JP2020504221A - High stability lubricating oil basestock and method for preparing it - Google Patents

Abstract

Wherein R 1 is a C 1 -C 5000 alkyl group, and R 2 is (i) a C 4 -C 30 linear alkyl group, or (ii) a compound represented by the following formula (F-II) ): (F-II) wherein R5 and R6 at each occurrence are each independently hydrogen or a C1-C30 straight-chain alkyl group, n is a positive integer, provided that all R5 And at least one of R6 is a C1-C30 straight-chain alkyl group, R7 is hydrogen or a C4-C5000 branched-chain alkyl having a C1-C30 straight-chain alkyl group, and R3 is hydrogen or Wherein the R 1 is a C 1 -C 5000 alkyl group and R 4 is a C 1 -C 50 alkyl group or an aromatic group. Also provided are methods for preparing compounds of formula (FI) and basestock and lubricating oil compositions containing compounds of formula (FI).

Description

This application claims the benefit of Provisional Application No. 62 / 446,943, filed January 17, 2017, the disclosure of which is incorporated herein by reference.
The present disclosure relates to sulfur-containing compounds, methods for producing sulfur-containing compounds, and lubricating oil basestocks and lubricating oils containing sulfur-containing compounds with improved thermal and oxidative stability.

Lubricants used commercially today are prepared from a variety of natural and synthetic basestocks mixed with various additive packages and solvents depending on their intended use. Basestocks typically include mineral oil, polyalphaolefin (PAO), gas-to-liquid base oil (GTL), silicone oil, phosphate esters, diesters, polyol esters, and the like.
A major trend in passenger car engine oils (PCEOs) is an overall improvement in quality as higher quality base stocks have become more readily available. Typically, the highest quality PCEO product is blended with a base stock, eg, a PAO or GTL stock.
PAO and GTL stocks are an important class of lubricating oil basestocks with many excellent lubricating properties, including high viscosity index (VI), but may have lower thermal and oxidative stability. Thermal and oxidative stability are important because they tend to require smaller sump sizes that can cause additional thermal and oxidative stress to the lubricating oil. In addition, the performance requirements of lubricating oils have become more stringent and the demand for longer discharge intervals continues to increase.
Sulfur may be incorporated into base stocks due to its antioxidant capacity. Sulfurized PAO (S-PAO) base stock can improve oxidative stability and improve durability when exposed to high temperatures, and can prolong the life of lubricating oil as a whole. The synthesis of base stocks may introduce tertiary CH bonds in addition to the sulfur atom. For example, under radical initiation conditions, the following known scheme A, where R may be an alkyl group or an aromatic compound:

スキームA
に示す通り、硫黄付加は、周知の「反マルコフニコフ付加」にしたがい、硫黄原子は、非水素化ＰＡＯオリゴマーからの二重結合のより低置換の炭素原子に結合して、Ｓ−ＰＡＯ内で第三級Ｃ−Ｈ結合を形成する。Ｃ−Ｈ結合のこの水素原子は、第三級Ｃ−Ｈ結合解離エネルギーが低いために酸化的開裂が特に起こりやすい可能性がある。したがって、そのような第三級Ｃ−Ｈ結合は、酸化的分解が起こりやすくなり、それによってＳ−ＰＡＯの酸化安定性が低下する可能性がある。
したがって、熱安定性および酸化安定性が向上したＳ−ＰＡＯ、ならびに酸化的変化を受けやすい第三級Ｃ−Ｈ結合を導入しない、Ｓ−ＰＡＯを製造するための方法が必要とされている。さらに具体的には、非水素化ＰＡＯオリゴマーからの二重結合のより高置換の炭素原子に硫黄原子が結合するＳ−ＰＡＯおよびそれを調製する方法が必要とされている。

Scheme A
The sulfur addition follows the well-known "anti-Markovnikov addition", in which the sulfur atom is attached to the lower-substituted carbon atom of the double bond from the non-hydrogenated PAO oligomer, resulting in a S-PAO Form a tertiary CH bond. This hydrogen atom of the CH bond may be particularly susceptible to oxidative cleavage due to the low tertiary CH bond dissociation energy. Thus, such tertiary C—H bonds can be susceptible to oxidative degradation, thereby reducing the oxidative stability of S-PAO.
Accordingly, there is a need for a method for producing S-PAO with improved thermal and oxidative stability, and for introducing S-PAO that does not introduce tertiary CH bonds susceptible to oxidative changes. More specifically, there is a need for S-PAOs from a non-hydrogenated PAO oligomer in which a sulfur atom is attached to a more highly substituted carbon atom of a double bond and a method for preparing the same.

(F-I)
［式中、Ｒ¹はＣ₁−Ｃ₅₀₀₀アルキル基であり、Ｒ²は、（ｉ）Ｃ₄−Ｃ₃₀直鎖アルキル基、または（ｉｉ）以下の式（Ｆ−ＩＩ）：

(F-II)
（式中、Ｒ⁵およびＲ⁶は、それぞれの出現において、それぞれ独立して水素またはＣ₁−Ｃ₃₀直鎖アルキル基であり、ｎは正の整数であり、ただし、すべてのＲ⁵およびＲ⁶のうち、少なくとも１つはＣ₁−Ｃ₃₀直鎖アルキル基であり、Ｒ⁷は、水素またはＣ₁−Ｃ₃₀直鎖アルキル基である）
を有するＣ₄−Ｃ₅₀₀₀分岐鎖アルキル基であり、Ｒ³は、水素またはＣ₁−Ｃ₅₀₀アルキル基であり、Ｒ⁴は、Ｃ₁−Ｃ₅₀アルキル基または芳香族基である］
を有する化合物を含む潤滑油ベースストックに関する。 Surprisingly, it has been found that a more stable S-PAO can be selectively synthesized by acid-catalyzed synthesis without introducing a tertiary CH bond susceptible to oxidative change.
Accordingly, the present disclosure is directed, in part, to the following formula (FI):

(FI)
[Wherein, R ¹ is a C ₁ -C ₅₀₀₀ alkyl group, and R ² is (i) a C ₄ -C ₃₀ linear alkyl group, or (ii) a compound represented by the following formula (F-II):

(F-II)
Wherein R ⁵ and R ⁶ at each occurrence are each independently hydrogen or a C ₁ -C ₃₀ straight-chain alkyl group, n is a positive integer, provided that all R ⁵ and R 6 ⁶ , at least one is a C ₁ -C ₃₀ straight-chain alkyl group, and R ⁷ is hydrogen or a C ₁ -C ₃₀ straight-chain alkyl group)
A C ₄ -C ₅₀₀₀ branched chain alkyl group having the formula: wherein R ³ is hydrogen or a C ₁ -C ₅₀₀ alkyl group, and R ⁴ is a C ₁ -C ₅₀ alkyl group or an aromatic group.
A lubricating oil basestock comprising a compound having the formula:

(F-Ia)
を有する化合物を含むオレフィン含有材料と反応させる工程を含む、方法に関する。 The present disclosure also provides, in part, a method for producing a compound of formula (FI) and / or a base stock comprising a compound of formula (FI), wherein HS-R ^{4 comprises} an acid catalyst. In the presence of the following formula:

(F-Ia)
Reacting with an olefin-containing material comprising a compound having the formula:

The present disclosure further relates, in part, to a compounded lubricating oil comprising one or more of the lubricating oil basestocks described herein.
Other embodiments, including specific aspects of the embodiments summarized above, will be apparent from the detailed description that follows.

FIG. 2 shows a ¹ H NMR spectrum of a product I. FIG. 3 is a chart showing a ¹ H NMR spectrum of Comparative Product 1. FIG. 2 is a chart showing ¹ H NMR structural assignments of compound-I and compound-II. FIG. 4 shows a ¹ H NMR spectrum of product IV. FIG. 6 is a diagram showing ¹ H NMR structural assignments of compounds VII and VIII. FIG. 3 shows the oxidative stability of Product I, Product III, Comparative Product 1, PAO 4 and Synesstic ™ 5.

In various aspects of the invention, catalysts and methods for preparing the catalysts are provided.
I. Definitions In the present invention and the appended claims, the numbering system for the groups of the Periodic Table is according to the IUPAC Periodic Table of the Elements, dated January 1, 2017.
The term "and / or" as used herein in phrases such as "A and / or B" includes "A and B", "A or B", "A" and "B" Is intended.
The terms "substituent,""radical,""group," and "moiety" may be used interchangeably.
As used herein, unless otherwise specified, the term “C _n ” means a hydrocarbon having n carbon atoms per molecule, where n is a positive integer.
As used herein, unless otherwise specified, the term “hydrocarbon” refers to a class of compounds that contain hydrogen bonded to carbon and includes (i) saturated hydrocarbon compounds, (ii) ) Unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different values of n.

As used herein, unless otherwise specified, the term “alkyl” refers to a saturated hydrocarbon group having 1 to 1000 carbon atoms (ie, C ₁ -C ₁₀₀₀ alkyl). Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and the like. The alkyl group may be straight, branched or cyclic. "Alkyl" is intended to include all structural isomeric forms of the alkyl group. For example, as used herein, propyl includes both n-propyl and isopropyl, and butyl includes n-butyl, sec-butyl, isobutyl, tert-butyl, and the like. As used herein, “C ₁ alkyl” refers to methyl (—CH ₃ ), “C ₂ alkyl” refers to ethyl (—CH ₂ CH ₃ ), and “C ₃ alkyl” refers to propyl ( It refers to -CH ₂ CH ₂ CH _3), and isopropyl, "C ₄ alkyl", butyl group _{(e.g., -CH 2 CH 2 CH 2 CH} 3, -CH (CH 3) CH 2 CH 3, -CH 2 CH It refers to such (CH _{3) 2).} Further, as used herein, “Me” refers to methyl, “Et” refers to ethyl, “i-Pr” refers to isopropyl, “t-Bu” refers to tert-butyl, "Np" refers to neopentyl.

As used herein, unless otherwise specified, the term "aromatic" refers to an unsaturated hydrocarbon containing an aromatic ring in its structure, wherein the aromatic ring has a delocalized π-conjugated system. And preferably has 4 to 20 carbon atoms. Exemplary aromatics include benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene, benzanthracene, fluoranthrene, Including, but not limited to, pyrene, chrysene, triphenylene, and the like, and combinations thereof. The aromatic may be substituted, for example, with one or more alkyl groups, alkoxy groups, halogens, and the like.
The aromatic ring may contain one or more heteroatoms. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen and / or sulfur. Aromatics having one or more heteroatoms in the aromatic ring therein include, but are not limited to, furan, benzofuran, thiophene, benzothiophene, oxazole, thiazole, and the like, and combinations thereof. The aromatic ring may be monocyclic, bicyclic, tricyclic and / or polycyclic (in some embodiments, at least monocyclic rings, monocyclic and bicyclic rings only, or monocyclic rings). Or only a condensed ring.

As used herein, the term "olefin" refers to an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon-carbon double bond in its structure. Heavy bonds do not form part of an aromatic ring. The olefin may be linear, branched or cyclic. "Olefin" is intended to include all structural isomeric forms of the olefin, unless stated to mean a single isomer, or unless the context clearly indicates otherwise.
As used herein, the term “alpha-olefin” refers to an olefin having a terminal carbon-carbon double bond ((R ₁ R ₂ ) —C ＝ CH ₂ ) in its structure.

As used herein, "polyalphaolefin"("PAO") includes any oligomers and polymers of one or more alpha-olefin monomers. Thus, the PAO can be a dimer, trimer, tetramer, or any other oligomer or polymer containing two or more structural units derived from one or more alpha-olefin monomers. PAO molecules can be very regioregular, as the bulk material exhibits isotacticity or syndiotacticity as measured by ¹³ C NMR. PAO molecules can be very regio-irregular, such that the bulk material is substantially atactic as measured by ¹³ C NMR. PAO materials made using metallocene-based catalyst systems are commonly referred to as metallocene-PAO ("mPAO") and use conventional non-metallocene-based catalysts (eg, Lewis acids, supported chromium oxide, etc.). The manufactured PAO material is commonly referred to as conventional PAO ("cPAO").

