078 may contain various levels of 1, 2-disubstituted vinylidene olefin(s) and trisubstituted vinylidene olefin(s). If the concentrations of the 1, 2-disubstituted vinylidene olefin(s) and the trisubstituted vinylidene olefin(s) are acceptable for the intended use of the present invention, the batch process disclosed in U.S. patent No.4658078 can be used to produce dimers having the above formula (F-III) that can be used in the process for preparing the neo-acid products of the present invention.
Such dimerization may also be carried out in the presence of a trialkylaluminum such as tri (t-butyl) aluminum as disclosed in U.S. patent No.4987788, the contents of which are incorporated herein by reference in their entirety.
Desirably, the vinylidene olefin feed of formula (F-III) used in the process of the invention for producing the neo-acid product comprises a single vinylidene olefin of formula (F-III) having a purity of at least 90 wt%, preferably at least 92 wt%, more preferably at least 94 wt%, still more preferably at least 95 wt%, still more preferably 96 wt%, still more preferably at least 97 wt%, still more preferably at least 98 wt%, still more preferably at least 99 wt%, based on the total weight of the olefins contained in the feed.
Mixtures of two or more vinylidene olefins having different formula (F-III) can be used as the vinylidene olefin feed in a process for preparing a neo-acid product mixture as the neo-acid product. Desirably, each vinylidene olefin contained in the mixture has a similar molecular weight, i.e., the molecular weights differ by no more than, for example, 145, 130, 115, 100, 85, 70, 55, 45, 30, or even 15 grams/mole. Desirably, the individual vinylidene olefins contained in the mixture differ in the total number of carbon atoms contained therein by no more than 10, 9, 8, 7, 6, 5, 4, 3, 2, or even 1. Each vinylidene olefin contained in the mixture may be a structural isomer. Vinylidene olefins having different chemical formulas and/or molecular weights can be converted to neo-acid compounds having different chemical formulas and/or molecular weights according to the same reaction mechanism under the same reaction conditions. As long as the mixture of neo-acid compounds can be used to make a mixture neo-alcohol acceptable for the target application, the corresponding mixture of vinylidene olefins can be used as the vinylidene olefin feed for making the neo-acid product using the process of the present invention.
It is highly desirable that the vinylidene olefin feed used in the process for producing the neo-acid product comprises 1, 2-disubstituted vinylidene olefin(s) and trisubstituted vinylidene olefin(s) as impurities in a total concentration of no greater than 5 weight percent, preferably no greater than 4 weight percent, even more preferably no greater than 3 weight percent, even more preferably no greater than 2 weight percent, and no greater than 1 weight percent, based on the total weight of the olefins contained in the feed.
The above olefin R1-CH＝CH2And R2-CH＝CH2May be carried out in the presence of a catalyst system, such as a catalyst system comprising a metallocene compound. Co-pending, commonly assigned U.S. provisional patent application No. 62/551081 (entitled "Process for Making vinylideneolefin Olefi", filed as 8.8.28.2017) discloses vinylideneolefin dimers useful in the preparation of terminal olefins useful in the preparation of neo-acids of the neo-alcohols of the present invention, and a Process for preparing such vinylidenedimers, the contents of which are incorporated herein by reference in their entirety.
Carboxylation of vinylidene olefins to produce neo-acid compounds
Koch chemistry can be used to make neo-acids from the vinylidene olefins described above. Koch chemistry includes the step of reacting an olefin with carbon monoxide in the presence of a strong acid at an effective reaction temperature and an effective partial pressure of CO (referred to herein as "carboxylation"). Typically in a subsequent step, the reaction mixture from the carboxylation step, which is reacted with CO, is contacted with water to produce carboxylic acid. It is highly desirable that the step of reacting the vinylidene olefin with the CO is carried out in a batch reactor due to the pressurized nature. The reaction can be schematically illustrated as follows:
the acid catalyst used in the carboxylation step may be any strong organic or inorganic acid. Non-limiting examples are: (i) bronsted acids such as HF; HCl; sulfuric acid; phosphoric acid; and mixtures thereof; (ii) solid acids such as activated clays; an acid clay; faujasite zeolite; zeolites such as X-type zeolite, Y-type zeolite and mordenite; oxides of transition metals such as zirconium, titanium, vanadium, tungsten, molybdenum, niobium, tantalum, and mixtures and compounds thereof; and compositions and mixtures thereof; (iii) an acid resin; and (iv) Lewis acids such as BF3，AlCl3Etc.; and (v) any mixtures and combinations of any of the classes (i), (ii) and (iii), e.g. HF and BF3And (3) mixing.
