CN105658776A

CN105658776A - Monoester-based lubricants and methods of making same

Info

Publication number: CN105658776A
Application number: CN201480046323.2A
Authority: CN
Inventors: S·A·埃勒玛丽; S·J·米勒
Original assignee: Chevron USA Inc
Current assignee: Chevron USA Inc
Priority date: 2014-05-15
Filing date: 2014-05-15
Publication date: 2016-06-08
Also published as: WO2015174992A1; CA2918575A1; JP2017515965A; MX2016001758A; EP3143106A4; EP3143106A1

Abstract

Disclosed herein are monoester-based lubricant compositions and methods of making these monoester-based lubricant compositions. The monoester lubricant compositions comprise an isomeric mixture of at least one monoester species having a carbon number ranging from C8 to C40. In some embodiments, the methods for making the monoester-based lubricants utilize a biomass precursor and/or low value Fischer-Tropsch (FT) olefins and/or alcohols to produce high value monoester-based lubricants. In some embodiments, the monoester-based lubricants are derived from FT olefins and fatty acids. The fatty acids can be from a bio-based source (i.e., biomass, renewable source) or can be derived from FT alcohols via oxidation.

Description

Monoesters base lubricating agent and its preparation method

Invention field

The present invention relates to ester-based lubricant, particularly monoesters base lubricating agent and their preparation method.

Background of invention

Ester is used as lubricating oil more than 50 years. They are applied to from the various application of jet engine, refrigerator and engine oil. In fact, ester is synthesis crankcase engine oil the earliest in automotive vehicles applications. But, owing to poly-alpha olefins (PAO) cost is lower and their formula is similar to mineral oil and make ester make way for PAO. But, in complete synthesis machine oil, ester almost always combinationally uses with PAO with by improving oilness to balance the impact that stopping property, interpolation property, solvability, volatility reduction and energy efficiency are improved.

Usually, the polarity of the ester molecule that ester-based lubricant comprises because of it and there is excellent oilness. The polarity ester group of these molecules is attached to the metallic surface of positively charged and generates the protective membrane that can slow down honing. The volatility of this kind of lubricant is lower than conventional lubricant and often has much higher flash-point and much low vapour pressure. Ester lubricant is excellent solvent and dispersion agent, and is easy to dissolve and disperse the degradation by-products of oil. Therefore, they greatly reduce the accumulation of greasy filth. Heat and oxidising process are stable by ester lubricant, but compared with its mineral oil based analogue, ester function group makes microorganism can more efficiently and effectively carry out biological degradation process. But, the preparation of ester is more complicated and may be more expensive than the preparation of its PAO contrast.

In view of above-mentioned viewpoint, the method simply, more efficiently producing ester-based lubricant will be very useful, and particularly this kind of method can utilize renewable raw materials and combine low value Fischer-Tropsch (FT) alkene and alcohol is converted into the ester lubricant of high level.

Invention summary

Broad sense of the present invention relates to monoesters based lubricant composition. The present invention also relates to the method for these lubricant compositions of preparation and other similar lubricant compositions. In some embodiments, the method preparing this kind of monoesters base lubricating agent make use of biomass precursor. In these or other embodiment, lubricant precursor species also can be derived from or derived from fischer-tropsch (FT) reaction product.

In some embodiments, the present invention relates to the lubricant compositions of the isomer mixture comprising at least one monoesters species. The structure of described monoesters species as shown in Figure 2, wherein R₁��R₂And R₃Independently it is selected from alkyl to form the monoesters isomer mixture of total carbon number in 8-40 scope. Therefore, R₁��R₂And R₃It is selected from alkyl and may be the same or different. In one embodiment, lubricant compositions comprises the isomer mixture of the total carbon number of at least one at the monoesters species of 10-24 scope.In another embodiment, total carbon number of monoesters species is in 12-18 scope, and total carbon number of monoesters species is in 12-16 scope in still another embodiment.

In one embodiment, the present invention relates to the method comprised the following steps: (a) by alpha-olefin isomerization to provide the isomer mixture of internal olefin; (b) by the internal olefin epoxidation of step (a) to provide interior epoxide; C () makes the oxirane ring of the epoxide of step (b) open to provide secondary alcohol by reduction method; D () is by the secondary alcohol C of step (c)₂-C₁₈Carboxylic acid carries out esterification to provide the isomer mixture of at least one monoesters species; (e) isomer mixture of at least one monoesters species that viscosity and pour point are suitable as lubricant is separated.

In certain embodiments, alpha-olefin can derived from Fischer-Tropsch process. In these other embodiments, C₂-C₁₈Carboxylic acid can derived from Fischer-Tropsch process or from biologically-derived lipid acid.

In certain embodiments, the present invention relates to the method comprised the following steps: (a) is by isomer mixture that carbon number is that the alpha-olefin of 6-22 or alpha-olefin mixture are isomerizated into internal olefin; B carbon number is that the internal olefin isomer mixture epoxidation of 6-22 is to form the interior epoxide isomer mixture comprising oxirane ring by (); C oxirane ring is opened to form secondary alcohol isomers mixture by () by reduction method; D () is by secondary alcohol isomers mixture C₂-C₁₈Carboxylic acid or its acylated derivatives such as acyl chlorides or acid anhydrides carry out esterification to form the isomer mixture of at least one monoesters species of interior (second month in a season); (e) isomer mixture of at least one monoesters species that viscosity and pour point are suitable as lubricant is separated. Carboxylic acid can derived from Fischer-Tropsch process or from biologically-derived lipid acid. Carboxylic acid or its acylated derivatives are if acyl chlorides or anhydride derivable are from Fischer-Tropsch process or from biologically-derived lipid acid. Described alpha-olefin can derived from Fischer-Tropsch process.