PAO molecules obtained without polymerizing or oligomerizing the alpha-olefin monomer and further hydrogenating it usually contain an ethylenically unsaturated C = C double bond in their structure. Non-hydrogenated PAOs are sometimes referred to herein as "uPAOs." uPAO materials include, inter alia, vinyl (the following FA where R is alkyl), 2,2-disubstituted olefins (the same or different R- and R2 where the following F- B), 1,2-disubstituted (di-substitued) olefin (same or different R ₁ and R ₂ are alkyl, disubstituted as vinylene following known F-C1 and F-C2 E- And Z-isomers) and trisubstituted olefins (the following FD, also known as trisubstituted vinylene, wherein the same or different R ₁ , R ₂ and R ₃ are alkyl). Vinyl and vinylidene are terminal olefins, and di- and trisubstituted vinylene olefins are internal olefins.

uPAO can be hydrogenated in the presence of hydrogen and a hydrogenation catalyst to reduce its ethylenic unsaturation and obtain a hydrogenated PAO. Such hydrogenated PAOs can be more stable and provide higher heat and oxidation resistance compared to the corresponding uPAOs. Otherwise, uPAO can be chemically modified to obtain its derivatives if there is a chemical reactivity of the ethylene C = C double bond. Derivatives can provide a variety of interesting physical and chemical properties depending on the functional groups attached to the carbon chain as a result of the modification.
As used herein, the term "lubricating oil" is a substance that can be introduced between two or more moving surfaces to reduce the level of friction between two adjacent surfaces moving relative to each other. Point to. A lubricating oil "basestock" is a material that is normally fluid at the operating temperature of the lubricating oil and is used to formulate the lubricating oil by mixing with other components. Non-limiting examples of suitable base stocks in lubricating oils include API Group I, Group II, Group III, Group IV, Group V and Group VI base stocks. PAOs, especially hydrogenated PAOs, have recently been widely used as Group IV basestocks in lubricating oil formulations.

NMR spectroscopy gives important structural information about the synthetic polymer. Proton NMR ⁽¹ H-NMR) analysis uPAO, the olefin structure type (i.e., vinyl, 1,2-disubstituted vinylene, trisubstituted vinylene and vinylidene) to quantitatively analyze the. In the present disclosure, the composition of a mixture of olefins including terminal olefins (vinyl and vinylidene) and internal olefins (1,2-disubstituted vinylene and trisubstituted vinylene) is determined by using ¹ H-NMR. Specifically, an NMR instrument of at least 500 MHz is operated under the following conditions: RF pulse flip angle 30 °, 120 scans and 5 seconds delay between pulses; sample dissolved in CDCl ₃ (deuterated chloroform) And a signal collection temperature of 25 ° C. When determining the concentration of various olefins among all olefins from the NMR graph, the following approach is taken. First, peaks corresponding to various types of hydrogen atoms in vinyl (T1), vinylidene (T2), 1,2-disubstituted vinylene (T3) and trisubstituted vinylene (T4) are shown in Table I below. In the peak region. Then, second, the area of each of the above-mentioned peaks (A1, A2, A3 and A4, respectively) is integrated. Third, the amount of each type of olefin (Q1, Q2, Q3 and Q4 respectively) is calculated in moles (as A1 / 2, A2 / 2, A3 / 2 and A4 respectively). Fourth, the total amount (Qt) of all olefins is calculated in moles as the sum of all four types (Qt = Q1 + Q2 + Q3 + Q4). Then, finally, the molar concentration of each type of olefin (in C1, C2, C3 and C4, respectively, in mol%) based on the total molar amount of all olefins is calculated (in each case, Ci = 100 × Qi / Qt).

Carbon-13 NMR ( ^13C -NMR) is used to determine the tacticity of the PAOs of the present invention. The triads represented as (m, m) -triads (ie, meso, meso), (m, r)-(ie, meso, racemic) and (r, r)-(ie, racemic, racemic) triads, respectively. Carbon-13 NMR can be used to determine the concentration. The concentration of these triads reveals whether the polymer is isotactic, atactic, or syndiotactic. In the present disclosure, the concentration of (m, m) -triad is reported as the isotacticity of the PAO material in mol%. The spectrum of the PAO sample is obtained as follows. Dissolve about 100-1000 mg of the PAO sample in 2-3 ml of chloroform-d for ¹³ C-NMR analysis. The sample is measured with a delay of 60 seconds and a pulse of 90 ° and at least 512 transients. Tacticity was calculated using the peak at about 35 ppm (CH ₂ peak next to the branch point). Analysis of the spectrum is described by Kim, I. et al. , Zhou, J .; -M. And Chung, H .; The Journal of Polymer Science: Part A: Polymer Chemistry 2000, 38 1687-1697. The tacticity is calculated as follows: mm × 100 / (mm + mr + rr) for the mole percentage of (m, m) -triad, mr × 100 / (mm + mr + rr), (r, r) for the mole percentage of (m, r) -triad. The molar percentage of) -triad is rr × 100 / (mm + mr + rr). (M, m) -triad at 35.5 to 34.55 ppm, (m, r) -triad at 34.55 to 34.1 ppm, and (r, r) -triad at 34.1 to 33.2 ppm. Corresponding.

II. Sulfur-Containing Compounds Useful in Basestocks The present disclosure relates to sulfur-containing compounds, which are useful in basestock compositions due to their improved thermal and oxidative stability. In particular, a sulfur-containing compound is provided herein, wherein the sulfur-containing compound has a sulfur atom attached to the lower substituted carbon to avoid the formation of tertiary CH bonds susceptible to oxidative changes. Alternatively, selective synthesis from non-hydrogenated PAO (uPAO) and thiol compounds using an acid catalyst such that the sulfur atom is primarily attached to the higher substituted carbon atom of the double bond in the uPAO Can be. Therefore, the following equation (FI).

(F-I)
［式中、
Ｒ¹はＣ₁−Ｃ₅₀₀₀アルキル基であり、
Ｒ²は、（ｉ）Ｃ₄−Ｃ₃₀直鎖アルキル基、または（ｉｉ）以下の式（Ｆ−ＩＩ）：

(F-II)
（式中、Ｒ⁵およびＲ⁶は、それぞれの出現において、それぞれ独立して水素またはＣ₁−Ｃ₃₀直鎖アルキル基であり、ｎは正の整数であり、ただし、すべてのＲ⁵およびＲ⁶のうち、少なくとも１つはＣ₁−Ｃ₃₀直鎖アルキル基であり、Ｒ⁷は、水素またはＣ₁−Ｃ₃₀直鎖アルキル基である）
を有するＣ₄−Ｃ₅₀₀₀分岐鎖アルキルであり、
Ｒ³は、水素またはＣ₁−Ｃ₅₀₀₀アルキル基であり、
Ｒ⁴は、Ｃ₁−Ｃ₅₀アルキル基または芳香族基である］
を有する化合物が本明細書において提供される。

(FI)
[Where,
R ¹ is a C ₁ -C ₅₀₀₀ alkyl group;
R ² represents (i) a C ₄ -C ₃₀ linear alkyl group, or (ii) a compound represented by the following formula (F-II):

(F-II)
Wherein R ⁵ and R ⁶ at each occurrence are each independently hydrogen or a C ₁ -C ₃₀ straight-chain alkyl group, n is a positive integer, provided that all R ⁵ and R 6 ⁶ , at least one is a C ₁ -C ₃₀ straight-chain alkyl group, and R ⁷ is hydrogen or a C ₁ -C ₃₀ straight-chain alkyl group)
C ₄ -C ₅₀₀₀ branched chain alkyl having the formula:
R ³ is hydrogen or a C ₁ -C ₅₀₀₀ alkyl group;
R ⁴ is a C ₁ -C ₅₀ alkyl group or an aromatic group]
Provided herein are compounds having the formula:

In one embodiment, R ³ may be hydrogen, for example, when the uPAO used during synthesis is a vinylidene olefin.
Alternatively, R ³ is, C ₁ -C ₅₀₀₀ alkyl group, C ₁ -C ₄₀₀₀ alkyl group, C ₁ -C ₃₀₀₀ alkyl group, C ₁ -C ₂₀₀₀ alkyl group, C ₁ -C ₁₀₀₀ alkyl group, C ₁ -C ₉₀₀ alkyl group, C ₁ -C ₈₀₀ alkyl group, C ₁ -C ₇₀₀ alkyl group, C ₁ -C ₆₀₀ alkyl group, C ₁ -C ₅₀₀ alkyl group, C ₁ -C ₄₀₀ alkyl group, C ₁ -C ₃₀₀ alkyl group, C ₁ -C ₂₀₀ alkyl group, C ₁ -C ₁₀₀ alkyl group, C ₁ -C ₅₀ alkyl group or a C ₁ -C ₃₀ alkyl group or a C ₁ -C ₁₀ alkyl group. The alkyl group may be straight or branched. In particular, R ³ may be a C ₁ -C ₁₀₀ alkyl group.
Additionally or alternatively, R ¹ is a linear or branched C ₁ -C ₅₀₀₀ alkyl group, a C ₁ -C ₄₀₀₀ alkyl group, a C ₁ -C ₃₀₀₀ alkyl group, a C ₁ -C ₂₀₀₀ alkyl group, ₁ -C ₁₀₀₀ alkyl group, C ₁ -C ₉₀₀ alkyl group, C ₁ -C ₈₀₀ alkyl group, C ₁ -C ₇₀₀ alkyl group, C ₁ -C ₆₀₀ alkyl group, C ₁ -C ₅₀₀ alkyl group, C ₁ - C ₄₀₀ alkyl group, C ₁ -C ₃₀₀ alkyl group, C ₁ -C ₂₀₀ alkyl group, C ₁ -C ₁₀₀ alkyl group, C ₁ -C ₅₀ alkyl group, C ₁ -C ₃₀ alkyl group or C ₁ -C ₁₀ alkyl group. It may be an alkyl group.

In particular variation, R ² are each independently C ₄ -C ₃₀ straight-chain alkyl group, C ₄ -C ₂₄ straight-chain alkyl group, C ₄ -C ₂₀ straight-chain alkyl group, C ₄ -C ₁₈ straight It may be a chain alkyl group or a C ₄ -C ₁₆ straight chain alkyl group.
In another embodiment, R ¹ is a C ₁ -C ₁₀₀ straight chain alkyl group, a C ₁ -C ₅₀ straight chain alkyl group, a C ₁ -C ₃₀ straight chain alkyl group or a C ₁ -C ₁₀ straight chain alkyl group. Often, R ² is a C ₄ -C ₃₀ linear alkyl group, a C ₄ -C ₂₄ linear alkyl group, a C ₄ -C ₂₀ linear alkyl group, a C ₄ -C ₁₈ linear alkyl group, a C ₄ -C _It may be a ₁₆ linear alkyl group or a C ₁ -C ₁₄ linear alkyl group.

In particular variation, R ¹ or R ² (wherein, n greater than 1) of the above formula (F-II) may be a C ₄ -C ₅₀₀₀ branched-chain alkyl group represented by R ^5, At least 50% (eg, at least 60%, 70%, 80%, 90% or even 95%) is hydrogen and at least 50% (eg, at least 60%, 70%, 80%, 90% or 90%) of R ^6. even 95%) is a C ₁ -C ₃₀ straight chain alkyl group independently. In particular variation of the case at least a portion of a part of R ⁵ and R ⁶ are alkyl groups, at least 80% of their R ⁵ is an alkyl group in C ₁ -C ₄ straight chain alkyl group And at least 80% of R ⁶ is a C ₄ -C ₃₀ straight chain alkyl group. In certain variations, all of R ⁵ are hydrogen, all R ⁶ same or different is a C ₁ -C ₃₀ straight chain alkyl group independently. In certain variations, all of R ⁵ are hydrogen, all R ⁶ are the same C ₁ -C ₃₀ straight chain alkyl group.

