KR20190097179A - Highly stable lubricant base stock and preparation method thereof - Google Patents

Abstract

상기 식에서, R¹은 C₁-C₅₀₀₀ 알킬 기이고;
R²는 (i) C₄-C₃₀ 선형 알킬 기 또는 (ii) 하기 화학식 (F-II)를 갖는 C₄-C₅₀₀₀ 분지형 알킬이고:

;
여기서, 각 경우 R⁵ 및 R⁶은 각각 독립적으로 수소 또는 C₁-C₃₀ 선형 알킬 기이고 n은 양의 정수이며, 단, 전체 R⁵ 및 R⁶ 중에서, 적어도 하나는 C₁-C₃₀ 선형 알킬 기이고; R⁷은 수소 또는 C₁-C₃₀ 선형 알킬 기이고; R³은 수소 또는 C₁-C₅₀₀₀ 알킬 기이고; R⁴는 C₁-C₅₀ 알킬 기 또는 방향족 기이다. 또한 화학식 (F-I)의 화합물을 비롯하여 화학식 (F-I)의 화합물을 함유하는 베이스 스톡 및 윤활제 조성물을 제조하는 방법이 제공된다. Provided herein are compounds having the formula (FI):

In which R ¹ is a C ₁ -C ₅₀₀₀ alkyl group;
R ² is (i) a C ₄ -C ₃₀ linear alkyl group or (ii) C ₄ -C ₅₀₀₀ branched alkyl having the formula (F-II):

;
Wherein in each case R ⁵ and R ⁶ are each independently hydrogen or a C ₁ -C ₃₀ linear alkyl group and n is a positive integer, provided that at least one of all R ⁵ and R ⁶ is C ₁ -C ₃₀ linear An alkyl group; R ⁷ is hydrogen or a C ₁ -C ₃₀ linear alkyl group; 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. Also provided are methods of making base stock and lubricant compositions containing a compound of Formula (FI), including a compound of Formula (FI).

Description

Highly stable lubricant base stock and preparation method thereof

Priority claim

This application is filed on January 17, 2017. Claimed benefit of Provisional Application No. 62 / 446,943, the disclosure of which is incorporated herein by reference.

Field of invention

The present disclosure relates to sulfur containing compounds, methods for the preparation of sulfur containing compounds, and lubricant base stocks and lubricants comprising sulfur containing compounds with increased thermal and oxidative stability.

Lubricants for commercial use today are made from a variety of natural and synthetic base stocks mixed with various additive packages and solvents, depending on their intended application. Base stocks typically include mineral oils, polyalpha-olefins (PAO), gas liquefied (GTL) base oils, silicone oils, phosphate esters, diesters, polyol esters, and the like.

A major trend in passenger engine oil (PCEO) is the improvement in overall quality as higher quality base stocks become more readily available. Typically the highest quality PCEO products are combined with base stocks such as PAO or GTL stocks.

PAO and GTL stocks are an important class of lubricant base stocks with many good lubricating properties, including high viscosity index (VI), but can have low thermal and oxidative stability. Thermal and oxidative stability is important because of the tendency to require smaller sump sizes that can result in more thermal and oxidative stress in the lubricant. Furthermore, the performance requirements for lubricants have become stricter and the demand for longer drainage intervals continues to increase.

Sulfur may enter the base stock due to its antioxidant capacity. Sulfated PAO (S-PAO) base stocks can provide improved oxidative stability, improved durability during exposure to high temperatures, and can extend the life of the lubricant as a whole, but the synthesis of S-PAO base stocks is not limited to 3 Differential CH bonds can be introduced. For example, under radical initiation conditions, as shown in Scheme A, known below, wherein R can be an alkyl group or an aromatic compound,

Sulfur addition follows the well known "anti-Markovnikov addition", where the sulfur atom is bonded to a less substituted carbon atom of a non-hydrogenated PAO oligomer derived double bond and tertiary CH at S-PAO. To form a bond. Such hydrogen atoms of C-H bonds may be particularly unstable for oxidative cleavage due to low tertiary C-H bond dissociation energy. Thus, such tertiary C-H bonds may tend to be oxidatively degraded, thus lowering the oxidative stability of S-PAO.

Therefore, there is a need for a process for producing S-PAO with increased thermal and oxidative stability and S-PAO without introducing oxidatively unstable tertiary C-H bonds. More particularly, there is a need for S-PAO wherein a sulfur atom is bonded with a more highly substituted carbon atom of a double bond derived from an unhydrogenated PAO oligomer and a method of making the same.