In other embodiments, the present invention relates to the method comprised the following steps: (a) by carbon number be 6-22 multiple alpha-olefin isomerization to provide the isomer mixture of multiple internal olefin; (b) by internal olefin isomer mixture epoxidation to form the isomer mixture of multiple interior epoxide; C interior epoxide isomer mixture is converted into the isomer mixture of multiple secondary alcohol by (); D () is by secondary alcohol isomers mixture C₂-C₁₈Esterifying agent carries out esterification to form the isomer mixture of multiple interior monoesters; (e) isomer mixture of the multiple monoesters species that viscosity and pour point are suitable as lubricant is separated. In certain embodiments, esterifying agent can be carboxylic acid or its acylated derivatives such as acyl chlorides or acid anhydrides, derived from Fischer-Tropsch process or from biologically-derived lipid acid. In these and other embodiment, alpha-olefin can derived from Fischer-Tropsch process.

Alkene disclosed herein can be become the alpha-olefin prepared by liquid technique (GTL) treating process, petrochemical process, plastic waste pyrolysis and other process by gas. By alpha-olefin isomerization to provide the isomer mixture of internal olefin, and this internal olefin isomer mixture is changed into monoesters. Use comprises silicoaluminophosphamolecular molecular sieve such as SAPO-39, with middle hole aluminium silicone zeolite such as the double bond isomerizing catalyst of SSZ-32 and ZSM-23, alpha-olefin isomerization is become internal olefin.

The monoesters prepared from internal olefin is isomer mixture and has excellent oxidation and hydrocracking stability. This kind of isomer mixture of these monoesters also has desired cold property, such as low cloud point and pour point. This causes because there is monoesters isomer mixture suppressing crystal formation.

List the feature of the present invention above quite widely, so that the detailed description that next the present invention may be better understood.The other feature and advantage of the present invention will be described below, and forms the theme of the claims in the present invention.

Brief description

For the present invention and advantage thereof are had more complete understanding, carry out now following description by reference to the accompanying drawings as ginseng

Fig. 1 illustrates the schema of the method preparing monoesters based lubricant composition according to some scheme of the present invention.

Fig. 2 (A) shows the general formula of monoesters, and Fig. 2 (B) shows the pungent ester of caproic acid and Fig. 2 (C) shows caproic acid ester in the last of the ten Heavenly stems, and according to some scheme of the present invention, this is two exemplary monoesters based mixtures being suitable as lubricant.

Fig. 3 (scheme 1) illustrates the chemical flowsheet that alpha-olefin is changed into internal olefin.

Fig. 4 (scheme 2) is the chemical flowsheet illustrating the epoxidation step of embodiment 1 in monoesters preparation process.

Fig. 5 (scheme 3) illustrates epoxide open loop (reduction) in monoesters preparation process to generate the chemical flowsheet of the step of embodiment 2 alcohol.

Fig. 6 (scheme 4) illustrates that octanol caproyl chloride carries out esterification and carrys out the pungent ester of synthesizing hexanoic acid.

Detailed Description Of The Invention

Introduction

The present invention relates to the monoesters based lubricant composition comprising at least one monoesters species isomer mixture. The present invention also relates to the method for these and other similar lubricant compositions of preparation. In some embodiments, the method preparing this kind of monoesters base lubricating agent make use of the monoesters base lubricating agent that biomass precursor and/or low value fischer-tropsch (FT) alkene and/or alcohol carry out production high level. In some embodiments, such monoesters base lubricating agent is derived from FT alkene and fat (carboxylic) acid. In these or other embodiment, lipid acid can come from bio-based source (i.e. biomass, renewable source) or can derived from the FT alcohol through oxidizing reaction.

Owing to biological lubricants and biofuel rise gradually, becoming hot topic in the many fields of petroleum industry, when preparing these lubricants above-mentioned, use biomass can be attractive from some different angles. In the monoesters base lubricating agent of preparation the present invention, biomass economy reaches to a certain degree, therefore such lubricant is considered as biological lubricants.

Definition

" lubricant " defined herein is introduced between two translational surfaces with the material (being generally fluid in the operating condition) of the frictional force that reduces between them and abrasion. Base oil as automotive engine oil is divided into mineral oil (I, II and Group III) or synthetic oil (IV and V class) usually by American Petroleum Institute (API). See American Petroleum Institute (API) (API) publication numbering 1509.

" pour point " defined herein represents the minimum temperature that fluid can pour out or flow. For example, see ASTM international standard testing method D5950-96, D6892-03 and D97.

" cloud point " defined herein represents makes fluid start the temperature being separated owing to forming crystal. For example, see ASTM international standard testing method D5773-95, D2500, D5551 and D5771.

Oxidizer BN alleged by herein is the test (R.W.Dornte " OxidationofWhiteOils ", IndustrialandEngineeringChemistry, Vol.28, p26,1936) measuring oxidation-resistance in Dornte-type oxygen absorption equipment. Under normal circumstances, test conditions is the 340 pure oxygen of next normal atmosphere, absorbs 1000mlO with 100g oil₂Hours used is reported the result. In oxidizer BN tests, every 100g oil uses 0.8ml catalyzer, and oil comprises catalyzer bag. Catalyzer is soluble metal-naphthenate mixture, simulates the average metal analysis value of crankcase oils used. Additive-package is that every 100g oil is containing the two many propylidene phenyl zinc dithiophosphate of 80mmol.Oxidizer BN is the response measuring lubricating oil in simulation application. The time length of numerical value height or absorption 1 liter of oxygen represents that oxidative stability is good.