In particular variation, R ¹ or R ² may be a C ₄ -C ₅₀₀₀ branched-chain alkyl group represented by the aforementioned formula (F-II), at least 50% of the R ⁶ (e.g., at least 60%, 70%, 80%, 90% or even 95%) is hydrogen, at least 50% of the R ⁵ (e.g., at least 60%, 70%, 80%, 90% or even 95%) are, independently C _{It is a 1- C30} straight-chain alkyl group. In certain variations where some of R ⁶ and at least some of R ⁵ are alkyl groups, at least 80% of those R ⁶ that are alkyl groups are C ₁ -C ₄ linear alkyl groups. There, at least 80 percent of R ⁵ is C ₄ -C ₃₀ straight-chain alkyl group. In certain variations, all of R ⁶ is hydrogen, both of R ⁵ the same or different is a C ₁ -C ₃₀ straight chain alkyl group independently. In certain variations, all of R ⁶ is hydrogen, both of R ⁵ are the same C ₁ -C ₃₀ straight chain alkyl group.

Additionally or alternatively, R ⁴ is, C ₁ -C ₅₀₀ alkyl group, C ₁ -C ₃₀₀ alkyl group, C ₁ -C ₁₀₀ alkyl group, C ₁ -C ₅₀ alkyl group, C ₁ -C ₃₀ alkyl group Alternatively, it may be a C ₁ -C ₁₀ alkyl group. The alkyl group may be straight or branched. In particular, R ⁴ may be a C ₁ -C ₅₀ alkyl group, especially a C ₁ -C ₅₀ linear alkyl group or a C ₁ -C ₃₀ linear alkyl group.

Additionally or alternatively, R ⁴ may be an aromatic group. Suitable aromatic groups include one or more alkyl, alkoxy, or halogen (eg, F, Cl, Br), hydroxyl, nitro groups, and heteroatoms (eg, N, O, S), including but not limited to one or more phenyl groups that may contain. For example, aromatic groups include 4-methylphenyl, 4-methoxyphenyl, benzyl, 2-naphthyl, 1-naphthyl, pyridinyl, 2,3,4,5,6-pentafluorophenyl, 2,3,5 2,6-tetrafluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4-difluorophenyl, 3,4 -Difluoro phenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2 -Chlorobenzyl, 4-chlorobenzyl yl), 3-nitrobenzyl, 4-nitrobenzyl, 2-benzyl (benzyl) alcohol, 4-nitrophenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2-aminophenyl, 3-aminophenyl , 4-aminophenyl, 2- (trifluoromethyl) phenyl, 4-bromo-2-fluorobenzyl, 4-chloro-2-fluorobenzyl, 3,4-difluorobenzyl, 3,5-difluorobenzyl, 2-bromo Benzyl, 3-bromobenzyl, 4-bromobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4- ( Methylsulfanyl) phenyl, 2-phenoxy Tyl, 3-ethoxyphenyl, 4-methoxybenzyl, 2,5-dimethoxyphenyl, 3,4-dimethoxyphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 1,3 , 5-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 2-phenylethyl, 1,2-xylyl, 1,3-xylyl, 1,4-xylyl, 2-isopropylphenyl, 4-isopropylphenyl , 4- (dimethylamino) phenyl, 2,4,6-trimethylbenzyl, 4-tert-butylbenzyl, 4-tert-butylphenyl, tert-dodecylmercaptan, tribenzyl, 9-fluorenylmethyl, 9-fluorenyl and the like Or a combination thereof, but is not limited thereto.

Examples of compounds of formula (FI) are shown below in Table II.

  The compounds of formula (FI) described herein may have varying levels of regioregularity. For example, each compound of formula (FI) may be substantially atactic, isotactic, or syndiotactic. However, these compounds may be a mixture of different molecules, each of which may be atactic, isotactic, or syndiotactic. However, without wishing to be bound by any particular theory, regioregular molecules, especially isotactic molecules, are described herein due to the regular distribution of pendant groups, especially longer pendant groups. Is believed to tend to contribute to improved performance (eg, electrohydrodynamic lubrication performance) of basestocks containing the compound of Formula (FI) Thus, at least about 50 mol%, or at least about 60 mol%, or at least about 70 mol%, or at least about 75 mol%, or at least about 80 mol%, or at least about 90 mol% of a compound of Formula (FI) described herein. %, Or even about 95 mol%, is regioregular. At least about 50 mol%, or at least about 60 mol%, or at least about 70 mol%, or at least about 75 mol%, or at least about 80 mol%, or at least about 90 mol%, of a compound of Formula (FI) described herein; Or even more preferably about 95 mol% is isotactic.

(F-Ia)
［式中、Ｒ¹、Ｒ²、Ｒ³およびＲ⁴は、式（Ｆ−Ｉ）に関連して上述の通りである］
を有する化合物を含むオレフィン含有材料と反応させる工程を含む。
上述の通り、ラジカル開始条件下のスキームＡによるＳ−ＰＡＯの合成は、反マルコフニコフ付加にしたがい、硫黄原子に加えて第三級Ｃ−Ｈ結合を導入する。この第三級Ｃ−Ｈ結合は、酸化的分解が起こりやすくなり、それによってＳ−ＰＡＯの酸化安定性が低下する可能性がある。意外にも、本明細書に記載の方法により、酸化的変化を受けやすい第三級Ｃ−Ｈ結合も同時に導入されることなく、酸化安定性を向上させる硫黄原子が導入され得ることを見出した。実際、熱安定性および酸化安定性が向上した式（Ｆ−Ｉ）の化合物（Ｓ−ＰＡＯ）は、ｕＰＡＯオリゴマーからの二重結合のより高置換の炭素原子に硫黄原子が結合するように、酸触媒条件下、ｕＰＡＯをチオール化合物と反応させることにより調製され得る。 III. Methods for Producing Sulfur-Containing Compounds Provided herein are methods for producing compounds of formula (FI). In particular, the method comprises converting HS-R ⁴ (ie, thiol) to the following formula (F-Ia) in the presence of an acid catalyst:

(F-Ia)
Wherein R ¹ , R ² , R ³ and R ⁴ are as described above in relation to formula (FI)
Reacting with an olefin-containing material containing a compound having the formula:
As described above, the synthesis of S-PAO according to Scheme A under radical initiation conditions introduces a tertiary C—H bond in addition to the sulfur atom according to the anti-Markovnikov addition. This tertiary C—H bond is susceptible to oxidative degradation, which can reduce the oxidative stability of S-PAO. Surprisingly, it has been found that the method described herein can introduce a sulfur atom that improves oxidative stability without simultaneously introducing a tertiary CH bond susceptible to oxidative change. . In fact, the compound of formula (F-I) with improved thermal and oxidative stability (S-PAO) has the advantage that the sulfur atom is bonded to the more highly substituted carbon atom of the double bond from the uPAO oligomer. It can be prepared by reacting uPAO with a thiol compound under acid catalyzed conditions.

  Thus, advantageously, the methods described herein have a high selectivity for the formation of compounds that conform in structure to Formula (FI). For example, at least about 50 mol%, at least about 60 mol%, at least about 70 mol%, at least about 80 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 99 mol% of the produced compound has the formula (FI) Matches. Additionally or alternatively, about 50 mol% to about 99 mol%, about 70 mol% to about 99 mol%, about 80 mol% to about 99 mol%, or about 90 mol% to about 99 mol% of the compound produced has the formula (F -I). Theoretically, even if this reaction has a selectivity of less than 90 mol%, it is still possible to purify the product mixture to obtain a final product with a purity of more than 90 mol% of the expected product it can. In some cases, the balance of the S-PAO compound formed has a sulfur atom attached to a primary or secondary carbon from uPAO.

In various embodiments, R ³ may be hydrogen. Optionally, the olefin-containing material comprises at least about 1.0% by weight, at least about 1.0% by weight, based on the total weight of the olefin-containing material, of one or more olefinic compounds of Formula (F-Ia) wherein R ³ is hydrogen. 10 wt%, at least about 20 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 75 wt%, at least about 80 wt% %, At least about 90% by weight, at least about 99% by weight or about 100% by weight. In particular, the olefin-containing material may comprise a compound of formula (F-Ia) wherein R ³ is hydrogen in an amount of at least about 75% by weight. Additionally or alternatively, the olefin-containing material, about 1.0% wt% to about 100% by weight R ³ is hydrogen, about 1.0% wt% to about 99 wt%, 1.0% wt% About 90%, about 20% to about 90%, about 40% to about 90%, about 50% to about 90%, about 60% to about 90%, It may comprise from about 75% to about 90% by weight or from about 80% to about 90% by weight of a compound of formula (F-Ia).

Alternatively, R ³ is, C ₁ -C ₅₀₀₀ alkyl group, C ₁ -C ₄₀₀₀ alkyl group, C ₁ -C ₃₀₀₀ alkyl group, C ₁ -C ₂₀₀₀ alkyl group, C ₁ -C ₁₀₀₀ alkyl group, C ₁ -C ₉₀₀ alkyl group, C ₁ -C ₈₀₀ alkyl group, C ₁ -C ₇₀₀ alkyl group, C ₁ -C ₆₀₀ alkyl group, C ₁ -C ₅₀₀ alkyl group, C ₁ -C ₄₀₀ alkyl group, C ₁ -C ₃₀₀ alkyl group, C ₁ -C ₂₀₀ alkyl group, C ₁ -C ₁₀₀ alkyl group, C ₁ -C ₅₀ alkyl group or a C ₁ -C ₃₀ alkyl group or a C ₁ -C ₁₀ alkyl group. In some cases, the olefin-containing material can include one or more compounds of Formula (F-Ia) wherein R ³ is an alkyl group (eg, a C ₁ -C ₁₀₀ alkyl group) based on the total weight of the olefin-containing material. At least about 1.0%, at least about 10%, at least about 20%, at least about 25%, at least about 30%, at least about 40%, at least about 50%, at least about 60% by weight. , At least about 70%, at least about 75%, at least about 80%, at least about 90%, at least about 99% or about 100% by weight. In particular, the olefin-containing materials, R ³ is an alkyl group (e.g., C ₁ -C ₁₀₀ alkyl group) may contain an amount of about 50 wt% of the compound of at least the formula is (F-Ia). Additionally or alternatively, the olefin-containing materials, R ³ is an alkyl group (e.g., C ₁ -C ₁₀₀ alkyl group) from about 1.0% weight percent to about 100 weight percent is 1.0% by mass% About 99%, 1.0% to about 90%, about 10% to about 60%, about 10% to about 50%, about 10% to about 40% by weight or It may comprise from about 10% to about 25% by weight of a compound of formula (F-Ia).

In some embodiments, the olefin-containing material may include a mixture of compounds of Formula (F-Ia). For example, the olefin-containing material comprises (i) one or more olefinic compounds of formula (F-Ia), wherein R ³ is hydrogen, and (ii) a formula (F-Ia) wherein R ³ may be a mixture of one or more compounds of an alkyl group (eg, a C ₁ -C ₁₀₀ alkyl group). In some embodiments, the olefin-containing material comprises (i) from about 1.0% to about 99% by weight of one or more of Formula (F-Ia), wherein R ³ is hydrogen. and olefinic compound, (ii) about 1.0% weight percent to about 99 weight percent of the formula (F-Ia) (wherein, R ³ is an alkyl group (e.g., C ₁ -C ₁₀₀ alkyl group)) And a mixture with one or more olefin compounds. In particular, the olefin-containing material comprises (i) from about 50% to about 90% or from about 75% to about 90% by weight of Formula (F-Ia) of Formula (F-Ia), wherein R ³ is hydrogen. One or more olefin compounds, and (ii) from about 10% to about 50% or from about 10% to about 25% by weight of Formula (F-Ia), wherein R ³ is an alkyl group ( For example, a C ₁ -C ₁₀₀ alkyl group) may be included in a mixture with one or more olefin compounds.