The acid catalyst may be used in an amount of R1 to R2, where R is expressed as a molar ratio of catalyst to vinylidene olefin1And R2May independently be 0.01, 0.02, 0.04, 0.05, 0.06, 0.08, 0.1, 0.2, 0.4, 0.5, 0.6, 0.8, 1, 2, 4, 5, 6, 8, 10, 20, 40 or 50, provided that r1 is present<r 2. Preferably, r 1-0.02 and r 2-80. More preferably, r 1-0.05 and r 2-50. Still more preferably, r 1-0.1 and r 2-10. Still more preferably, r 1-0.2 and r 2-5. The molar amount of the catalyst means the molar amount of molecules, ions or functional groups in the catalyst material that provide a catalytic effect in the carboxylation reaction between vinylidene olefin and CO. Thus, BF3Molar amount of catalyst expressed as BF3·1.1H2Molar amount of O. BF (BF) generator3·2H2O is believed not to be catalytically effective for the reaction between vinylidene olefin and CO. However, the anhydrous BF is subsequently3BF may be added to the reaction system3·2H2Conversion of O into catalytically active form BF3·1.1H2And O. Thus, in the present invention, in BF3·2H2O and anhydrous BF3Are introduced separately in stoichiometric amounts into the reaction system to form BF3·1.1H2In case of O, BF is calculated3For the purpose of molar quantity of catalyst, it is assumed that the total BF is3Is BF of3·1.1H2The O form exists in the reaction system. The molar amount of HF catalyst represents the molar amount of protons provided by the catalyst (which is considered to be equal to the amount of HF, due to the strong acidity of HF). For solid phase catalyst materials such as zeolites, solid acids and acidic resins, the molar amount represents the molar amount of functional groups or ions provided by the catalyst material.
Since the vinylidene olefin(s) may undergo oligomerization in the presence of an acid catalyst in addition to the reaction according to Koch chemistry, it is highly desirable not to contact the active acid catalyst with the olefin until after the olefin has formed a mixture with CO at a high partial pressure of CO in the reaction mixture. Therefore, it is desirable that the active acid catalyst is not added to the reaction system until after the partial pressure of CO in the reaction system has reached 2.0 megapascals ("MPa"), preferably 2.5MPa, more preferably 3.0MPa, still more preferably 3.5kPa, still more preferably 5.0MPa, and still more preferably 7.0 MPa.
When BF3When used as an acid catalyst for the reaction between vinylidene olefin and CO, it is highly desirable to add a certain amount of BF before the CO partial pressure in the reactor is increased to 2.0MPa3·2H2O is mixed with the vinylidene olefin feed in the reactor. Without intending to be bound by a particular theory, it is believed that BF3·2H2O is not catalytically effective for oligomerization of vinylidene olefins or carboxylation reactions between vinylidene olefins and CO. Thus, in order to catalyze the carboxylation reaction, it is desirable to pass anhydrous BF after the CO partial pressure has reached the above-mentioned certain level3Introduced into a reactor to effect carboxylation between vinylidene olefin and CO. Preferably BF3·2H2O and anhydrous BF3In a substantially stoichiometric ratio to form BF3·1.1H2O。
Also, if a Bronsted acid such as H is used2SO4HF or H3PO4For use as an acid catalyst, it is highly desirable that the acid is not introduced into the reactor until after the partial pressure of CO in the reactor has reached a certain level as described above.
If a solid acid is used as the catalyst in the carboxylation reaction, it is highly desirable to distribute the solid acid catalyst into the inert dispersant and introduce it into the reactor after the partial pressure of CO within the reactor has reached the certain level described above.
If it is desired to raise the temperature of the reaction medium in the reactor to a higher level to achieve the desired conversion and/or reaction rate, it is highly desirable that the partial pressure of CO within the reactor also has reached a certain level as described above. Preferably, the temperature ramp process is initiated after at least a portion of the active catalyst has been introduced into the reactor.
The catalyst may be added to the carboxylation reaction system as a solution in an inert solvent, as a substantially pure material or as a dispersion in an inert dispersant. Non-limiting examples of inert solvents and/or dispersants include: benzene, toluene, any xylene, ethylbenzene, and mixtures thereof; n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and its saturated isomers, and mixtures thereof; n-heptane and its branched isomers, and mixtures thereof; n-octane and its branched isomers, and mixtures thereof; n-nonane and its branched isomers, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and mixtures of any of the foregoing;
a solvent; and so on.
The carboxylation reaction of vinylidene olefins with CO is desirably carried out in an atmosphere comprising CO at an absolute partial pressure of CO of from p1 to p2 MPa, where p1 and p2 may independently be 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, 9.5, 10.0, 10.5, 11.0, 11.5, 12.0, 12.5, 13.0, 13.5 or 14.0, as long as p1< p 2. The high total partial pressure of CO favors high conversion of vinylidene. Desirably, the conversion of vinylidene in the carboxylation reaction is at least 70%, preferably at least 75%, more preferably at least 80%, more preferably at least 85%, more preferably at least 90%, still more preferably at least 95%.