" centistoke ", is abbreviated as " cSt ", is the unit of fluid (such as lubricant) kinematic viscosity, and wherein 1 centistoke equals 1 millimeter squared per second (1cSt=1mm²/ s). For example, see ASTM standard guide and testing method D2270-04, D445-06, D6074 and D2983.

" alkyl " is the straight chain containing 1-40 carbon atom or the univalence hydrocarbyl of branching. The example of alkyl comprises methyl, ethyl, n-propyl, normal-butyl, sec.-propyl, the tertiary butyl, own base, octyl group and analogue. As defined herein, R₁��R₂And R₃Independently selected from alkyl, thus R₁��R₂And R₃It can be identical or different alkyl.

Referring to alkyl about molecule described herein and/or molecule fragment " Rn ", wherein " n " is that index, molecule and/or molecule fragment can be straight chain and/or branching. As defined herein, what " Cn " described is hydrocarbon molecule or fragment (such as alkyl), and wherein " n " is integer, and " n " represents the carbonatoms in this fragment or molecule.

Prefix used herein " biology " refers to relevant with the renewable resources of biogenetic derivation, such as, be generally the resource except fossil oil.

Term used herein " internal olefin " refers to the alkene (i.e. alkene) with non-end position carbon-carbon double bond (C=C). It is different from " alpha-olefin " with end position carbon-carbon double bond.

Term used herein " isomer " and " isomer mixture " comprise there is identical chemical formula but atomic arrangement different compound. Therefore, the isomer mixture of monoesters species comprises the compound with identical chemical formula, and therefore its carbon number is identical, but ester moiety is connected in the different positions of carbochain and carbochain and has different branching.

Term used herein " isomer mixture " is meant to comprise the composition more than a kind of isomer of monoesters species. " monoesters species " are the monoesters of single carbon number. The isomer of monoesters species has identical chemical formula, and therefore its carbon number is identical, but ester moiety is connected in the different positions of carbochain and carbochain and has different branching. Such as, the isomer mixture of single monoesters species comprises Hecogenin and isomer thereof (ester moiety of isomer is connected in the different positions of carbochain and carbochain has different branching).

" isomer mixtures of at least one monoesters species " optionally comprise the isomer more than a kind of monoesters. Thus, isomer mixture comprises more than one (namely two or more) isomer of single monoesters species, it is also possible to comprise the isomer more than a kind of (namely two or more plant) difference monoesters species. Different monoesters species have different chemical formula, and therefore carbon number is different. Such as, the isomer mixture of at least one monoesters species comprises the own ester of Hecogenin and isomer and capric acid thereof and isomer thereof (ester moiety of isomer is connected in the different positions of carbochain and carbochain has different branching).

These isomer mixtures disclosed herein and single monoester compound are completely different.

Monoesters lubricant compositions

In some embodiments, the present invention relates to the lubricant compositions of the isomer mixture comprising at least one monoesters species. The structure of described monoesters species as shown in Figure 2, wherein R₁��R₂And R₃Independently it is selected from alkyl to form the monoesters isomer mixture of total carbon number in 8-40 scope. Therefore, R₁��R₂And R₃Independently it is selected from alkyl and may be the same or different.In one embodiment, lubricant compositions comprises the isomer mixture of the total carbon number of at least one at the monoesters species of 10-24 scope. In another embodiment, total carbon number of the isomer mixture of at least one monoesters species is in 12-18 scope, and in still another embodiment, total carbon number of the isomer mixture of at least one monoesters species is in-12-16 scope.

In one embodiment, R₁And R₂Derived from isomer mixture and the R of alkene₃Derived from carboxylic acid. In certain embodiments, in the synthesis of monoesters species, total carbon number range of used source alkene is C₆-C₂₂In synthesizing with monoesters species, used source carboxylic acid (provides R₃) total carbon number range be C₂-C₁₈��

As described herein, total carbon number of the isomer mixture of at least one monoesters obtained is in 8-40 scope. As described herein, this isomer mixture can comprise the isomer of a kind of monoesters and the isomer of multiple monoesters. R₁��R₂And R₃Independently it is selected from alkyl to provide described monoesters species. In one embodiment, total carbon number of the isomer mixture of at least one monoesters species is in 10-24 scope. In another embodiment, total carbon number of the isomer mixture of at least one monoesters species is in 12-18 scope. In an also embodiment, total carbon number of the isomer mixture of at least one monoesters species is in 12-16 scope.

For above-mentioned monoesters species, R₁��R₂And R₃Selection can defer to the arbitrary or whole of several standards. Such as, in some embodiments, selected R₁��R₂And R₃100 DEG C of kinematic viscosity of monoesters composition should be made generally at 0.5-2 centistoke. In some or other embodiment, selected R₁��R₂And R₃₃The pour point of gained lubricant should be made to be-20 DEG C or lower. In certain embodiments, the pour point of gained lubricant is-20 DEG C to-60 DEG C or lower. The pour point of monoesters species described herein can be-20 DEG C or lower and in certain embodiments for-60 DEG C or lower. In some embodiments, selected R₁��R₂And R₃The oxidizer BN value that should make gained lubricant is about 25-about 65 hours.

In some embodiments, selected R₁And R₂There is the merging carbon number (i.e. total carbon number) of 6-22. In other embodiments, selected R₁And R₂Provide C₄-C₁₄Merging carbon number. In other embodiments, selected R₁And R₂Provide C₄-C₈Merging carbon number. In these or other embodiment, selected R₃Carbon number be C₂-C₁₈. In certain embodiments, selected R₃Carbon number be C₅-C₁₄Or C₅-C₁₀. According to different embodiments, the monoesters species obtained like this can have the molecular mass of 144-592 atomic mass unit (a.m.u.).