Olefin-containing materials used in this method, PAO (mPAO, cPAO and mixtures thereof) dimers (C ₄ -C _100), trimer (C ₆ -C _100), tetramer (C ₈ - C ₁₀₀ ), pentamers, hexamers and higher oligomers, and the like, or alpha-olefins (eg, C ₂ -C ₃₀ alpha-olefins). Suitable alpha-olefins include, for example, alkyl olefins, such as 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, and the like.

A PAO dimer (eg, mPAO, cPAO) can be any dimer with a terminal C = C double bond prepared by using a metallocene or other single-site catalyst. Dimer, alpha - olefins (e.g., C ₂ -C ₃₀ alpha - olefins), e.g., 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene or alpha - olefins From a combination of In particular, the olefin-containing material in the methods provided herein, C ₁ -C ₁₀₀ alpha in the presence of a metallocene compound - may be generated by the oligomerization of olefins. Metallocene catalyzed alpha-olefin oligomerization processes are described in U.S. Patent Nos. 5,688,887 and 6,043,401 and WO 2007/011973, each of which is incorporated by reference in its entirety. And incorporated herein by reference for details of feed, metallocene catalyst, process conditions and product characterization.
In some examples, at least about 50 mol%, or at least about 60 mol%, or at least about 70 mol%, or at least about 75 mol%, or at least about 80 mol%, or at least about 90 mol% of the olefin-containing materials described herein. Or even about 95 mol% is isotactic. In particular, at least about 60 mol%, or at least about 75 mol%, or at least about 80 mol% of the olefin-containing materials described herein are isotactic.

CPAO may be produced using a conventional catalyst to form an olefin-containing material having the formula (F-Ib). Examples of conventional catalysts suitable Lewis acid compound, e.g., BF _3, AlCl _3, including but trialkyl aluminum or a combination thereof, without limitation. When using conventional catalysts, the resulting olefin-containing material tends to be a mixture of olefin compounds with widely differing R ¹ , R ² and R ³ . At least one of R ¹ , R ² and R ³ may be an alkyl having a carbon backbone with a plurality of pendant groups attached to the carbon backbone, and many of the pendant groups are short chain alkyl, eg, methyl , Ethyl and the like. The distribution of such pendant groups on the backbone can be irregular. Non-hydrogenated cPAOs, such as those obtained by using conventional catalysts, can typically be atactic. Methods for the production of cPAO are described, for example, in the following patents: US Pat. Nos. 3,149,178, 3,382,291, 3,742, each of which is incorporated herein by reference in its entirety. Nos. 082, 3,769,363, 3,780,128, 4,172,855, and 4,956,122 and Shubkin, RL (Ed.) (1992) Synthetic Lubricants and High- Performance Functional Fluids (Chemical Industries) New York: disclosed by Marcel Dekker Inc.

PAO lubricating oil compositions with little double bond isomerization resulted in various classes of high viscosity index PAO (HVI-PAO). These are also contemplated for use in the present invention. In one class of HVI-PAO, a reduced chromium catalyst is reacted with an alpha-olefin monomer. Such PAOs are disclosed in U.S. Patent Nos. 4,827,073, 4,827,064, 4,967,032, 4,926,004, each of which is incorporated herein by reference in its entirety. No. 4,914,254.
As described herein, R ⁴ is an alkyl group (eg, a C ₁ -C ₅₀₀ alkyl group, a C ₁ -C ₃₀₀ alkyl group, a C ₁ -C ₁₀₀ alkyl group, a C ₁ -C ₅₀ alkyl group, etc.). Alternatively, it may be an aromatic group. Thus, exemplary thiols useful in the methods described herein include, for example, aliphatic thiols and aromatic thiols. Exemplary aliphatic thiols include, for example, 1-butanethiol, 1-hexanethiol, 1-octanethiol, 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, 1-octadecanethiol, and the like. included. Other exemplary aliphatic thiols useful in the present disclosure include, for example, methanethiol (m-mercaptan), ethanethiol (e-mercaptan), 1-propanethiol (n-P mercaptan), 2-propanethiol ( 2C3 mercaptan), 1-butanethiol, (n-butylmercaptan), tert-butylmercaptan, 1-pentanethiol (pentylmercaptan), 1-hexanethiol, 1-heptanethiol (heptylmercaptan), 1-octanethiol, 1 -Nonanethiol, 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, 1-octadecanethiol, cyclohexanethiol, 2,4,4-trimethyl-2-pentanethiol, and the like, or a combination thereof.

  Exemplary aromatic thiols include, for example, thiophenol, 4-methylbenzenethiol, 4-methoxythiophenol, benzylmercaptan, 4-mercaptopyridine, 2-mercaptopyrimidine, 1-naphthalenethiol, 2-naphthalenethiol, and the like. included. Other exemplary aromatic thiols useful in the present disclosure include, for example, 2,3,4,5,6-pentafluorothiophenol, 2,3,5,6-tetrafluorothiophenol, 2,3 -Dichlorothiophenol, 2,4-dichlorothiophenol, 2,5-dichlorothiophenol, 3,4-dichlorothiophenol, 3,5-dichlorothiophenol, 2,4-difluorothiophenol, 3, 4-difluoro thiophenol, 2-bromothiophenol, 3-bromothiophenol, 4-bromothiophenol, 2-chlorothiophenol, 3-chlorothiophenol, 4-chlorothiophenol, 2-fluorothiophenol , 3-fluorothiophenol, 4-fluorothiophenol, 2- Rollo benzene methanethiol, 4-chlorobenzene methanethiol, (3-nitrobenzyl) mercaptan (Marcaptan),

(4-nitrobenzyl) mercaptan, 2-mercaptobenzyl (benzeyl) alcohol, 4-nitrothiophenol, 2-mercaptophenol, 3-mercaptophenol, 4-mercaptophenol, 2-aminothiophenol, 3-amino Thiophenol, 4-aminothiophenol, 2- (trifluoromethyl) benzenethiol, 4-bromo-2-fluorobenzylmercaptan, 4-chloro-2-fluorobenzylmercaptan, 3,4-difluorobenzylmercaptan, 3,5 -Difluorobenzyl mercaptan, 2-bromobenzyl mercaptan, 3-bromobenzyl mercaptan, 4-bromobenzyl mercaptan, 3-fluorobenzyl mercaptan, 4-fluorobenzyl mercaptan 2-methoxythiophenol, 3-methoxythiophenol, 2-methylbenzenethiol, 3-methylbenzenethiol, benzylmercaptan, 4- (methylsulfanyl) thiophenol, 2-phenoxyethanethiol, 3-ethoxythiol Phenol, 4-methoxy-α-toluenethiol, 2,5-dimethoxythiophenol, 3,4-dimethoxythiophenol, 2,4-dimethylthiophenol, 2,5-dimethylthiophenol, 2,6-dimethylthiophenol 1,3,5-dimethylthiophenol, 2,6-dimethylthiophenol, 2-ethylbenzenethiol, 2-phenylethanethiol, 1,2-benzenedimethanethiol, 1,3-benzenedimethanethiol, 4-b Benzene dithiol, 2-isopropylbenzenethiol, 4-isopropylbenzenethiol, 4- (dimethylamino) thiophenol, 1-naphthalene thiol, 2-naphthalene thiol, 2,4,6-trimethylbenzyl mercaptan, 4-tert- Butylbenzyl mercaptan, 4-tert-butylbenzenethiol, tert-dodecylmercaptan, triphenylmethanethiol, 9-fluorenylmethylthiol, 9-mercaptofluorene, and the like, or combinations thereof.

Suitable acid catalysts that can be used in the methods described herein for making compounds having formula (FI) include, for example, Lewis acids. Lewis acid catalysts useful for the coupling reaction include metal halides and metalloid halides conventionally used as Friedel-Crafts catalysts. Suitable examples include AlCl ₃ , BF ₃ , AlBr ₃ , TiCl ₃ and TiCl _{4 as} such or with a protic promoter. Other examples include solid Lewis acid catalysts, such as synthetic or natural zeolites; acid clay; polymeric acidic resins; amorphous solid catalysts, such as silica alumina; and heteropolyacids such as tungsten zirconate, tungsten molybdate, vanadate Tungsten, phosphotungstate and molybdung tungstovanado germanate (eg, WO _x / ZrO ₂ and WO _x / MoO ₃ ) are included. In addition to these catalysts, acidic ionic liquids can also be used as catalysts for the coupling reaction. Of the various catalysts, polymeric acidic resins such as Amberlyst 15, Amberlyst 36 are most preferred. Typically, the amount of acid catalyst used is between 0.1 and 30% by weight, preferably between 0.2 and 5% by weight, based on the total weight of the feed. In particular, the acid catalyst may be a solid acid catalyst selected from the group consisting of solid Lewis acids, acid clay, polymeric acid resins, silica alumina, mineral acids and combinations thereof. Examples of suitable mineral acids include hydrochloric acid (HCl), hydrobromic acid (HBr), hydrofluoric acid (HF), sulfuric acid (H ₂ SO ₄ ), phosphoric acid (H ₃ PO ₄ ), nitric acid (HNO ₃ ) and combinations thereof, but are not limited thereto.

The reaction conditions of the methods described herein, such as temperature, pressure and contact time, may also vary widely, and any suitable combination of such conditions may be used herein. Reaction temperatures may range between about 25 ° C to about 250 ° C, preferably between about 30 ° C to about 200 ° C, and more preferably between about 60 ° C to about 150 ° C. The reaction may be carried out under ambient pressure and the contact time may vary from a few seconds or minutes to several hours or more. The reactants can be added to or combined with the reaction mixture in any order. The stirring time spent can range from 0.5 to 48 hours, preferably 1 to 36 hours, more preferably 2 to 24 hours.
In another embodiment, by reacting HS-R ⁴ (ie, a thiol) with an olefin-containing material described herein, including a compound having the following formula (F-Ia), in the presence of an acid catalyst: Also provided herein are compounds having formula (FI) as described herein that are prepared.

IV. Lubricating Oils and Basestock Compositions The present disclosure provides lubricating oils useful as engine oils and in other applications, characterized by excellent stability, solvency and dispersibility properties. Lubricating oils comprise the majority comprising one or more compounds that conform in structure to Formula (F-1) described herein, and further comprise Group I, II and / or III mineral oil basestocks, GTL, Based on high quality basestocks that may include other components such as Group IV (eg, PAO), Group V (eg, esters, alkylated aromatics, PAGs) and combinations thereof. The lubricating oil basestock can be any oil that boils within the boiling range of the lubricating oil, typically between about 100 and about 450 ° C. In this specification and in the claims, the terms base oil and base stock are used interchangeably.

The viscosity-temperature relationship of a lubricating oil is one of the very important criteria that must be considered when selecting a lubricating oil for a particular application. The Viscosity Index (VI) is an empirical infinity and indicates the rate of change of the viscosity of the oil within a given temperature range. Fluids that exhibit a relatively large change in viscosity with temperature are said to have a low viscosity index. For example, low VI oils dilute faster at higher temperatures than high VI oils. Generally, high VI oils are more desirable because they have higher viscosities at higher temperatures, which results in better or thicker lubricating films and better protection of contact mechanical elements.
In another embodiment, as the oil operating temperature decreases, the viscosity of the high VI oil does not increase as much as the viscosity of the low VI oil. This is advantageous because the excessively high viscosity of the low VI oil reduces the efficiency of the working machine. Thus, high VI (HVI) oils have performance advantages in both high and low temperature operation. VI is determined according to ASTM method D2270-93 [1998]. VI relates to kinematic viscosities measured at 40 ° C. and 100 ° C. using ASTM method D445-01.