The carboxylation of vinylidene olefins with CO is desirably carried out at a temperature of t1 ℃ to t2 ℃, where t1 and t2 may independently be-20, -15, -10, -5, 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 110 or 120, provided t1< t 2. Preferably t 1-0 and t 2-100. More preferably t 1-25 and t 2-80. Higher temperatures favor higher conversions and higher reaction rates, but at the expense of selectivity to the desired neo-acid derived from the vinylidene olefin. The reaction time may be 0.5 hour to 96 hours, preferably 1 hour to 60 hours, more preferably not longer than 48 hours, still more preferably not longer than 36 hours, still more preferably not longer than 24 hours, still more preferably not longer than 12 hours, still more preferably not longer than 6 hours.
In view of the pressurized reaction conditions, it is highly desirable that the carboxylation between vinylidene olefin and CO be carried out in a batch reactor that can withstand high internal pressures. At the end of the reaction, the reactor is cooled and depressurized, and the carboxylated product mixture (which contains unreacted vinylidene olefin, catalyst, desired neo-acid product and other undesired by-products) may advantageously be separated to obtain the neo-acid product.
The carboxylation reaction between vinylidene olefin and CO can be carried out in the presence or absence of an inert solvent. Non-limiting examples of inert solvents include: benzene, toluene, any xylene, ethylbenzene, and mixtures thereof; n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and its saturated isomers, and mixtures thereof; n-heptane and its branched isomers, and mixtures thereof; n-octane and its branched isomers, and mixtures thereof; n-nonane and its branched isomers, and mixtures thereof; n-decane and process for producing the sameBranched isomers, and mixtures thereof; and mixtures of any of the foregoing;
a solvent; and so on.
In the step of reacting the vinylidene olefin with CO in the presence of the acid catalyst, water may be included in the reactants in a small amount as long as the presence of water does not reduce the activity of the catalyst. After the reaction with CO is complete, the reaction mixture is typically contacted with water to complete the carboxylation of the vinylidene olefin to produce the desired neo-acid product. Contact with water may result in the formation of a mixture comprising an aqueous phase and an organic phase. The acid is typically preferentially distributed in the organic phase, and any acid catalyst that is soluble in or reactive with water may be preferentially distributed in the aqueous phase. In the case of solid catalysts such as solid zeolites, solid acids and acid resins, the catalyst may be conveniently filtered from the liquid, dried and reused in the carboxylation reaction as appropriate. The neo-acid product in the organic phase can be further purified to obtain a neo-acid product that contains predominantly the target acid of formula (F-II) having the desired purity. Purification can be carried out via conventional methods such as one or more of water washing, solvent extraction, distillation, liquid or gas chromatography, or by using an adsorbent.
In a process for producing a neo-acid product from vinylidene olefins, if the active catalyst is not added to the reaction until a high CO partial pressure has been established in the reaction system (e.g., a partial pressure of at least 5.0, 5.5, 6.0, 6.5, or 7.0MPa), high selectivity of the vinylidene olefin to the desired neo-acid can be achieved in the carboxylation process, which produces the neo-acid product of the desired neo-acid having a purity of at least 95 wt%, 96 wt%, at least 97 wt%, at least 98 wt%, or even at least 99 wt%, based on the total weight of the neo-acid product, after removal of the vinylidene olefin and heavy components. Such high purity neo-acids are very surprising.
The combination of the carboxylation Process and a continuous Process for Making high purity Vinylidene dimers of terminal Olefin monomers, which are Vinylidene olefins used in the carboxylation Process (the Process is described in CO-pending, commonly assigned U.S. divisional application No. 62551081 entitled "Process for Making vinylideneidene oxide", application date 2017, 8/28, the contents of which are incorporated herein by reference in their entirety) can produce a high conversion, high selectivity Process for Making the desired neo-acid from a terminal Olefin feed and a CO feed.
Commercially available terminal olefins that may be used in the process of the present invention include, but are not limited to: 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. They can be conveniently used for the preparation of the neo-acids 2-ethyl-2-methylhexanoic acid, 2-methyl-2-propylheptanoic acid, 2-butyl-2-methyloctanoic acid, 2-hexyl-2-methyldecanoic acid, 2-methyl-2-octyldodecanoic acid, 2-decyl-2-methyltetradecanoic acid, 2-dodecyl-2-methylhexadecanoic acid, 2-methyl-2-tetradecyl octadecanoic acid, 2-hexadecyl-2-methyleicosanoic acid, and 2-methyl-2-octadecyldidodecanoic acid, respectively.