In some embodiments, above-mentioned composition is substantially uniform with regard to its monoesters composition, therefore mainly comprises the isomer of a kind of monoesters. In other embodiments, monoesters component comprises multiple (i.e. mixture) monoesters species, and comprises the isomer of multiple monoesters equally. When composition comprises the isomer of multiple monoesters, composition comprises the isomer that two or more plant monoesters species. In some embodiments, composition comprises the isomer of 1-100 kind monoesters. In some embodiments, composition comprises the isomer of 1-70 kind monoesters. In other embodiments, composition comprises the isomer of 1-50 kind monoesters. In other embodiments, composition comprises the isomer of 1-20 kind monoesters. In some other embodiment, composition comprises the isomer of 1-10 kind monoesters.

In some embodiments, monoesters based lubricant composition comprises derived from C₆-C₂₂Alkene and C₂-C₁₈The isomer mixture of at least one monoesters species of carboxylic acid.Generally speaking, monoesters species are by being undertaken reacting making by the carboxylic acid of-OH base (secondary alcohol) from different carbon number. The species of monoesters also carry out esterification by the carboxylic acid of secondary alcohol and same carbon number to be prepared.

In some above-mentioned embodiments, preparing the alkene that precursor secondary alcohol uses can be one of following alkene: own alkene, heptene, octene, nonene, decene, undecylene, dodecylene, 13 carbenes, 14 carbenes, 15 carbenes, cetene, heptadecene, 18 carbenes, 19 carbenes, eicosylene, heneicosene and two dodecylenes or their mixture.

In embodiments described in some, prepare in monoesters species the carboxylic acid used and it is selected from propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad, n-nonanoic acid, capric acid, undecanoic acid, dodecylic acid, tridecanoic acid, tetradecanoic acid, pentadecylic acid, hexadecanoic acid, octadecanoic acid or their mixture.

In some above-mentioned embodiments, monoesters based lubricant composition comprises the isomer mixture that at least one is selected from following monoesters species: n-hexyl propionate and isomer, n-hexyl butyrate and isomer, hexyl hexanoate and isomer, Hecogenin and isomer, the own ester of capric acid and isomer, lauric acid hexyl ester and isomer, the own ester of palmitinic acid and isomer, the own ester of Palmitic acid and isomer, hexyl stearate and isomer, n-octyl propionate and isomer, n-octyl butyrate and isomer, the pungent ester of caproic acid and isomer, octyl octanoate and isomer, the pungent ester of capric acid and isomer, octyl laurate and isomer, Wickenol 155 and isomer, the pungent ester of Palmitic acid and isomer, octyl stearate and isomer, n-decyl propionate and isomer, n-decyl butyrate and isomer, caproic acid ester in the last of the ten Heavenly stems and isomer, sad last of the ten Heavenly stems ester and isomer, n-decyl decylate and isomer, lauric acid ester in the last of the ten Heavenly stems and isomer, palmitinic acid ester in the last of the ten Heavenly stems and isomer, Palmitic acid ester in the last of the ten Heavenly stems and isomer, stearic acid ester in the last of the ten Heavenly stems and isomer, propionic acid dodecane ester and isomer, butyric acid dodecane ester and isomer, caproic acid dodecane ester and isomer, sad dodecane ester and isomer, capric acid dodecane ester and isomer, lauric acid dodecane ester and isomer, palmitinic acid dodecane ester and isomer, Palmitic acid dodecane ester and isomer, stearic acid dodecane ester and isomer, propionic acid tetradecane ester and isomer, butyric acid tetradecane ester and isomer, caproic acid tetradecane ester and isomer, sad tetradecane ester and isomer, capric acid tetradecane ester and isomer, lauric acid tetradecane ester and isomer, palmitinic acid tetradecane ester and isomer, Palmitic acid tetradecane ester and isomer, stearic acid tetradecane ester and isomer, propionic acid n-Hexadecane ester and isomer, butyric acid n-Hexadecane ester and isomer, caproic acid n-Hexadecane ester and isomer, cetyl ester and isomer, capric acid n-Hexadecane ester and isomer, lauric acid n-Hexadecane ester and isomer, cetyl palmitate and isomer, Palmitic acid n-Hexadecane ester and isomer, cetyl stearic and isomer, propionic acid octadecane ester and isomer, butyric acid octadecane ester and isomer, caproic acid octadecane ester and isomer, sad octadecane ester and isomer, capric acid octadecane ester and isomer, lauric acid octadecane ester and isomer, palmitinic acid octadecane ester and isomer, Palmitic acid octadecane ester and isomer, stearic stearolactone and isomer, propionic acid eicosane ester and isomer, butyric acid eicosane ester and isomer, two caproic acid ten alkane ester and isomer, sad eicosane ester and isomer, capric acid eicosane ester and isomer, lauric acid eicosane ester and isomer, palmitinic acid eicosane ester and isomer, Palmitic acid eicosane ester and isomer, stearic acid eicosane ester and isomer, propionic acid docosane ester and isomer, butyric acid docosane ester and isomer, caproic acid docosane ester and isomer, sad docosane ester and isomer, capric acid docosane ester and isomer, lauric acid docosane ester and isomer, palmitinic acid docosane ester and isomer, Palmitic acid docosane ester and isomer, stearic acid docosane ester and isomer and their mixture.

In some embodiments, monoesters based lubricating oil composition comprises the base oil being selected from I class oil, II class oil, Group III oil and mixture thereof further.

It is noted that above-mentioned ester and composition itself thereof are unlikely used as lubricant in the application of majority, but it is typically used as blending stock. Therefore, the ester with higher pour point can be used as the blending of lubricating oils material with other, because they are easily molten in hydrocarbon and alkyl oil.