IV. A. Lubricating oil basestocks A wide variety of lubricating oils are known in the art. Lubricating oils useful in the present disclosure are both natural and synthetic. Natural and synthetic oils (or mixtures thereof) may be used as unrefined, refined or rerefined oils, the latter also being known as reclaimed or reprocessed oils. Unrefined oils are those obtained directly from a natural or synthetic source and used without further purification. These include shale oil obtained directly from retort harvesting operations, petroleum oil obtained directly from primary distillation, and ester oil obtained directly from the esterification process. Refined oils are similar to the oils described for the unrefined oils. The exception is that refined oils have been subjected to one or more refining steps to improve at least one lubricating oil property. Those skilled in the art are familiar with many purification processes. These processes include solvent extraction, secondary distillation, acid extraction, base extraction, filtration and leaching. Rerefined oils are obtained by a similar process to refined oils, but use the oils conventionally used as feedstocks.
Groups I, II, III, IV and V are rough classifications of base oil stocks created and defined by the American Petroleum Institute, which produces guidelines for lubricant base oils (API Publication 1509; www.API.org). . Group I basestocks generally have a viscosity index of 80-120 and contain more than 0.03% sulfur and less than 90% saturates. Group II basestocks generally have a viscosity index of 80-120 and contain no more than 0.03% sulfur and no less than 90% saturates. Group III stocks generally have a viscosity index of greater than 120 and contain no more than 0.03% sulfur and more than 90% saturates. Group IV contains polyalphaolefin (PAO). Group V base stocks include base stocks not included in Groups I-IV. Table III below summarizes the characteristics of each of these five groups.

Natural oils include animal oils, vegetable oils (eg, castor oil and lard oil) and mineral oils. Animal and vegetable oils having advantageous thermo-oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary greatly with respect to their source of crude, for example, whether they are paraffinic, naphthenic, or mixed paraffinic-naphthenic. Oils derived from coal or shale are also useful in the present disclosure. Natural oils also differ in the method used for their production and refining, for example, their distillation range and whether they are straight run or cracked, hydrorefined or solvent extracted.
Group II and / or Group III hydrotreated or hydrocracked basestocks, and synthetic oils such as polyalphaolefins, alkylaromatics and synthetic esters, ie, basestock oils, also known as Group IV and Group V oils It is.

Synthetic oils include hydrocarbon oils, for example, polymerized and copolymerized olefins (eg, polybutylene one, polypropylene, propylene isobutylene copolymer, ethylene-olefin copolymer and ethylene-alpha-olefin copolymer). Polyalphaolefin (PAO) oil basestocks, which are Group IV API basestocks, are commonly used synthetic hydrocarbon oils. _{Examples, C 8, C 10, C} 12, C 14 PAO or mixtures thereof derived from olefins may also be used. See U.S. Patent Nos. 4,956,122, 4,827,064 and 4,827,073, which are incorporated herein by reference in their entireties. Group IV oils, i.e., PAO basestocks, preferably have a viscosity index greater than 130, more preferably greater than 135, and even more preferably greater than 140.
In one particular embodiment, a lubricant basestock is provided. The lubricating oil basestock may comprise one or more of the compounds of formula (FI) described herein. Also contemplated herein are compounded lubricating oil compositions that include one or more of the lubricating oil basestocks described herein.
As mentioned herein, the compounds of formula (FI) have surprisingly improved oxidative and thermal stability. Thus, a composition comprising a compound of formula (F-I), such as a lubricating oil basestock composition provided herein, has a composition of at least about 200 minutes, at least about 300 minutes, measured according to ASTM Standard D-2272. Minutes, at least about 400 minutes, at least about 500 minutes, at least about 600 minutes, at least about 700 minutes, at least about 800 minutes, at least about 850 minutes, at least about 900 minutes, or about 1000 minutes of the Rotating Pressure Vessel Oxidation Test (RPVOT) interruption May have time. Additionally or alternatively, a composition comprising a compound of formula (F-I), such as a lubricating oil basestock composition provided herein may comprise from about 200 to about 1000 minutes, from about 200 to about 900 minutes. , About 300 to about 900 minutes, about 400 to about 900 minutes, about 500 to about 900 minutes, or about 400 to about 850 minutes.

Further, compositions comprising a compound of formula (FI), such as a lubricating oil basestock composition provided herein, may have a composition of from about 1 to about 20 cSt, from about 1 to about 20 cSt, measured according to ASTM standard D-445. It may have a kinematic viscosity at 100 ° C. (KV100) of from about 15 cSt, preferably from about 2 to about 20 cSt, preferably from about 2 to about 10 cSt, more preferably from about 2 to about 5 cSt.
Additionally or alternatively, a composition comprising a compound of Formula (F-I), such as a lubricating oil basestock composition provided herein, may have a composition of about 5 to about 5 measured according to ASTM Standard D-445. Kinematic viscosity of about 100 cSt, preferably about 5 to about 75 cSt, preferably about 5 to about 500 cSt, preferably about 5 to about 35 cSt, preferably about 9 to about 30 cSt, more preferably about 9 to about 25 cSt at 40C. Rate (KV40).

Additionally or alternatively, a composition comprising a compound of formula (FI), such as a lubricating oil basestock composition provided herein, may have a composition of about 5 to about 5%, measured according to ASTM Standard D-2270. It may have a viscosity index (VI) of about 200, preferably about 10 to about 200, preferably about 10 to about 180, preferably about 10 to about 150, more preferably about 10 to about 130.
Additionally or alternatively, a composition comprising a compound of formula (F-I), such as a lubricating oil basestock composition provided herein, can have up to about 35%, preferably up to about 30%, Preferably, it may have a Noack volatility of about 25% or less. As used herein, Noack evaporability is determined by ASTM D-5800.
Additionally or alternatively, a composition comprising a compound of formula (FI), such as a lubricating oil basestock composition provided herein, may be less than about -30C, less than about -40C, less than about -40C. It may have a pour point of less than -50C, less than about -60C or -70C. Preferably, the compositions provided herein can have a pour point of less than about -60C. The compositions provided herein can have a pour point of about -70C to about -30C, about -70C to about -40C, or about -70C to about -50C.

  Small amounts of esters may be useful in the lubricating oils of the present disclosure. The dissolving power and seal compatibility properties of the additives can be ensured by the use of esters such as esters of dibasic acids with monoalkanols and polyol esters of monocarboxylic acids. Esters of the former type include, for example, dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, malonic acid, alkyl malonic acid, alkenyl malonic acid and the like. And esters with various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol and the like. 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, and dioctyl phthalate. Didecyl, diicosyl sebacate and the like.

Particularly useful synthetic esters are one or more polyhydric alcohols, preferably hindered polyols, such as neopentyl polyol; for example, neopentyl glycol, trimethylolethane, 2-methyl-2-propyl-1,3. - propanediol, trimethylolpropane, pentaerythritol and dipentaerythritol, alkanoic acids containing at least 4 carbon atoms, preferably C ₅ -C ₃₀ acids, for example, caprylic acid, capric acid, lauric acid, myristic acid , Saturated linear fatty acids, including palmitic acid, stearic acid, arachiic acid and behenic acid, or the corresponding branched or unsaturated fatty acids, such as oleic acid, or a mixture of any of these materials. It is something that can be done.
The ester should be used in an amount such that the improved wear and corrosion resistance provided by the lubricating oil of the present disclosure is not adversely affected.

  Non-conventional or non-conventional base stocks and / or base oils include one or a mixture of base stocks and / or base oils derived from: (1) one or more Gas-to-liquid (GTL) materials, and (2) synthetic waxes, natural waxes or waxy feeds, mineral oils and / or non-mineral oil waxy feeds, such as gas oils, slack waxes (solvents of natural, mineral or synthetic oils) Derived by dewaxing; for example, Fischer-Tropsch feedstocks), natural waxes and waxy stocks, such as gas oils, waxy fuel hydrocracker bottoms, waxy raffinates, hydrocracked products, pyrolysis Products, waxy or other minerals, mineral oils or even non-petroleum derived waxy materials, such as Waxy material recovered from coal liquefied oil or shale oil, hydrodewaxing or hydroisomerizing / catalyzing (and / or) derived from linear or branched hydrocarbyl compounds having 20 or more, preferably 30 or more carbon atoms Solvents) Dewaxed base stocks and / or base oils and mixtures of such base stocks and / or base oils.

GTL materials are gaseous carbon-containing compounds, hydrogen-containing compounds and / or elements as feedstocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane. , A material derived from butylene and butyne by one or more synthesis, compounding, transformation, rearrangement and / or degradation / deconstruction processes. GTL basestocks and / or base oils are hydrocarbons derived themselves from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and / or elements as feedstocks; for example, those typically derived from waxy synthetic hydrocarbons. GTL material with lubricating viscosity. The GTL basestock and / or base oil is separated / fractionated from the synthetic GTL material, for example, by distillation, to produce (1) reduced pour point / low pour point tube oil; An oil boiling in the boiling range of the lubricating oil, which has been subjected to a final waxing step with one or both of a catalytic or solvent dewaxing process; (2) for example hydrodewaxing or hydroisomerization (3) hydrodewaxed or hydroisomerized catalyst and / or solvent dewaxed Fischer, comprising the synthesized catalyst and / or solvent dewaxed synthetic wax or waxy hydrocarbon. Tropsch (FT) material (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibly similar oxygenates); preferably Hydrodewaxed or hydroisomerized / subsequent catalyst and / or solvent dewaxed dewaxed FT waxy hydrocarbon, or hydrodewaxed or hydroisomerized / subsequent catalyst (or solvent) dewaxing Dewaxed FT wax or mixtures thereof are included.
GTL materials, in particular GTL basestocks derived from hydrodewaxed or hydroisomerized / subsequent catalyst and / or solvent dewaxed waxes or waxy feeds and / or base oils, preferably FT materials derived base stocks and / or base oil, typically characterized by having a kinematic viscosity at 100 ° C. of 2mm ² / s~50mm ² / s to (ASTM D445). They are further characterized by typically having a pour point (ASTM D97) of -5 ° C to -40 ° C or less. They are also typically characterized by having a viscosity index (ASTM D2270) of 80 to 140 or higher.

Furthermore, GTL basestocks and / or base oils are typically highly paraffinic (> 90% saturates) and contain a mixture of monocycloparaffins and multicycloparaffins in combination with acyclic isoparaffins. You may. The ratio of naphthenic (ie, cycloparaffin) content in such combinations varies with the catalyst and temperature used. Further, GTL basestocks and / or base oils typically have very low sulfur and nitrogen contents and generally contain less than 10 ppm, more typically less than 5 ppm, of each of these elements. I do. The sulfur and nitrogen content of GTL basestocks and / or base oils obtained from FT materials, especially FT waxes, is substantially zero. Moreover, the absence of phosphorus and aromatics makes this material substantially particularly suitable for low SAP product formulations.
The terms GTL basestock and / or base oil and / or wax isomerate basestock and / or base oil refer to individual fractions of a wide viscosity range of materials as recovered in the production process, two or more such fractions. Of one or more low viscosity fractions and one, two or more higher viscosity fractions to produce a blend exhibiting a target kinematic viscosity Should be understood to encompass
The GTL material from which the GTL basestock and / or base oil is derived is preferably an FT material (i.e., hydrocarbon, waxy hydrocarbon, wax).