It was unexpectedly found that higher stability S-PAO can be selectively synthesized via acid catalysis without introducing oxidatively unstable tertiary C-H bonds.

Accordingly, the present disclosure relates, in part, to lubricant base stocks comprising compounds having the formula (F-I):

In which R ¹ is a C ₁ -C ₅₀₀₀ alkyl group; R ² is (i) a C ₄ -C ₃₀ linear alkyl group or (ii) a C ₄ -C ₅₀₀₀ branched alkyl group having the formula (F-II):

;

;

Wherein in each case R ⁵ and R ⁶ are each independently hydrogen or a C ₁ -C ₃₀ linear alkyl group and n is a positive integer, provided that at least one of all R ⁵ and R ⁶ is C ₁ -C ₃₀ linear An alkyl group; R ⁷ is hydrogen or a C ₁ -C ₃₀ linear alkyl group; R ³ is hydrogen or a C ₁ -C ₅₀₀ alkyl group; R ⁴ is a C ₁ -C ₅₀ alkyl group or an aromatic group.

The present disclosure also relates in part to a process for preparing a base stock comprising a compound of formula (FI) and / or a compound having formula (FI), wherein the process comprises HS-R ⁴ and Reacting an olefin containing material comprising a compound having the formula:

.

.

The present disclosure also relates in part to formulated lubricants comprising at least one of the lubricant bases described herein.

Other embodiments, including specific aspects of the embodiments summarized above, will become apparent through the following detailed description.

1 illustrates a ¹ H NMR spectrum of product I.
2 illustrates a ¹ H NMR spectrum of Comparative Product 1. FIG.
3 illustrates the ¹ H NMR structural arrangement of Compound-I and Compound-II.
4 illustrates a ¹ H NMR spectrum of product IV.
5 illustrates the ¹ H NMR structural arrangement of compounds VII and VIII.
6 illustrates the oxidative stability of Product I, Product III, Comparative Product 1, PAO 4 and Synesstic ™ 5. FIG.

In various aspects of the invention, catalysts and methods of making the catalysts are provided.

I. Definition

For purposes of the present invention and claims therein, the numbering system for periodic table groups is in accordance with the IUPAC Periodic Table of January 1, 2017.

As used herein in phrases such as "A and / or B", "and / or" is intended to include "A and B", "A or B", "A", and "B".

The terms "substituent", "radical", "group", and "moiety" may be used interchangeably.

As used herein, unless otherwise specified, the term “C _n ” refers to hydrocarbon (s) having n carbon atom (s) per molecule, where n is a positive integer.

As used herein, unless otherwise specified, the term "hydrocarbon" refers to a class of compounds containing hydrogen bonded to carbon, including (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and ( iii) encompassing 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" means a saturated hydrocarbon radical having 1 to 1000 carbon atoms (ie, C ₁ -C ₁₀₀₀ alkyl). Examples of alkyl groups include, without limitation, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl and the like. Alkyl groups may be linear, branched or cyclic. "Alkyl" is intended to encompass all structural isomers of the alkyl group. For example, as used herein, propyl encompasses both n-propyl and isopropyl; Butyl encompasses n-butyl, sec-butyl, isobutyl and tert-butyl and the like. As used herein, "C ₁ alkyl" means methyl (-CH ₃ ), "C ₂ alkyl" means ethyl (-CH ₂ CH ₃ ), and "C ₃ alkyl" means propyl (-CH ₂ CH ₂ CH ₃ ) and isopropyl, "C ₄ alkyl" means a butyl group (eg, -CH ₂ CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) CH ₂ CH ₃ , -CH ₂ CH (CH ₃ ) _2, etc.). In addition, as used herein, "Me" means methyl, "Et" means ethyl, "i-Pr" means isopropyl, "t-Bu" means tert-butyl and "Np" means neopentyl.

As used herein, unless otherwise specified, the term "aromatic" means an unsaturated hydrocarbon comprising an aromatic ring in its structure, which aromatic ring has an unlocalized conjugated π system and preferably has 4 to 20 carbons. Has an atom. Exemplary aromatics include, but are not limited to, benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, naphthalene, methylnaphthalene, dimethylnaphthalene, ethylnaphthalene, acenaphthalene, anthracene, phenanthrene, tetraphene, naphthacene, benzanthracene, fluorine Tren, pyrene, chrysene, triphenylene, and the like, and combinations thereof. Aromatics can optionally 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, without limitation, nitrogen, oxygen, and / or sulfur. Aromatics having one or more heteroatoms in the aromatic ring include, without limitation, 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, only monocyclic and bicyclic rings, or only monocyclic rings) and may be fused rings.