When adjusting mixed with base oil, described monoesters based lubricant composition can comprise the isomer mixture of about 5-50wt% at least one monoesters species.

Prepare the method for monoesters lubricant

As mentioned above, it is necessary, the present invention relates to the method for the lubricant compositions preparing the above-mentioned isomer mixture comprising at least one monoesters species in addition.

With reference to the schema shown in figure 1, in some embodiments, prepare the above-mentioned method with the monoesters species of typical lube base oil viscosity with pour point to comprise the following steps: alpha-olefin isomerization is become the isomer mixture of internal olefin by (step 101); The internal olefin isomer mixture that carbon number is 6 to 22 is carried out epoxidation to form epoxide or epoxide mixture by (step 102); (step 103) opens oxirane ring to form corresponding single secondary alcohol by reduction method; (step 104) is by secondary alcohol C₂-C₁₈Carboxylic acid carries out esterification (namely through esterification treatment) to form the isomer mixture of interior monoesters species. Usually, the lubricant compositions comprising this kind of monoesters species has the viscosity of 0.5-2 centistoke scope at 100 DEG C of temperature.

In some embodiments, the monoesters species formed can be homogeneity substantially, and thus composition mainly comprises the isomer of a kind of monoesters species. In other embodiments, the monoesters species formed comprise different monoesters species (i.e. mixture) thus composition comprise the isomer that two or more plant monoesters. In some embodiments, composition comprises the isomer of 1-100 kind monoesters. In other embodiments, composition comprises the isomer of 1-20 kind monoesters.

In the embodiment of some aforesaid methods, alkene used is the reaction product of Fischer-Tropsch process. In these or other embodiment, carboxylic acid can be can be biologically-derived lipid acid derived from the alcohol produced by Fischer-Tropsch process and/or carboxylic acid.

In some embodiments, alkene is alpha-olefin (that is, chain end has the alkene of double bond). In these embodiments, it usually needs by isomerisation of olefin so that double bond internalization. Such isomerization reaction generally to be used and include but not limited to that the catalyzer of crystal aluminosilicate and analogous material and aluminate or phosphate carries out catalysis. For example, see United States Patent (USP) 2537283,3211801,3270085,3327014,3304343,3448164,4593146,3723564 and 6281404, what United States Patent (USP) 6281404 was claimed is haveThe crystalline aluminium phosphate base catalyzer in the one dimension hole in aperture.

As the example of this above-mentioned isomerization method and as shown in scheme 1 (Fig. 3), alhpa olefin (alpha-olefin) can be isomerizated into corresponding internal olefin. In some embodiments, these alpha-olefins can derived from Fischer-Tropsch process. Then these internal olefins are carried out epoxidation, as shown in scheme 2 (Fig. 4). Then by the reduction reaction of epoxide ring, epoxide is converted into corresponding single secondary alcohol, then by carrying out esterification (that is, two-ester) with suitable carboxylic acid or its acylated derivatives.Generally alpha-olefin must be converted into internal olefin, because the monoesters of alpha-olefin, especially short chain alpha-olefin solid or wax often. Alpha-olefin " internalization " is then converted in the ester that monoesters functional group makes to produce and introduces side chain along chain, because this reducing the symmetry of molecule and be minimized the pour point of expection product. Ester internalization also can be improved oxidation and stability to hydrolysis. Lactone presents wondrous hydrolysis and oxidative stability, is greatly better than those terminal ester. Ester internalization makes its space steric hindrance bigger, oxidation and stability to hydrolysis can be contributed to.

The ester group with polar character will improve the viscosity of final product further. The branching introduced by the internalization of ester group will strengthen low-temperature performance such as pour point and cloud point. Viscosity can be improved by increasing the carbon number of internal olefin or esterification acid used.

For epoxidation reaction (i.e. epoxidation step), in some embodiments, can by above-mentioned alkene (preferred internal olefin) and superoxide (such as H₂O₂) or peroxy acid (such as Peracetic Acid) reaction generate epoxide. For example, see D.Swern is at OrganicPeroxidesVol.II (Wiley-Interscience, NewYork, 1971) 355-533 page and B.Plesnicar are at OrganicChemistry, PartC (W.Trahanovsky (ed.), AcademicPress, NewYork1978) Oxidation 221-253 page described in. By highly selective reagent such as perosmic anhydride (M.Schroder, Chem.Rev.vol.80, p.187,1980) and potassium permanganate (Sheldon and Kochi is at Metal-CatalyzedOxidationofOrganicCompounds,, AcademicPress, NewYork, 1981, described in 162-171 and 294-296 page) alkene can be converted into corresponding glycol efficiently.

Epoxide open loop being become to the step of corresponding single secondary alcohol, epoxide ring was also originally completed (such as scheme 3, namely shown in Fig. 5) by this step with the use of metal hydride reduction method or precious metal catalyst hydrogenation method. These two methods are by being very effective in secondary alcohol needed for inner ring Preparation.

For esterif iotacation step (esterification), general acid carrys out the esterification (such as scheme 4, namely shown in Fig. 6) of catalytic alcohol and carboxylic acid. The acid being suitable for esterification includes but not limited to sulfuric acid (Munch-Peterson, Org.Synth., V, p.762,1973), sulfonic acid (AllenandSprangler, OrgSynth., III, p.203,1955), hydrochloric acid (Elieletal., OrgSynth., IV, p.169,1963) and phosphoric acid (etc.). In some embodiments, first carboxylic acid used in this step is converted into acyl chlorides (such as by thionyl chloride or PCl₃). Or can directly use acyl chlorides. When use acyl chlorides time, it is not necessary to acid catalyst and generally can add alkali such as pyridine, 4-dimethylaminopyridine (DMAP) or triethylamine (TEA)) with generate HCl reaction. When using pyridine or DMAP, it is believed that the acylated intermediate that these amine more easily react by generating also plays catalyst action. For example, see Fershetal., J.Am.Chem.Soc., vol.92, pp.5432-5442,1970; AndHofleetal., Angew.Chem.Int.Ed.Engl., vol.17, p.569,1978.