  Base oils for use in compounded lubricating oils useful in the present disclosure include API Group I, Group II, Group III, Group IV due to their exceptional volatility, stability, viscosity and cleanliness characteristics. , Group V and Group VI oils and mixtures thereof, preferably API Group II, Group III, Group IV, Group V and Group VI oils and mixtures thereof, more preferably corresponding to Group III to Group VI base oils One of the various oils you want. For example, small amounts of Group I stock used in diluting additives for blending purposes in blended lubricating oil products should be acceptable but kept to a minimum, i.e., The amount should be kept as relevant for their use as diluents / carrier oils for additives used on an "as received" basis. Further, with respect to Group II stocks, the Group II stock is in the higher quality range associated with it, ie, the Group II stock has a viscosity index in the range of 100 <VI <120. Is preferred.

Furthermore, GTL basestocks and / or base oils are typically highly paraffinic (> 90% saturates) and contain a mixture of monocycloparaffins and multicycloparaffins in combination with acyclic isoparaffins. You may. The ratio of naphthenic (ie, cycloparaffin) content in such combinations varies with the catalyst and temperature used. In addition, GTL basestocks and / or base oils and hydrodewaxing or hydroisomerization / catalytic (and / or solvent) dewaxing basestocks and / or base oils typically have very low sulfur and nitrogen contents. And generally contains less than 10 ppm, more typically less than 5 ppm of each of these elements. The sulfur and nitrogen content of GTL, basestock and / or base oil obtained from FT materials, especially FT wax, is substantially zero. Further, the absence of phosphorus and aromatics makes this material particularly suitable for low sulfur, low sulfated ash and low phosphorus (low SAP) product formulations.
The base stock component of the lubricating oil present is typically from about 50% to about 99% by weight of the total composition (all percentages and percentages described herein are not stated to be so). Unless otherwise noted) and more usually in the range of about 80% to about 99% by weight.

IV. B. Other Additives Useful lubricating oils useful in the present disclosure may additionally include dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other antiwear agents and / or extreme pressure additives. Agents, anti-seizing agents, wax modifiers, viscosity index improvers, viscosity modifiers, fluid loss additives, seal compatibility agents, other friction modifiers, lubricants, stain inhibitors, chromophore agents, defoamers, anti- One or more of other commonly used lubricating oil performance additives including, but not limited to, emulsifiers, emulsifiers, densifying agents, surfactants, gelling agents, tackifiers, colorants, and others. May be contained. For a review of many commonly used additives, see Klamann in Lubricants and Related Products, Verlag Chemie, Deerfield Beach, Fla .; ISBN 0-89573-177-0. Similarly, reference can be made to “Lubricant Additives Chemistry and Applications” edited by Leslie R. Rudnick, Marcel Dekker, Inc. New York, 2003 ISBN: 0-8247-0857-1.
The types and amounts of performance additives used in combination with the present disclosure in lubricating oil compositions are not limited by the examples provided herein by way of illustration.

IV. C. Viscosity enhancers Viscosity enhancers (also known as viscosity index modifiers and VI improvers) increase the viscosity of oil compositions at elevated temperatures, which increases film thickness while having a limited effect on viscosity at low temperatures. It is.
Suitable viscosity improvers include high molecular weight hydrocarbons, polyesters and viscosity index improver dispersants that function as both viscosity index improvers and dispersants. Typical molecular masses of these polymers are between 10,000 and 1,000,000, more typically between 20,000 and 500,000, and even more typically between 50,000 and 200,000.
Examples of suitable viscosity improvers are polymers and copolymers of methacrylate, butadiene, olefin or alkylated styrene. Polyisobutylene is a commonly used viscosity index improver. Another suitable viscosity index improver is polymethacrylate (eg, a copolymer of alkyl methacrylates of various chain lengths), some formulations of which also function as pour point depressants. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (eg, copolymers of acrylates of various chain lengths). Specific examples include styrene-isoprene or styrene-butadiene based polymers with a molecular weight of 50,000-200,000.
The amount of the viscosity modifier may range from 0 to 8% by weight, preferably 0 to 4% by weight, more preferably 0 to 2% by weight, based on the active ingredient, depending on the particular viscosity modifier used. .

IV. D. Antioxidants Typical antioxidants include phenolic antioxidants, amine antioxidants and oil-soluble copper complexes. A detailed description of such antioxidants and their usage can be found, for example, in WO 2015/060984, the relevant parts of which are incorporated herein by reference in their entirety.
IV. E. FIG. Detergents In addition to the alkali or alkaline earth metal salicylate detergents that are an essential component of the present disclosure, other detergents may also be present. While such other detergents may be present, the amounts used are preferably such that they do not interfere with the synergistic effects that may be due to the presence of the salicylate. Thus, most preferably, such other cleaning agents are not used.
If such additional detergents are present, they can include alkali and alkaline earth metal phenates, sulfonates, carboxylates, phosphonates and mixtures thereof. These additional detergents have a total base number (TBN) ranging from neutral to strongly overbased, i.e., a TBN of greater than 0-500, preferably 2-400, more preferably 5-300. These can be present individually or in combination with one another in amounts ranging from 0 to 10% by weight, preferably from 0.5 to 5% by weight (active ingredient), based on the total weight of the formulated lubricating oil. I can do it. However, as described above, it is preferred that such other detergents are not present in the formulation.
Such other cleaning agents include, by way of example and not limitation, calcium carbonate, calcium sulfonate, magnesium carbonate, magnesium sulfonate and other related components (including borated cleaning agents).

IV. F. Dispersants During operation of the engine, non-oil-soluble oxidation by-products are formed. Dispersants help keep these by-products in solution, thus reducing their adhesion to metal surfaces. The dispersant may be ashless or ash-producing in nature. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that do not substantially produce ash when burned. For example, metal-free or borated metal-free dispersants are considered ashless. On the other hand, the above-mentioned metal-containing detergent generates ash when burned.
Suitable dispersants typically comprise a polar group attached to a relatively high molecular weight hydrocarbon chain. The polar group usually contains at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain 50-400 carbon atoms.

A particularly useful class of dispersants is the alkenyl succinic acid derivatives typically formed by the reaction of a long chain substituted alkenyl succinic compound, usually a substituted succinic anhydride, with a polyhydroxy or polyamino compound. The long chain groups that make up the lipophilic portion of the molecule that confers solubility in oil are usually polyisobutylene groups. Many examples of this type of dispersant are well known both commercially and in the literature. Exemplary patents that describe such dispersants are U.S. Patent Nos. 3,172,892, 3,219,666, 3,316,177 and 4,234,435. is there. Other types of dispersants are described in U.S. Patent Nos. 3,036,003 and 5,705,458.
Hydrocarbyl-substituted succinic compounds are generally preferred dispersants. In particular, a succinimide, succinate or succinate prepared by reacting a hydrocarbon-substituted succinic compound, preferably having at least 50 carbon atoms in the hydrocarbon substituent, with at least one equivalent of an alkyleneamine Amides are particularly useful.
Succinimide is formed by a condensation reaction between an alkenyl succinic anhydride and an amine. The molar ratio can vary depending on the amine or polyamine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from 1: 1 to 5: 1.

Succinates are formed by a condensation reaction between an alkenyl succinic anhydride and an alcohol or polyol. The molar ratio can vary depending on the alcohol or polyol used. For example, the condensation product of alkenyl succinic anhydride and pentaerythritol is a useful dispersant.
Succinic amides are formed by the condensation reaction between alkenyl succinic anhydrides and alkanolamines. For example, suitable alkanolamines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenyl polyamines, such as polyethylene polyamine. One example is propoxylated hexamethylenediamine.
The molecular mass of the alkenyl succinic anhydride typically ranges between 800 and 2,500. The products described above can be post-reacted with various reagents, for example, sulfur, oxygen, formaldehyde, carboxylic acids, for example, oleic acid, and boron compounds, for example, borate esters or highly borated dispersants. it can. The dispersant can be borated using from 0.1 to 5 moles of boron per mole of dispersant reaction product.
Mannich base dispersants are made by the reaction of alkylphenols, formaldehyde and amines. Processing aids and catalysts, such as oleic and sulfonic acids, can also be part of the reaction mixture. The molecular weight of the alkyl phenol ranges from 800 to 2,500.

Typical high molecular weight fatty acid modified Mannich condensation products can be prepared from high molecular weight alkyl-substituted hydroxyaromatic or HN (R) ₂ group containing reactants.
Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenol, polybutylphenol and other polyalkylphenols. These polyalkylphenols, alkylation catalysts, for example, the presence of BF _3, the polymer mass polypropylene provide an alkyl substituent having a molecular weight average in the phenolic benzene ring 600～100,000, polybutylene and other poly It can be obtained by alkylation of phenol with an alkylene compound.
Examples of HN (R) ₂ group containing reactants are alkylene polyamines, mainly polyethylene polyamines. Other representative organic compounds containing at least one HN (R) ₂ group suitable for use in the preparation of Mannich condensation products are well known and include mono- and di-aminoalkanes and their substitution. Analogs include, for example, ethylamine and diethanolamine; aromatic diamines, such as phenylenediamine, diaminonaphthalene; heterocyclic amines, such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; melamine and substituted analogs thereof. .

Examples of alkylene polyamine reactants include ethylenediamine, diethylenetriamine, triethylenetetraamine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptaamine, heptaethyleneoctamine, octaethylenenonaamine, nonaethylenedecamine and decaethyleneundeamine. Kamin and mixtures of amines such as those having a nitrogen content corresponding to alkylene polyamines of the formula _{H 2 N- (Z-NH-)} n H of the foregoing are included, Z of the above equation is a divalent ethylene, n Is 1 to 10. The corresponding propylene polyamines such as propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamine are also suitable reactants. Alkylene polyamines are usually obtained by reacting ammonia with a dihaloalkane, for example a dichloroalkane. Thus, alkylene polyamines obtained by reacting 2 to 11 moles of ammonia with 1 to 10 moles of dichloroalkane having 2 to 6 carbon atoms and chlorine on different carbons are suitable alkylene polyamine reactants.

Aldehyde reactants useful in preparing the polymeric products useful in the present disclosure include aliphatic aldehydes such as formaldehyde (as well as paraformaldehyde and formalin), acetaldehyde and aldol (β-hydroxybutyraldehyde). Formaldehyde or reactants that give formaldehyde are preferred.
Preferred dispersants include borated and non-borated succinimides, including mono-succinimides, leis-succinimides and / or derivatives from mixtures of mono- and bis-succinimides. The hydrocarbyl succinimide is derived from hydrocarbylene groups, for example polyisobutylene having a Mn of 500 to 5000 or a mixture of such hydrocarbylene groups. Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine linked Mannich adducts, capped derivatives thereof, and other related components. Such additives are used in an amount of from 0.1 to 20% by weight, based on the weight of the total lubricating oil (on an arrival basis), preferably from 0.1 to 8% by weight, more preferably from 1 to 6% by weight. May be done.
IV. G. FIG. Pour point depressants Conventional pour point depressants (also known as lube oil flow improvers) may also be present. Pour point depressants may be added to lower the minimum temperature at which the fluid will flow or can be poured. Examples of suitable pour point depressants include alkylated naphthalene polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes with aromatic compounds, vinyl carboxylate polymers and vinyl esters of dialkyl fumarate and fatty acids. And terpolymers of allyl vinyl ether. Such additives may be used in an amount of 0.0-0.5%, preferably 0-0.3%, more preferably 0.001-0.1% by weight on an as-received basis. .

IV. H. Corrosion Inhibitors / Metal Deactivators Corrosion inhibitors are used to reduce the degradation of metal parts in contact with the lubricating oil composition. Suitable corrosion inhibitors include arylthiazines, alkyl-substituted dimercaptothiodiazole thiadiazoles and mixtures thereof. Such additives may comprise from 0.01 to 0.5%, preferably from 0.01 to 1.5%, more preferably from 0.01 to 0.5% by weight (based on arrival) based on the total weight of the lubricating oil composition. -0.2% by weight, even more preferably 0.01-0.1% by weight.
IV. I. Seal Compatibility Additives Seal compatibility agents help expand elastomer seals by causing chemical reactions in the fluid or physical changes in the elastomer. Suitable seal compatibility agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (eg, butylbenzyl phthalate) and polybutenyl succinic anhydride and sulfolane-type seal swelling agents, eg, Lubrizol 730 type A seal swell additive is included. Such additives may be used in an amount of 0.01 to 3% by weight, preferably 0.01 to 2% by weight on an as-received basis.