Non-limiting examples of neo-acids that are obtainable by the above-described process and useful in the process of the present invention for making a neo-alcohol product include: 2-ethyl-2-methylhexanoic acid; 2-methyl-2-propylheptanoic acid; 2-butyl-2-methyloctanoic acid; 2-methyl-2-pentylnonanoic acid; 2-hexyl-2-methyldecanoic acid; 2-heptyl-2-methylundecanoic acid; 2-methyl-2-octyldodecanoic acid; 2-decyl-2-methyltetradecanoic acid; 2-dodecyl-2-methylhexadecanoic acid; 2-methyl-2-tetradecyl octadecanoic acid; and 2-methyl-2-hexadecyleicosanoic acid.
Co-pending, commonly assigned U.S. provisional patent application serial No. 62/565,560 (entitled "Neo-acids and Process for Making the Same", filed date 2017, 9/29), the contents of which are incorporated herein by reference in their entirety, discloses Neo-acids suitable for use in the Process of the present invention for the preparation of Neo-alcohols and a Process for the preparation of Neo-acids.
Reducing neo-acid product to produce neo-alcohol product
Reduction of the neo-acid having formula (F-II) produces the novel alcohol of the present invention having formula (F-I). The reduction of the carboxylic acid can be carried out in a number of known ways by contacting the acid with a reducing agent under reducing conditions. Among these, mention may be made of hydrogenation in the presence of a hydrogenation catalyst, or contact with other reducing agents in solution or dispersion.
The hydrogenation of the neo-acid is desirably carried out by contacting the neo-acid with a hydrogen atmosphere in the presence of a hydrogenation catalyst comprising a hydrogenation metal. The absolute hydrogen partial pressure of the hydrogen atmosphere may be in the range of, for example, p1 to p2 megapascals ("MPa"), where p1 and p2 may independently be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 2.0, 4.0, 5.0, 6.0, 8.0, 10, 15, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900, or even 1000, as long as p1< p 2. Preferably p2 ≦ 100. More preferably p2 ≦ 10. The hydrogenation metal may be selected from the group consisting of Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, and combinations thereof. The hydrogenation metal may be supported on an inorganic support such as silica, alumina, and the like. One of ordinary skill in the art can select a suitable reaction temperature to achieve reduction of the neo-acid to the neo-alcohol with the desired conversion of the neo-acid and the desired selectivity to the neo-alcohol.
Other common reducing agents that may be used to convert the neo-acids of the present invention to neo-alcohols include, but are not limited to: sodium borohydride (NaBH)4) (ii) a Lithium aluminum hydride; dithionate; a thiosulfate salt; hydrazine; NaBH4And a mixture of iodine; NaBH4And H2SO4A mixture of (a); NaBH4Catechol and CF3A mixture of COOH; NaBH4And ZnCl2And NaBH4And cyanuric chloride. A stoichiometric amount of reducing agent can be used to convert substantially all of the neo-acid to the neo-alcohol. It is desirable that the reduction conditions are relatively mild, for example, the reaction temperature is from 0 to 100 ℃, preferably from 0 to 80 ℃, more preferably from 10 to 60 ℃, and still more preferably from 20 to 50 ℃, and the reaction time is from 0.5 to 24 hours, preferably from 0.5 to 20 hours, more preferably from 0.5 to 18 hours, more preferably from 0.5 to 15 hours, still more preferably from 1 to 12 hours, and still more preferably from 1 to 6 hours.
The reduction of the neo-acid can be carried out in the presence or absence of an inert solvent. Non-limiting examples of inert solvents include: benzene, toluene, any xyleneBenzene, ethylbenzene and mixtures thereof; n-pentane and branched isomers thereof, and mixtures thereof; n-hexane and branched isomers thereof, and mixtures thereof; cyclohexane and its saturated isomers, and mixtures thereof; n-heptane and its branched isomers, and mixtures thereof; n-octane and its branched isomers, and mixtures thereof; n-nonane and its branched isomers, and mixtures thereof; n-decane and branched isomers thereof, and mixtures thereof; and mixtures of any of the foregoing;
a solvent; and so on.