No matter the source of alkene is how, in some embodiments, and carboxylic acid derivatives authigenic material used in aforesaid method. Such as, in certain embodiments, this relates to the extraction of some oil carrying out authigenic material (tri-glyceride) components and forms the hydrolysis of the tri-glyceride of oil ingredient thus form free carboxy acid.In some embodiments, carboxylic acid derivatives is from Fischer-Tropsch process.

Adopt according to the synthetic schemes shown by scheme 1 (Fig. 3), scheme 2 (Fig. 4), scheme 3 (Fig. 5) and scheme 4 (Fig. 6), by the acylation reaction of octanol intermediate and caproyl chloride and decanoyl chloride, interior octene mixture is separately converted to the mixture of corresponding interior monoester derivates and the pungent ester of caproic acid and the pungent ester of capric acid. The following examples illustrate in more detail present method. The pungent ester of caproic acid and the last of the ten Heavenly stems ester be specially adapted in drilling fluid composition.

Work-around solution

The work-around solution (i.e. alternate embodiment) of above-mentioned lubricant compositions includes but not limited to utilize the mixture of different structure alkene and have the mixture of different carbon number. This can cause the isomer mixture having multiple monoesters species in product composition

The work-around solution of aforesaid method includes but not limited to use the carboxylic acid obtained from FT alcohol by oxidizing reaction.

Embodiment

Following examples are provided to show specific embodiment of the invention scheme. The technician of this area is understood that disclosed method only represents illustrative embodiments of the invention in the examples below, but those skilled in the art should understand described specific embodiments according to present disclosure can do many changes and still can obtain similar or similar result and not depart from the spirit and scope of the present invention.

Embodiment 1-3 describes monoesters and the synthesis step of the pungent ester of caproic acid, exemplarily property synthesis step. This synthesis step is the exemplary steps preparing monoesters by some embodiments of the present invention by internal olefin and carboxylic acid chloride's (acyl chlorides).

Embodiment 1

The present embodiment is for illustrating by the secondary alcohol synthetic method of some embodiments of the present invention in monoesters species building-up process.

Octene epoxidation becomes octylene oxide

Following general step (scheme 1) is adopted to carry out epoxidation as follows by purchased from the mixture (1:1:1 mixture) of the 2-octene of AldrichChemicalcompany, 3-octene and 4-octene. Stirring and be added dropwise to feed hopper in the solution of the 77%mCPBA (metachloroperbenzoic acid) of 509g (2.95mol) in 2000ml normal hexane under condition of ice bath the mixture of 265g (2.36mol) 2-octene, 3-octene and 4-octene (1:1:1), last 60 minutes. Stir at the reaction mixture 0 DEG C obtained 2 hours. Then, remove ice bath and reaction is stirred and spends the night. Subsequently the milky solution obtained is filtered to remove the m-chlorobenzoic acid wherein formed. Then filtrate is washed with 10% sodium bicarbonate aqueous solution. Organic over anhydrous dried over mgso, stirs 1 hour simultaneously. Organic solvent (normal hexane) is steamed at normal atmosphere and 67-71 DEG C. IR and NMR analysis and the GCMS of remaining solution is stayed to compose alleged occurrence epoxide mixture and remain normal hexane on a small quantity. This solution is used for next step (epoxide is reduced to corresponding secondary alcohol) and need not remove residual hexane further by every means. Epoxide has some volatility, it is necessary to carefully prevent any remarkable loss when distillation or condensation on rotatory evaporator.

Also formic acid/the superoxol of 1:1.5 part can be used to realize epoxidation.

Embodiment 2

2,3-octylene oxide is reduced to sec-octyl alcohol

Synthetic example:

The octylene oxide containing a small amount of residual hexane embodiment 1 prepared in the steps below reduces by lithium aluminium hydride in THF (tetrahydrofuran (THF)).

The product of embodiment 1 is divided into two equal portions, every part of anhydrous THF of each leisure reduces by lithium aluminium hydride. If the octene in embodiment 1 is all converted into epoxide, then every part of supposition comprises 1.18mol (151.3g) octylene oxide.Therefore, the suspension of 56g (1.48mol) lithium aluminum hydride in the anhydrous THF of 1000ml is cooled to 0 DEG C being furnished with in the 3L tri-neck reaction flask of overhead and reflux exchanger ice bath. Dropping funnel through a sealing drips one of part octylene oxide mixture part that adds two (assuming that 151.3g in this suspension; 1.18mol), stir simultaneously. After adding, add other 100mlTHF through dropping funnel. Continue at reaction mixture 0 DEG C to stir 2 hours. Then move and remove ice bath and reaction continuation stirring is spent the night. Then reactant is heated to backflow one hours, to guarantee that reduction reaction completes. Reaction process is monitored by little part inspection NMR and IR. Once react, thermal source is replaced as ice bath, and reaction carries out aftertreatment, first dilutes with the THF of 500ml, then adds 550ml15%NaOH solution through dropping funnel under strong agitation and do not allow temperature of reaction be raised to more than room temperature (slowly adding). Continue to add until all grey solution transforms milky solution, then continue to stir 30 minutes. Stop stirring, solution is separated into completely transparent liquid phase and the thin throw out of white. Filtering mixt, filtrate is dry through anhydrous MgSO4, and then concentrated except desolventizing THF, to obtain sec-n-octyl alcohol, 3-octanol and 4-octanol mixture, to be colorless viscous oily matter in a rotary evaporator, left at room temperature turns into soft waxy substance after several days. Reduction reaction obtains the alcohol of 132g or says that two reaction yields described in embodiment 1 and 2 are that the reduction reaction of the 86%, two part of octylene oxide obtains similar results, and total recovery is 84%.