IV. J. Defoamers Defoamers can be advantageously added to the lubricating oil composition. These agents slow the formation of stable foam. Silicones and organic polymers are typical antifoams. For example, a polysiloxane, such as silicone oil, or polydimethylsiloxane, provides defoaming properties. Defoamers are commercially available and may be used in conventional small amounts in combination with other additives, such as demulsifiers, and usually the amount of these additives combined is the total weight of the lubricating oil composition. Less than 1%, preferably 0.001 to 0.5% by weight, more preferably 0.001 to 0.2% by weight, even more preferably 0.0001 to 0.15% by weight (based on arrival basis) It is.

IV. K. Corrosion Inhibitors and Rust Inhibitors Rust inhibitors (or corrosion inhibitors) are additives that protect lubricating metal surfaces from chemical attack by water or other contaminants. One type of rust inhibitor is a polar compound that preferentially wets the metal surface and protects it with an oil film. Another type of rust inhibitor absorbs water by incorporating it into a water-in-oil emulsion, so that only oil contacts the surface. Yet another type of rust inhibitor chemically adheres to the metal to produce a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in an amount of 0.01 to 5% by weight, preferably 0.01 to 1.5% by weight on an as-received basis.
Other antiwear additives including zinc dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiocarbamate, other organic molybdenum-nitrogen complexes, sulfided olefins, etc., in addition to the ZDDP antiwear additive which is an essential component of the present disclosure May exist.
The term "organic molybdenum-nitrogen complex" includes the organic molybdenum-nitrogen complexes described in U.S. Pat. No. 4,889,647. The complex is the reaction product of a fatty oil, diethanolamine, and a molybdenum source. No specific chemical structure is assigned to the complex. In U.S. Patent No. 4,889,647, have been reported infrared spectrum of a typical reaction product of the disclosure, the spectrum, the identification amide carbonyl band of the ester carbonyl band and 1620 cm ^-1 in 1740 cm ^-1 Is done. Fatty oils are glyceryl esters of higher fatty acids containing at least 12 up to and including 22 carbon atoms. Molybdenum sources are oxygen containing compounds such as ammonium molybdate, molybdenum oxide and mixtures.

Other organomolybdenum complexes that can be used in the present disclosure are the trinuclear molybdenum-sulfur compounds described in EP 1040115 and WO 99/31113 and the molybdenum complexes described in US Pat. No. 4,978,464. It is.
In the foregoing detailed description, certain embodiments of the present disclosure have been described, together with preferred embodiments thereof. However, as long as the above description is specific to a particular embodiment or particular use of the present disclosure, this is intended to be merely exemplary and merely a brief description of the exemplary embodiment. Accordingly, the disclosure is not limited to the specific embodiments described above, but rather, the disclosure includes all alternatives, modifications, and equivalents as fall within the true scope of the appended claims. Various modifications and variations of this disclosure will be apparent to those skilled in the art, and it is understood that such modifications and variations are to be included within the scope of the present application and within the spirit and scope of the appended claims. It should be.

General Methods The lubricating oil properties of the products produced in Examples 1 and 2 were evaluated as described. The kinematic viscosity (KV) of the product was measured using ASTM standard D-445 and reported at a temperature of 100 ° C (KV100) or 40 ° C (KV40). The viscosity index (VI) was measured according to ASTM standard D-2270 using the kinematic viscosity measured for each product. The Noack evaporability of the product was measured according to ASTM standard D-5800. The pour point of the product was measured according to ASTM D5950.
In this and the following examples, unless otherwise stated, the C16 uPAO dimer used was present predominantly as (> 95%) vinylidene olefin isomer, with less than 5% trisubstitution or 1,1 With 2-disubstituted olefin isomers. C16 uPAO dimer was prepared according to the method described in WO 2007/011973, which is incorporated herein by reference in its entirety. Thus, the major C16 uPAO dimer will take one of the following forms:

この例および以下の例において、他に記載されていない限り、使用されたＣ２０ ｕＰＡＯ二量体は、ビニリデン対三置換オレフィンの質量比が２０／８０〜６０／４０の範囲内のビニリデンおよび三置換オレフィンのほぼ混合物であった。その全体が参照により本明細書に組み込まれる米国特許出願公開第２０１３／００９０２７７号の例１に記載の方法にしたがってＣ２０ ｕＰＡＯ二量体を調製した。したがって、Ｃ２０ ｕＰＡＯ二量体は、次の主要な形態をとるであろう。

In this and the following examples, unless otherwise stated, the C20 uPAO dimer used was vinylidene and trisubstituted with a mass ratio of vinylidene to trisubstituted olefin in the range of 20/80 to 60/40. It was almost a mixture of olefins. C20 uPAO dimers were prepared according to the method described in Example 1 of US Patent Application Publication No. 2013/0090277, which is incorporated herein by reference in its entirety. Thus, the C20 uPAO dimer will take the following major forms:

スキーム1 Example 1-Acid catalyzed synthesis of product I containing compound-I and compound-II To form product I containing compound-I and compound-II, 4 as shown in Scheme 1 below The C16 uPAO dimer was alkylated with acid catalyst using -methylbenzenethiol.

Scheme 1

Glass reactor under a N ₂ atmosphere C16 UPAO dimer (242.1g, 1.07mol), 4- methylbenzenethiol (160.4g, 1.29mol) (available from Sigma-Aldrich) and Amberlyst-15H ( 6.89 g, 1.7% by weight) (obtained from Sigma-Aldrich) were charged to form a mixture. The mixture was heated with stirring at 120 ° C. for 20 hours. The mixture was filtered to remove the catalyst. The filtrate was distilled at 160-205 [deg.] C under vacuum to remove unreacted olefins and thiols. The distillation pot resid was recovered as Product I containing Compound-I and Compound-II in a molar ratio of about 97.5-2.5. The lubricating oil properties of Product I were determined as described above. They are shown below in Table IV.

スキームA Example 2 Comparative Radical Synthesis of Comparative Product 1 Containing Compound-I and Compound-II To form Comparative Product 1 containing Compound-I and Compound-II, the following Scheme A The C16 uPAO dimer was alkylated with a radical initiator using 4-methylbenzenethiol as indicated.

Scheme A

Glass reactor under a N ₂ atmosphere C16 UPAO dimer (325.0g, 1.44mol), 4- methylbenzenethiol (309.0g, 2.49mol) (available from Sigma-Aldrich) and AIBN (23. (1 g, 0.17 mol) was charged to form a mixture. The reactor contents were heated with stirring at 70 ° C. for 18 hours. The reaction mixture was placed under vacuum and stripped to 185 ° C. to remove unreacted olefins and thiols. The distillation pot residue was treated with decolorizing carbon and filtered. The filtrate was recovered as Comparative Product 1 containing Compound-I and Compound-II in a molar ratio of I: II of about 1:99. The lubricating oil properties of Comparative Product 1 were determined as described above. They are shown in Table V below.

生成物Ｉおよび比較生成物１は、アルキル化チオールの同じタイプの異性体を含有するが、それらの割合は異なる。使用される触媒およびプロセス条件の性質により、二重結合への硫黄付加の位置化学を制御することができる。分子構造のこの違いは、¹Ｈおよび¹³Ｃ ＮＭＲにより明らかにすることができる。
生成物の構造を区別するために使用できる、¹Ｈ ＮＭＲにより同定できる重要な構造的特徴が少数存在する。生成物Ｉおよび比較生成物１の¹Ｈ ＮＭＲスペクトルを決定した。これらをそれぞれ図１および図２に示した。さらに、化合物−Ｉおよび化合物−ＩＩの¹Ｈ ＮＭＲ構造帰属を図３に示す。示す通り、図３において、化合物−Ｉの分子構造は、脂肪族Ｃ−Ｓ結合に隣接して位置するメチル基を含む。化学シフト１．１４ｐｐｍの一重線ピークとしてメチル基が同定できた。脂肪族Ｃ−Ｓ結合の炭素原子は水素原子を持たないため、¹Ｈ ＮＭＲには特徴がなかった。

Product I and Comparative Product 1 contain the same type of isomer of the alkylated thiol, but in different proportions. Depending on the nature of the catalyst and process conditions used, the regiochemistry of the sulfur addition to the double bond can be controlled. This difference in molecular structure can be revealed by ¹ H and ¹³ C NMR.
There are a few important structural features that can be identified by ¹ H NMR that can be used to distinguish the structure of the product. ¹ H NMR spectra of product I and comparative product 1 were determined. These are shown in FIGS. 1 and 2, respectively. FIG. 3 shows the ¹ H NMR structural assignments of Compound-I and Compound-II. As shown, in FIG. 3, the molecular structure of Compound-I contains a methyl group located adjacent to an aliphatic CS bond. A methyl group was identified as a singlet peak with a chemical shift of 1.14 ppm. Since the carbon atom of the aliphatic CS bond did not have a hydrogen atom, ¹ H NMR had no feature.

In contrast, the molecular structure of Compound-II contains a methylene group attached to a sulfur atom. This could be identified as a doublet peak at 2.85 ppm chemical shift. The carbon atom adjacent to this methylene group had one hydrogen atom, which could be identified as a heptaline peak with a chemical shift of 1.59 ppm.
Whether the structure of the product or basestock contains a sulfur atom attached to the tertiary carbon (ie, compound-I) or a sulfur atom attached to the primary carbon of the PAO moiety (ie, the compound The presence or absence of any of these ¹ H NMR peaks can be used to determine -II). These identifiable markers can be used to determine the molecular structure of the base stock and, if a blend of isomers is present, quantify the relative amounts of the different molecular isomers.

For example, the ¹ H NMR spectrum of product I shown in FIG. 1 shows a singlet peak at 1.14 ppm, indicating the presence of compound-I. It also shows a small doublet peak at 2.85 ppm, indicating the presence of a small amount of compound-II. The normalized integral indicates that the molar ratio of Compound-I to Compound-II in this product was about 97.7 to 2.5.
On the other hand, the ¹ H NMR spectrum of the comparative product 1 shown in FIG. However, no identifiable singlet peak was present at 1.14 ppm, indicating that the composition of Comparative Product I was almost quantitatively (> 99%) Compound-II.

スキーム2
Ｎ₂雰囲気下のガラス反応器にＣ２０ ｕＰＡＯ二量体（１００１．１２ｇ、３．５７ｍｏｌ）、４−メチルベンゼンチオール（５００．１０ｇ、４．０２ｍｏｌ）（Ｓｉｇｍａ−Ａｌｄｒｉｃｈから入手）およびＡｍｂｅｒｌｙｓｔ １５−Ｈ（２０．０ｇ、１．３１質量％）（Ｓｉｇｍａ−Ａｌｄｒｉｃｈから入手）を装入し、混合物を生成した。混合物を撹拌しながら１２０℃で３日間加熱した。反応混合物をＣｅｌｉｔｅに通して濾過し、触媒を除去した。濾液を真空下１４０℃で蒸留して未反応のチオールを除去し、次いで、２１５℃で蒸留して未反応のオレフィンを除去した。蒸留ポット残油を脱色炭（２０ｇ）で処理し、Ｃｅｌｉｔｅに通して濾過した。化合物−ＩＩＩと化合物−ＩＶとを含有する生成物ＩＩとして濾液を回収した。生成物ＩＩの潤滑油特性を上述の通り決定した。それらを以下に表ＶＩに示す。 Example 3-Acid catalyzed synthesis of product II containing compound-III and compound-IV To produce product II containing compound-III and compound-IV, 4 as shown below in Scheme 2 -C20 uPAO dimer was alkylated with acid catalyst using -methylbenzenethiol (obtained from Sigma-Aldrich).