The reaction mixture resulting from the reduction reaction may include, among other things, unreacted residual neo-acid, the desired neo-alcohol compound, the catalyst (if used), and the inert solvent (if used). Known methods, such as filtration, solvent extraction, distillation, chromatography, use of adsorbents, and the like, can be employed to obtain a novel alcohol product comprising one or more novel alcohol compounds of the present invention in a desired purity. For example, filtration may be used to separate solid materials, such as hydrogenation catalyst particles, from the liquid. The solid catalyst thus separated can be regenerated and recycled. With alkaline aqueous solution (e.g. NaCO)3，NaHCO3And aqueous solutions of NaOH, etc.) resulting in the formation of metal salts (e.g., NaBH)4) And residual neo-acids are converted to water-soluble salts and when two immiscible phases (water/organic phase) are present in the extraction mixture, the water-soluble salts are distributed in the aqueous phase and the neo-alcohols are distributed in the organic phase. Removal of the organic solvent from the organic phase may yield a crude new alcohol product. The crude neo-alcohol product can be further purified by distillation, washing, extraction, adsorbent, and the like, to obtain a neo-alcohol product comprising one or more neo-alcohol compounds of the present invention having a desired purity. Desirably, the novel alcohol product consists essentially of the novel alcohol compound(s) of the present invention. Preferably, the neo-alcohol product comprises the neo-alcohol compound(s) of the present invention at a concentration of at least 95 weight percent, more preferably at least 96 weight percent, more preferably at least 97 weight percent, even more preferably at least 98 weight percent, even more preferably at least 99 weight percent, based on the total weight of the neo-alcohol product. Superior foodOptionally, the neo-alcohol product consists essentially of a single neo-alcohol of the present invention. More preferably, the neo-alcohol product comprises the single neo-alcohol compounds of the present invention at a concentration of at least 95 weight percent, more preferably at least 96 weight percent, more preferably at least 97 weight percent, even more preferably at least 98 weight percent, even more preferably at least 99 weight percent, based on the total weight of the neo-alcohol product.
The novel alcohol products produced by the process of the present invention may be desirably used in a variety of applications. One contemplated application is as an additive component in lubricating oil compositions. Other examples of applications include: detergents, such as household laundry detergents and soaps; personal care products such as lotions, hair care products, and the like; pharmaceutical products, such as pharmaceutical syrups; industrial products, such as degreasers and industrial cleaners; a pesticide; a herbicide; and so on. The novel alcohol products produced by the process of the present invention are also useful as plasticizers in plastics.
Examples of techniques that can be used to characterize the above-described neoalcohols include, but are not limited to, analytical gas chromatography, nuclear magnetic resonance, thermogravimetric analysis (TGA), inductively coupled plasma mass spectrometry, Differential Scanning Calorimetry (DSC), volatility, and viscosity measurements.
The invention is further illustrated by the following non-limiting examples.
Examples
In the examples below, the kinematic viscosity at 100 ℃ ("KV 100") and the kinematic viscosity at 40 ℃ ("KV 40") of the fluids were determined according to ASTM standard D-445; viscosity index ("VI") is determined according to ASTM standard D-2270; and Noack volatility ("NV") was determined using thermogravimetric analysis ("TGA").
Part A: synthesis of 2-methyl-2-octyldodecanoic acid
Example a 1: synthesis of 9-methylenenonadecane
5000g of 1-decene (98.6% of 1-decene, 0.7% of 1-octene, 0.7% of 1-dodecene) was charged into a batch reactor, 50g of a 10% MAO solution was added thereto, and maintained at 80 ℃ for 60 minutes. 450g of catalyst solution (1.4% by weight of biscyclopentadienylzirconium (IV) dichloride dissolved in toluene) are subsequently added over 52 minutes. The reactor was kept at 80 ℃ for 6 hours, then the reaction was cooled and quenched with 10 ml. Gas chromatography showed that the reactor conversion was 74%, the selectivity to dimer was 88% and the selectivity to trimer and heavier materials was 12%.
Thereafter, a filter aid is added to the fluid and filtered to remove solid particles containing Zr and/or Al. The resulting mixture is then flashed to remove residual monomer and distilled to remove heavy products to separate the dimer material. The recovered dimer product was measured as dimer containing the starting olefin at a concentration of 99.5 wt% (determined by GC) and 9-methylenenonadecane at a concentration of 98 mol% (determined by GC)1H NMR measurement).
Example a 2: synthesis of 2-methyl-2-octyldodecanoic acid
To a1 gallon (3.78 liter) autoclave was added 1204g of the dimer product obtained from example B1 above. Then 613g of BF were added with stirring and cooling3A dihydrate. The reactor was then pressurized with CO to 1000 psig. Thereafter a further 330g of anhydrous BF were added3Bubbling into the reactor. The reactor was then pressurized with CO to 2000psig (13.79MPa, gauge) and the reactor temperature was increased to 50 ℃. The reaction was allowed to continue at the same CO pressure and the same temperature for 22 hours. Thereafter, the reactor was depressurized and allowed to cool to 30 ℃.
The reaction mixture was then forced into a 12 liter flask containing 4 liters of water. Nitrogen was bubbled through the mixture for 3 hours to remove residual BF3. The excess water was then drained off. The resulting mixture was then washed seven (7) times with water, using one (1) liter of deionized water each time to remove residual catalyst. The residual water in the resulting mixture was then removed with a rotary evaporator to obtain a crude product.