Also reduction can be realized, (see Fig. 5) as described in scheme 3 by mild hydrogenation on Pd/C catalyzer on a small scale.

Except metal hydride reduction method, epoxide also can adopt mild hydrogenation under 100-150PSI hydrogen pressure and 35-50 DEG C of temperature of Pt base and Pd base hydrogenation catalyst to carry out the reduction reaction of a certain amount of receipts rate.

Embodiment 3

With caproyl chloride esterification octanol: the synthesis of the pungent ester of caproic acid

As shown in Scheme 3, in the steps below the mixture caproyl chloride preparing sec-n-octyl alcohol, 3-octanol and 4-octanol in embodiment 2 is carried out esterification as esterifying agent. In the 3L tri-neck round bottom reaction flask being furnished with overhead and reflux exchanger, 126.5g (1.25mol) triethylamine and 6.5g (0.05mol) 4-N, N-dimethyl aminopyridine (DMAP) is added in the solution of 130.5g (1mol) octanol mixture in 1000ml hexanaphthene. Ice bath cooling mixture, about 0 DEG C is continued stir about 15 minutes. To in the cold soln stirred, it is added dropwise to 148g (1.1mol) caproyl chloride through dropping funnel, lasts 45 minutes. After all caproyl chlorides add, reaction continues to stir and is slowly warming up to room temperature. Then by reaction backflow and with NMR and IR research and application. After having reacted, the milky white butteriness solution obtained is carried out aftertreatment, add water until all solids disappeared form settled solution (two phase liquid). In separating funnel separation two phase liquid, organic phase washed with water and salt water washing and preserve. Aqueous phase is extracted with ethyl acetate. Acetic acid ethyl acetate extract is with salt water washing and merges with organic phase. By the anhydrous MgSO of the organic phase containing ester₄Dry, filter and concentrate in a rotary evaporator, obtain 218g ester mixture (96% receipts rate), be light orange oil. Product by 15cm �� 5cm silicagel column and is rinsed with hexane. Remove hexane on the rotary evaporator, obtain colorless oil product (reclaiming 214g).

Adopt identical synthesis step, synthesize caproic acid ester in the last of the ten Heavenly stems with similar receipts rate.

Embodiment 4

H ₃ PO ₄ Esterification is carried out as catalyzer caproic acid

By step as follows, the mixture of octanol also carries out esterification with caproic acid in toluene using phosphoric acid as catalyzer. By being furnished with, overhead, the reflux exchanger of band Dean-Stark water trap and the 1L tri-neck reaction flask of heating jacket are formed reaction unit. Reaction vessel loads 50g (0.38mol) octanol mixture, 66g (0.57mol) caproic acid, 85% phosphoric acid of 5g and 250ml toluene. Mixture is heated (about 110 DEG C) backflow 6 hours and maintain to stir and flow through night next time. Add more grams 85% H₃PO₄And reactant is continued under agitation backflow until observing and no longer including water formation (being indicated by the water level collected in Dean-Stark water trap). Reaction amounts to stir about 36 hours. Then reaction is cooled and remove toluene on the rotary evaporator, then extract in ether, and fully clean (4x500ml) with warm water, then with 300ml saturated sodium bicarbonate solution rinsing with remove any residual acid (organic and inorganic) and with salt brine solution (300ml) rinsing. Ethereal extract is used anhydrous MgSO₄Dry, filter and concentrated to remove ether in a rotary evaporator. It is obtained by reacting 76g light yellow oil. Oil is removed by 10cm �� 4cm silicagel column the acid of any residual. After final purification step, reclaim the ester (the pungent ester of caproic acid) desired by 73g, it is colourless sweet taste oil.

Embodiment 5

Repeat step described in embodiment 4, but with 2 liters of scales and the pungent ester of caproic acid adopting this scale production 2 gallons in indivedual synthesis.

Embodiment 6

The lubricity of the pungent ester of caproic acid

Following table 1 shows the pungent ester of caproic acid and the lubricity of caproic acid ester in the last of the ten Heavenly stems. This two classes ester is all specially adapted to drilling fluid.

Table I

The lubricity of the pungent ester of caproic acid and caproic acid ester in the last of the ten Heavenly stems

Embodiment 7

Require BN test

Adopt oxidizer BN test to absorb 1 liter of oxygen by measuring to quantitative ester and need the oxidative stability how long evaluating the pungent ester mixture of caproic acid. The pungent ester of caproic acid presents the excellent oxidation stability (see table 1 and 2, Fig. 7 (A) and 7 (B)) of 64 hours. For comparing, lower Table II provides the correlation data of the oxidizer BN of other lubricant comprising commercially available lubricant.

Table II

The correlation data of oxidizer BN

Lubricant	Oxidizer BN (hour)
		I series lubricant agent	7.2
Group III lubricant	41.2
		Two lauric acid two (tetradecyl) esters	26
Two lauric acid two (hexadecyl) esters	38
		Cargill Agri-Pur 75	0.17*
Cargill Agri-Pur 82	0.3*
		Cargill Agri-Pur 560	0.41*

Cargill product is commercially available ester type biological lubricants *

The correlation data of this oxidizer BN describes the excellent results of the oxidative stability that the pungent ester of caproic acid obtains.