Scheme 2
C20 uPAO dimer (1001.12 g, 3.57 mol), 4-methylbenzenethiol (500.10 g, 4.02 mol) (obtained from Sigma-Aldrich) and Amberlyst 15-H in a glass reactor under N ₂ atmosphere. (20.0 g, 1.31% by weight) (obtained from Sigma-Aldrich) was charged to produce a mixture. The mixture was heated at 120 ° C. with stirring for 3 days. The reaction mixture was filtered through Celite to remove the catalyst. The filtrate was distilled at 140 ° C. under vacuum to remove unreacted thiol and then at 215 ° C. to remove unreacted olefin. The distillation pot residue was treated with decolorizing carbon (20 g) and filtered through Celite. The filtrate was collected as product II containing compound-III and compound-IV. The lubricating oil properties of Product II were determined as described above. They are shown below in Table VI.

スキーム3 Example 4-Acid catalyzed synthesis of product III containing compound-V and compound-VI To produce product III containing compound-V and compound-VI, 1 as shown below in Scheme 3 -C16 uPAO dimer was alkylated by acid catalyst using octanethiol.

Scheme 3

Glass reactor under a N ₂ atmosphere C16 UPAO dimer (200.0g, 0.89mol), 1- octanethiol (157.0g, 1.07mol) (available from Sigma-Aldrich) and Amberlyst-15H (10 0.0 g, 2.7% by weight) (obtained from Sigma-Aldrich) to produce a mixture. The mixture was heated at 120 C for 20 hours. The mixture was filtered through Celite to remove the catalyst. The filtrate was distilled at 220 ° C. under vacuum to remove unreacted thiols and olefins. The distillation pot residue was treated with decolorizing charcoal and filtered through Celite. The filtrate was recovered as product III containing compound-V and compound-VI in a molar ratio of V: VI of about 78:22. The lubricating oil properties of Product III were determined as described above. They are shown below in Table VII.

スキーム4 Example 5-Acid catalyzed synthesis of product IV containing compound-VII and compound-VIII To form product IV containing compound-VII and compound-VIII, 1 -C20 uPAO dimer was alkylated by acid catalyst using octanethiol.

Scheme 4

C20 uPAO dimer (887.1 g, 3.16 mol), 1-octanethiol (554.3 g, 3.79 mol) (obtained from Sigma-Aldrich) and Amberlyst-15H (30) in a glass reactor under N ₂ atmosphere. .1 g, 3.3% by weight) (obtained from Sigma-Aldrich) were charged to form a mixture. The mixture was heated at 120 C for 20 hours. Another Amberlyst-15H (15.0 g, 1.6% by weight) was added and the reaction continued for 8 hours. The mixture was filtered through Celite to remove the catalyst. The filtrate was distilled at 100 ° C. under vacuum to remove unreacted thiol and then at 250 ° C. to remove unreacted olefin. The distillation pot residue was treated with decolorizing carbon (20 g) and filtered through Celite. The filtrate was collected as product IV containing compounds VII and VIII in a VII: VIII molar ratio of about 95: 5. The lubricating oil properties of Product IV were determined as described above. They are shown below in Table VIII.

The ¹ H NMR spectrum of the product IV was determined. They are shown in FIG. FIG. 5 shows the ¹ H NMR structural assignments of compounds VII and VIII. As shown, in FIG. 5, the molecular structure of Compound VII includes a methyl group located adjacent to an aliphatic CS bond. A methyl group was identified as a singlet peak with a chemical shift of 1.20 ppm. Since the carbon atom of the aliphatic CS bond from the PAO moiety has no hydrogen atom, ¹ H NMR was not characterized. The carbon atom of the aliphatic CS bond from the aliphatic thiol moiety has two hydrogen atoms, which could be recognized as a triplet peak at a chemical shift of 2.39 ppm.
One skilled in the art will appreciate that compound VIII will also give a triplet peak at about 2.39 ppm, but will also give another doublet peak in the range of 2.4 to 2.9 ppm. The presence or absence of this additional doublet peak was used to quantify the relative amounts of the different molecular isomers when a blend of isomers was present.

For example, in the ¹ H NMR spectrum of product IV of FIG. 4, a triplet peak at 2.39 ppm, which could indicate either compound VII or VIII, was observed. However, only the corresponding small doublet peak in the range of 2.4-2.9 ppm was observed. This, together with the observation of a strong singlet peak at 1.40 ppm, indicated that the primary structure in Product IV was Compound VII, a result of the Markovnikov addition of aliphatic thiols to the uPAO dimer. Normalization of the ¹ H NMR peak indicated that the product IV was present in a molar ratio of compound-VII to compound-VIII of 95: 5.

Example 6 Oxidation Stability Study The oxidative stability of Product I and Product III was compared to Comparative Product 1 and a conventional hydrocarbon synthesis basestock according to the method described in ASTM D2272. Conventional hydrocarbon synthetic basestocks tested were PAO 4 and Synesstic ™ 5 (both available from ExxonMobil Chemical Company, 27111 Springwoods Village Parkway, Spring, Texas 77389, USA). The Rotating Pressure Vessel Oxidation Test (RPVOT) interruption time for each product tested is shown in FIG. Aromatic moieties tend to impart improved oxidative stability to basestock molecules. Thus, aromatic-containing Synestic ™ 5 has a longer RPVOT downtime than aliphatic PAO 4 basestock. In particular, both the S-containing aromatic basestocks from Product I and Comparative Product 1 have a longer RPVOT interruption time than Synesstic ™ 5, which means that the S atoms are further added to the aromatic-containing basestock. It shows that oxidative stability can be provided. Furthermore, the presence of sulfur atoms in other aliphatic basestock molecules can improve oxidative stability. For example, the product III basestock has a longer RPVOT downtime compared to a hydrocarbon basestock, eg, PAO4.
The RPVOT downtime of the product I base stock is much longer than the comparative product 1 base stock, indicating that the regiochemistry of the sulfur addition and the location of the sulfur atom can strongly influence the oxidative stability. The base stock of product I, which is mainly derived from the Markovnikov addition of sulfur to the PAO olefin, has improved oxidative stability over the base stock of comparative product 1.

All patents and patent applications, test procedures (eg, ASTM methods, UL methods, etc.) and other documents cited herein are not allowed to incorporate such disclosures unless such disclosure conflicts with the present disclosure. Is incorporated by reference in its entirety for all jurisdictions.
When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While exemplary embodiments of the present disclosure have been described in detail, various other modifications will become apparent to those skilled in the art, and various other modifications may be made without departing from the spirit and scope of the present disclosure. It will be appreciated that modifications can be easily made by those skilled in the art. Accordingly, the claims appended hereto are not intended to be limited to the examples and illustrations set forth herein, but rather will be treated as equivalents by those skilled in the art to which this disclosure pertains. It is intended that the appended claims cover all features of patentable novelty that exist in this disclosure, including all features.

  The present disclosure has been described above with reference to a number of embodiments and examples. Many modifications will occur to those skilled in the art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims.

Claims (25)

The following formula (FI)

(FI)
[Where,
R ¹ is a C ₁ -C ₅₀₀₀ alkyl group;
R ² represents (i) a C ₄ -C ₃₀ linear alkyl group, or (ii) a compound represented by the following formula (F-II):

(F-II)
Wherein R ⁵ and R ⁶ at each occurrence are each independently hydrogen or a C ₁ -C ₃₀ straight-chain alkyl group, n is a positive integer, provided that all R ⁵ and R 6 ⁶ , at least one is a C ₁ -C ₃₀ straight-chain alkyl group, and R ⁷ is hydrogen or a C ₁ -C ₃₀ straight-chain alkyl group)
A C ₄ -C ₅₀₀₀ branched chain alkyl group having the formula:
R ³ is hydrogen or a C ₁ -C ₅₀₀₀ alkyl group;
R ⁴ is a C ₁ -C ₅₀ alkyl group or an aromatic group]
A lubricating oil basestock comprising a compound having the formula: R ³ is hydrogen, lubricating oil base stock according to claim 1. R ³ is C ₁ -C ₁₀₀ alkyl group, a lubricating oil base stock according to claim 1. R ¹ is C ₁ -C ₃₀ straight chain alkyl group, a lubricating oil base stock according to claim 1. R ² is C ₄ -C ₃₀ straight-chain alkyl group, a lubricating oil base stock according to claim 1. R ² is a branched alkyl group represented by the formula (F-II), and the following conditions:
(I) at least 50% hydrogen R ^5, at least 50% of the R ⁶ is, C ₁ -C is ₃₀ straight chain alkyl group independently; at least 50% and (ii) R ^5, independently ^6. The lubricating base stock of claim 5, wherein the base stock is a C ₁ -C ₃₀ straight chain alkyl group, wherein at least 50% of R ⁶ is hydrogen. Of all the R ⁵ and R ^6, at least 50 mole% is a C ₄ -C ₃₀ straight-chain alkyl group independently, lubricating oil base stock according to claim 1.   The lubricating oil base stock according to claim 1, wherein n is from 50 to 500.   The lubricating base stock according to claim 1, wherein n is 2-50. R ¹ and R ² are the same or different and are each independently C ₁ -C ₁₀₀ straight-chain alkyl group, a lubricating oil base stock according to claim 1. R ¹ and R ² are the same or different and are each independently C ₁ -C ₃₀ straight chain alkyl group, a lubricating oil base stock according to claim 1. R ⁴ is, C ₁ -C ₅₀ straight chain alkyl, preferably a C ₁ -C ₃₀ straight chain alkyl group, a lubricating oil base stock according to claim 1. R ⁴ is an aromatic group, a lubricating oil base stock according to claim 1.   A lubricating oil basestock according to claim 6, having an isotacticity of at least about 60 mol%, preferably at least about 75 mol%, more preferably at least about 80 mol%.   The lubricating oil basestock of claim 1 having a Rotating Pressure Vessel Oxidation Test (RPVOT) downtime of at least about 200 minutes. A method for producing a lubricating oil basestock according to claim 1, comprising:
In the presence of an acid catalyst, HS-R ⁴ is converted to the following formula (F-Ia)

(F-Ia)
Reacting with an olefin-containing material comprising a compound having the formula: Wherein the olefin comprises at least about 75% by weight of a compound of formula R ³ is hydrogen (F-Ia), A method according to claim 16. Wherein the olefin is, R ³ comprises at least about 50 wt% of the compound of formula is a C ₁ -C ₁₀₀ alkyl group (F-Ia), A method according to claim 16. The olefin comprises (i) about 50-90% by weight of a compound of formula (F-Ia) wherein R ³ is hydrogen; and (ii) a compound of formula (F-Ia) wherein R ³ is a C ₁ -C ₁₀₀ alkyl group. 17. The method of claim 16, comprising a mixture of the compound with about 10-50% by weight of the compound. Olefin-containing material, C ₁ -C ₁₀₀ alpha in the presence of a metallocene compound - are produced by the oligomerization of olefins, the method according to claim 16.   21. The method of claim 20, wherein the olefin-containing material has an isotacticity of at least about 60 mol%, preferably at least about 75 mol%, more preferably at least about 80 mol%.   17. The method of claim 16, wherein the acid catalyst is selected from the group consisting of Lewis acids, acid clay, polymeric acid resins, heteropoly acids, acidic ionic liquids and combinations thereof.   17. The method according to claim 16, wherein at least about 90 mol%, preferably at least about 95 mol%, of the compound produced is consistent in structure with formula (F-1).   A compounded lubricating oil composition comprising the lubricating oil basestock of claim 1.   25. The compounded lubricating oil composition of claim 24, wherein the lubricating oil basestock is present in an amount from about 50% to about 99% by weight.

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