The total conversion of vinylidene olefin in the carboxylation step was measured (by gas chromatography) to be 90.7%, and the yield of heavy dimer material to vinylidene olefin was measured to be 6.6%, and thus the yield to the desired neo-acid product was 84.1%.
The crude product is then batch distilled to remove lights (unreacted vinylidene olefin) and heavies to obtain the final neo-acid product. Gas chromatography of the final neo-acid product showed that the neo-acid concentration was about 98% and the concentration of the heavy components was about 2%.
The final neo-acid product was measured to be 8.51cSt for KV100 and 64.0cSt for KV 40.
13The C-NMR spectrum showed that the final neo-acid product contained 2-methyl-2-octyldodecanoic acid with a purity of 98.1 wt%.
And part B: synthesis of 2-methyl-2-octyldodecane-1-ol
In a 500ml four-necked round bottom flask, 7.0g of NaBH was added with stirring4Dissolved in 75ml of anhydrous THF. 30g of 2-methyl-2-octyldodecanoic acid (MW 326.57, 0.092mol, prepared according to part A of the above inventive example) in 50ml of THF solution are then added dropwise very slowly over a period of 2 hours. The mixture was stirred for 1 hour until hydrogen evaluation was stopped. A solution of iodine (18.7 grams) in 40ml THF was added dropwise to the stirred mixture over about 2.5 hours at 10 to 20 ℃, causing evolution of hydrogen gas, a significant exotherm and disappearance of the red color of the iodine. The solution was stirred overnight and heated to reflux for 1 hour. About 50ml of THF were then distilled off from the reaction mixture. To the cooled suspension from the distillation residue 100ml cyclohexane and 10% NaOH solution were added. The solution was stirred vigorously until the gas evolution ceased and the precipitated material disappeared. The mixture was then transferred to a separatory funnel. The cyclohexane solution thus separated was used with 50ml of 10% NH3The solution was washed three times with 50ml 15% NaHSO4The aqueous solution was washed once and once with brine solution. Evaporation of the solvent gave crude 2-methyl-2-octyldodecane-1-ol. Further distillation under vacuum gave 25 g(87%) of the final purified product of 2-methyl-2-octyldodecane-1-ol. The final purified product was confirmed by IR and NMR spectra. IR (cm)-1):3347,2925,2852,1467,1377,1036,721.1H NMR(CDCl3):δ3.25(s,2H,)HO-CH2-),1.25-1.12(m,33H,-CH2-),0.81-0.74(m,9H,CH3)。13C NMR(CDCl3):69.85,37.25,36.43,31.95,30.69,29.72,29.68,29.38,23.43,22.89.4.09。
Claims (25)
1. A compound having the following formula (F-1):
wherein R is1And R2The same or different, each independently a hydrocarbyl group containing at least two (2) carbon atoms.
2. The compound of claim 1, wherein R1And R2Each independently is C2To C30Linear or branched alkyl groups.
3. A compound according to claim 1 or claim 2, wherein R is1And R2At least one of which is a linear alkyl group.
4. The compound of claim 2, wherein R1And R2At least one of which is selected from the group consisting of ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-docosyl, n-tetracosyl, n-hexacosyl and n-octacosyl.
5. The compound of claim 4, wherein R1And R2At least one of which is selected from the group consisting of n-butyl, n-hexyl, n-octyl, n-decyl and n-dodecyl.
6. The preceding claimsA compound of any one of claims, wherein R1And R2Each independently is a linear alkyl group.
7. The compound of claim 6, wherein R1And R2Independently selected from ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-docosyl, n-tetracosyl, n-hexacosyl and n-octacosyl.
8. The compound of any one of the preceding claims 1-5, wherein R1And R2At least one of which is a branched alkyl group.
9. The compound of claim 7, wherein R1And R2At least one of which is selected from the group consisting of ethylhexyl, 2-propylheptyl, 2-butyloctyl, and 3, 5-dimethyloctyl.
10. A compound according to any one of the preceding claims wherein R is1And R2Are the same.
11. The compound of claim 10 selected from the group consisting of:
2-ethyl-2-methylhexan-1-ol;
2-methyl-2-propylhept-1-ol;
2-butyl-2-methyloctan-1-ol;
2-hexyl-2-methyldecan-1-ol;
2-methyl-2-octyldodecan-1-ol;
2-decyl-2-methyltetradecan-1-ol;
2-dodecyl-2-methylhexadecyl-1-ol;
2-methyl-2-tetradecyl octadecan-1-ol;
2-hexadecyl-2-methyl eicosan-1-ol;
2-methyl-2-octadecyldiehandol-1-ol;
2-eicosyl-2-methyltetracosan-1-ol;
2-docosyl-2-methyl hexacosanol-1-ol;
2-methyl-2-tetracosanyl octacosan-1-ol; and
2-hexacosanyl-2-methyltranstriacontan-1-ol.