As described in this article, monoesters species present the about 25-excellent oxidation device BN value of about 80 hours, and in some embodiments, oxidizer BN value is about 25-about 75 hours. The lubricant comprising the isomer mixture of at least one monoesters species presents the about 25-oxidizer BN value of about 65 hours.

Conclusion

In a word, the present invention provides a kind of monoesters based lubricant composition. Present invention also offers the method (process) of these and other similar lubricant compositions of preparation. In some embodiments, the method preparing monoesters base lubricating agent make use of biomass precursor and/or low value fischer-tropsch alkene and/or alcohol with production high level monoesters base lubricating agent. In some embodiments, monoesters base lubricating agent is derived from FT alkene and lipid acid. Lipid acid can be obtained by oxidation from bio-based source (i.e. biomass, renewable source) or by FT alcohol.

All patents of reference herein and publication are incorporated to not inconsistent with this paper degree by way of reference at this. It is to be understood that operating in of some said structure, function and above-mentioned embodiment is not necessary in actually operating of the present invention, and it is only the integrity illustrating embodiment or multiple embodiment and comprises in the description. Further, it is to be understood that concrete structure, function and the operation addressed in the patent of above-mentioned reference and publication can combine actually operating with the present invention, but actually operating is not essential by they. Thus, it is to be understood that the present invention can be different from the form specifically described but do not depart from the spirit and scope of the invention defined such as claims carries out actually operating.

Claims

1. comprising the lubricant compositions of the isomer mixture of at least one monoesters species, described monoesters species have following structure:

Wherein R₁��R₂And R₃Independently it is selected from alkyl to provide carbon number range as C₈-C₄₀Monoesters species or monoesters species mixture.

2. the lubricant compositions of claim 1, wherein R₁��R₂And R₃Independently it is selected from alkyl to provide carbon number range as C₁₀-C₂₄Monoesters species or monoesters species mixture.

3. the lubricant compositions of claim 1, wherein R₁��R₂And R₃Independently it is selected from alkyl to provide carbon number range as C₁₂-C₁₈Monoesters species or monoesters species mixture.

4. the lubricant compositions of claim 1, wherein R₁��R₂And R₃Independently it is selected from alkyl to provide carbon number range as C₁₂-C₁₆Monoesters species or monoesters species mixture.

5. the lubricant compositions of claim 1, wherein R₁And R₂Independently it is selected from alkyl and merges carbon number C to have₆-C₂₂And R₃Be carbon number it is C₂-C₁₈Alkyl.

6. the lubricant compositions of claim 1, wherein R₁And R₂Independently it is selected from alkyl and merges carbon number C to have₄-C₁₄And R₃Be carbon number it is C₅-C₁₄Alkyl.

7. the lubricant compositions of claim 1, wherein R₁And R₂Independently it is selected from alkyl and merges carbon number C to have₄-C₈And R₃Be carbon number it is C₅�CC₁₀Alkyl.

8. the lubricant compositions of claim 1, wherein said lubricant comprises the isomer mixture that two or more plant monoesters species.

9. the lubricant compositions of claim 1, wherein said lubricant comprises the isomer mixture of 1-100 kind monoesters species.

10. the lubricant compositions of claim 1, the kinematic viscosity range at wherein said composition 100 DEG C of temperature is 0.5-2 centistoke.

The lubricant compositions of 11. claims 1, wherein pour point is-20 DEG C or lower.

The lubricant compositions of 12. claims 1, wherein R₃Be carbon number it is the alkyl of 2-18.

The lubricant compositions of 13. claims 1, the molecular mass of wherein said at least one monoesters species is about 144 about 592a.m.u.

The lubricant compositions of 14. claims 1, wherein said at least one monoesters species are selected oneself misery ester, the pungent ester isomer of caproic acid, caproic acid ester in the last of the ten Heavenly stems, caproic acid ester isomer in the last of the ten Heavenly stems and their mixture.

The lubricant compositions of 15. claims 1, comprises the base oil being selected from I class base oil, II class base oil, Group III base oil and mixture thereof further.

The lubricant compositions of 16. claims 1, wherein the oxidizer BN value of lubricant compositions is about 25-about 65 hours.

17. prepare the method for monoesters lubricant compositions, comprising:

(a) by alpha-olefin isomerization to provide the isomer mixture of internal olefin;

(b) by the internal olefin epoxidation of step (a) to provide interior epoxide;

C () makes the oxirane ring of the epoxide of step (b) open to provide secondary alcohol by reduction method;

D () is by the secondary alcohol C of step (c)₂-C₁₈Carboxylic acid carries out esterification to provide the isomer mixture of monoesters species; With

The isomer mixture of e monoesters species that viscosity and pour point are suitable as lubricant by () is separated.

The method of 18. claims 17, wherein said alpha-olefin and C₂-C₁₈Carboxylic acid derivatives is from Fischer-Tropsch process.

The method of 19. claims 17, wherein said C₃-C₁₈Carboxylic acid is biologically-derived lipid acid.

The method of 20. claims 17, wherein said alpha-olefin is C₆-C₂₂Alpha-olefin and carboxylic acid are C₅-C₁₄Carboxylic acid.

The method of 21. claims 17, comprises further being undertaken the isomer mixture of monoesters species and the base oil being selected from I class base oil, II class base oil, Group III base oil and mixture thereof adjusting and mixes to provide monoesters lubricant compositions.

The method of 22. claims 21, wherein the kinematic viscosity range of monoesters lubricant compositions at 100 DEG C of temperature is that 0.5-2 centistoke and pour point are-20 DEG C or lower.

The method of 23. claims 21, wherein the oxidizer BN value of monoesters lubricant compositions is about 25-about 65 hours.