12. Use of a compound according to any one of the preceding claims in at least one of:
(i) as an additive component in a lubricating oil composition;
(ii) as a surfactant in detergent compositions;
(iii) as a surfactant and/or solvent in a pharmaceutical composition;
(iv) as a surfactant and/or solvent in the pesticide;
(v) as surfactants and/or solvents in herbicides; and
(vi) as a plasticizer in plastic materials.
13. A process for preparing a novel alcohol product comprising a novel alcohol compound having the following formula (F-1):
wherein R is1And R2Each independently a hydrocarbyl group containing at least two (2) carbon atoms, the process comprising:
(I) providing a neo-acid product comprising a neo-acid compound having the following formula (F-II):
(II) contacting the neo-acid product with a reducing agent under reducing conditions.
14. The process of claim 13, wherein in step (II), the reducing agent is hydrogen and the reducing conditions comprise the presence of a hydrogenation catalyst.
15. The method of claim 14, wherein in step (II), the reducing agent is selected from the group consisting of: sodium borohydride (NaBH)4) (ii) a Lithium aluminum hydride; dithionate; a thiosulfate salt; hydrazine; NaBH4And a mixture of iodine; NaBH4And H2SO4A mixture of (a); NaBH4Catechol and CF3A mixture of COOH; NaBH4And ZnCl2A mixture of (a); and NaBH4And cyanuric chloride.
16. The method of claim 15, wherein the reducing conditions include a temperature in the range of 10 to 60 ℃ and a reaction time in the range of 0.5 to 24 hours.
17. The method of any one of claims 13-16, wherein R1And R2Each independently is C2To C30A linear alkyl group.
18. The method of any one of claims 13 to 17, wherein R1And R2At least one of which is selected from the group consisting of ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, n-docosyl, n-tetracosyl, n-hexacosyl and n-octacosyl.
19. The method of claim 18, wherein R1And R2At least one of which is selected from the group consisting of n-butyl, n-hexyl, n-octyl, n-decyl and n-dodecyl.
20. The method of any one of claims 13 to 19, wherein R1And R2Each independently is a linear alkyl group.
21. The method of any one of claims 13 to 20, wherein R1And R2Are the same.
22. The method of any one of claims 13 to 21, wherein step (I) comprises:
(Ia) providing a vinylidene olefin feed comprising a vinylidene olefin having the following formula (F-III):
(Ib) contacting a vinylidene olefin with carbon monoxide in a reactor in the presence of an acid catalyst at a carbon monoxide partial pressure of at least 1.0MPa to obtain a reaction mixture;
(Ic) contacting the reaction mixture with water to obtain an acid product mixture; and
(Id) obtaining at least a portion of the neo-acid product from the acid product mixture.
23. The method of claim 22, wherein step (Ia) comprises the steps of:
(Ia.1) providing a monomer feed comprising a terminal olefin having the following formula (F-IV):
R1-CH＝CH2(F-IV)；R2-CH＝CH2(F-V); wherein R is1And R2Corresponding to R in the formula (F-1)1And R2；
(ia.2) oligomerizing a monomer feed in an oligomerization reactor in the presence of a catalyst system comprising a metallocene compound to obtain an oligomerization product mixture; and
(Ia.3) obtaining at least a portion of the vinylidene olefin feed from the oligomerization product mixture.
24. The process of claim 23, wherein step (ia.2) is carried out in a continuous process.
25. The process of any one of claims 13 to 24, wherein in step (I), the neo-acid compound is selected from the group consisting of: 2-ethyl-2-methylhexanoic acid; 2-methyl-2-propylheptanoic acid; 2-butyl-2-methyloctanoic acid; 2-methyl-2-pentylnonanoic acid; 2-hexyl-2-methyldecanoic acid; 2-heptyl-2-methylundecanoic acid; 2-methyl-2-octyldodecanoic acid; 2-decyl-2-methyltetradecanoic acid; 2-dodecyl-2-methylhexadecanoic acid; 2-methyl-2-tetradecyl octadecanoic acid; and 2-methyl-2-hexadecyleicosanoic acid.
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| PCT/US2018/041578 WO2019067062A1 (en) | 2017-09-29 | 2018-07-11 | Neo-alcohol compounds, processes for making same and sue thereof |
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| CN115417740B (en) * | 2022-09-01 | 2023-08-29 | 石家庄学院 | Preparation method of (R) -13-methyl heptadecane |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2460182A (en) * | 1943-08-04 | 1949-01-25 | Ag J R Geigy | Basic esters of aliphatic tertiary carboxylic acids |
| US3059007A (en) * | 1960-01-15 | 1962-10-16 | Shell Oil Co | Production of carboxylic acids |
| US3910963A (en) * | 1972-09-13 | 1975-10-07 | Agency Ind Science Techn | Method for manufacture of carboxylic acids or derivatives thereof |
| US4126585A (en) * | 1976-06-11 | 1978-11-21 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | 2-Methyl-2-ethyl-hexanoate ester perfume compositions |
| US4332738A (en) * | 1980-11-24 | 1982-06-01 | Exxon Research & Engineering Co. | Esterification of neo acids by the use of cation exchange resins |
| US4658078A (en) * | 1986-08-15 | 1987-04-14 | Shell Oil Company | Vinylidene olefin process |
| US5646332A (en) * | 1992-12-17 | 1997-07-08 | Exxon Chemical Patents Inc. | Batch Koch carbonylation process |
| US6239318B1 (en) * | 1998-09-16 | 2001-05-29 | Oxeno Olefinchemie Gmbh | Process for the selective hydrogenation of hydroformylation mixtures |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3836255A1 (en) | 1988-10-25 | 1990-04-26 | Opel Adam Ag | ELECTRIC MOTOR ACTUATOR |
| US20030191032A1 (en) | 2002-01-31 | 2003-10-09 | Deckman Douglas E. | Mixed TBN detergents and lubricating oil compositions containing such detergents |
| US8048833B2 (en) | 2007-08-17 | 2011-11-01 | Exxonmobil Research And Engineering Company | Catalytic antioxidants |
| US9422497B2 (en) | 2012-09-21 | 2016-08-23 | Exxonmobil Research And Engineering Company | Synthetic lubricant basestocks and methods of preparation thereof |
| US9458403B2 (en) | 2012-09-27 | 2016-10-04 | Exxonmobil Research And Engineering Company | High viscosity, functionalized metallocene polyalphaolefin base stocks and processes for preparing same |
-
2018
- 2018-07-11 WO PCT/US2018/041578 patent/WO2019067062A1/en unknown
- 2018-07-11 CN CN201880073050.9A patent/CN111344271A/en active Pending
- 2018-07-11 EP EP18740988.3A patent/EP3687964A1/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2460182A (en) * | 1943-08-04 | 1949-01-25 | Ag J R Geigy | Basic esters of aliphatic tertiary carboxylic acids |
| US3059007A (en) * | 1960-01-15 | 1962-10-16 | Shell Oil Co | Production of carboxylic acids |
| US3910963A (en) * | 1972-09-13 | 1975-10-07 | Agency Ind Science Techn | Method for manufacture of carboxylic acids or derivatives thereof |
| US4126585A (en) * | 1976-06-11 | 1978-11-21 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | 2-Methyl-2-ethyl-hexanoate ester perfume compositions |
| US4332738A (en) * | 1980-11-24 | 1982-06-01 | Exxon Research & Engineering Co. | Esterification of neo acids by the use of cation exchange resins |
| US4658078A (en) * | 1986-08-15 | 1987-04-14 | Shell Oil Company | Vinylidene olefin process |
| US5646332A (en) * | 1992-12-17 | 1997-07-08 | Exxon Chemical Patents Inc. | Batch Koch carbonylation process |
| US6239318B1 (en) * | 1998-09-16 | 2001-05-29 | Oxeno Olefinchemie Gmbh | Process for the selective hydrogenation of hydroformylation mixtures |
Non-Patent Citations (5)
| Title |
|---|
| AS.BHANU PRASAD等: "Convenient Methods for the Reduction of Amides, Nitriles, Carboxylic Esters, Acids and Hydroboration of Alkenes Using NaBH/I2 System", 《TETRAHEDRON》, vol. 48, no. 22, 31 December 1992 (1992-12-31), XP008122042 * |
| J.V.BHASKAR KANTH等: "Selective Reduction of Carboxylic Acids into Alcohols Using NaBH4 and I2", 《J.ORG.CHEM.》, vol. 56, 31 December 1991 (1991-12-31), pages 1 * |
| 化学工业出版社《化工百科全书》编辑部: "《化工百科全书》", 30 April 1998, 化学工业出版社, pages: 40 * |
| 张学铭等: "《化学小辞典第2版》", 31 August 1994, 科学技术文献出版社, pages: 23 * |
| 罗龙娟等: "中式酱油和日式酱油香气物质的对比研究", 《中国酿造》, no. 5, 31 December 2011 (2011-12-31), pages 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174906A (en) * | 2020-10-28 | 2021-01-05 | 山东兴强化工产业技术研究院有限公司 | Preparation method of intermediate 4, 4-dimethylisoxazol-3-one |
| CN112174906B (en) * | 2020-10-28 | 2023-07-04 | 山东兴强化工产业技术研究院有限公司 | Preparation method of intermediate 4, 4-dimethyl isoxazole-3-one |
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