As used herein, the term "olefin" refers to an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon to carbon double bond in its structure, wherein the carbon to carbon double bond does not form part of an aromatic ring. Do not. The olefin may be straight chain, branched chain, or cyclic. "Olefin" is intended to cover all structural isomeric forms of the olefin unless stated to mean a single isomer or otherwise clearly indicated in the context.

As used herein, the term "alpha-olefin" refers to an olefin having a terminal carbon to carbon double bond ((R ₁ R ₂ ) -C = CH ₂ ) in its structure.

As used herein, "polyalpha-olefin (s)"("PAO(s)") includes any oligomer (s) and polymer (s) of one or more alpha-olefin monomer (s). Thus, the PAO can be a dimer, trimer, tetramer, or any other oligomer or polymer comprising two or more structural units derived from one or more alpha-olefin monomer (s). PAO molecules can be highly regio-regular, such that bulk materials exhibit isotacticity or syndiotacticity as measured by ¹³ C NMR. PAO molecules can be highly position-irregular so that bulk materials are substantially atactic as measured by ¹³ C NMR. PAO materials prepared using metallocene-based catalyst systems are typically referred to as metallocene-PAO (“mPAO”) and are traditional non-metallocene-based catalysts (eg, Lewis acids, supported chromium oxides). PAO materials prepared using Etc.) are typically referred to as conventional PAO (“cPAO”).

Without further hydrogenation, PAO molecules obtained by polymerization or oligomerization of alpha-olefin monomers typically contain ethylenically unsaturated C═C double bonds in their structure. Non-hydrogenated PAOs are sometimes referred to herein as "uPAOs." The uPAO material is, in particular, vinyl (FA below, wherein R is alkyl), 2,2-double-substituted olefin (hereafter FB, also called vinylidene, wherein R1 and R2 are the same or different and alkyl ), 1,2-di-substituted olefins (also known as double-substituted vinylenes), the E- and Z-isomers of the following F-C1 and F-C2, wherein R ₁ and R ₂ are Same or different, and alkyl), and triple-substituted olefins (as FD below, also known as triple-substituted vinylene, wherein R ₁ , R ₂ , and R ₃ are the same or different, alkyl Im). Vinyl and vinylidene are terminal olefins, while double- and triple-substituted vinylene olefins are internal olefins.

uPAO can be hydrogenated in the presence of hydrogen and a hydrogenation catalyst to reduce its ethylenic unsaturation and yield hydrogenated PAO. Such hydrogenated PAOs can be more stable compared to corresponding uPAOs, providing higher heat and oxidation resistance. uPAO may be otherwise chemically modified to obtain derivatives thereof in view of the chemical reactivity of the ethylenic C═C double bonds therein. 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 modification.

As used herein, the term "lubricant" means a material that can flow between two or more moving surfaces and reduce the friction between two adjacent surfaces that move relative to each other. Lubricant "base stock" is a material, typically a fluid at the operating temperature of a lubricant, that is mixed with other components and used to blend the lubricant. Non-limiting examples of suitable base stocks for lubricants include API Group I, Group II, Group III, Group IV, Group V, and Group VI base stocks. PAOs, especially hydrogenated PAOs, have recently found widespread use in lubricant formulations as Group IV base stocks.

NMR spectroscopy provides key structural information about the synthesized polymer. Proton NMR ( ¹ H-NMR) analysis of uPAO provides quantitative analysis of olefinic structure types (ie, vinyl, 1,2-di-substituted vinylene, triple-substituted vinylene, and vinylidene). In the present disclosure, a composition of a mixture of olefins comprising terminal olefins (vinyl and vinylidene) and internal olefins (1,2-di-substituted vinylene and tri-substituted vinylene) uses ¹ H-NMR Is determined. In particular, NMR equipment of at least 500 MHz is operated under the following conditions: 30 ° flip angle RF pulse, 120 scans, 5 seconds delay between pulses; Sample dissolved in CDCl ₃ (deuterated chloroform); And signal acquisition temperature of 25 ° C. The following approach is considered in determining the concentration of various olefins among all the olefins from the NMR graph. First, the peaks corresponding to the different types of hydrogen atoms in vinyl (T1), vinylidene (T2), 1,2-disubstituted vinylene (T3), and triple-substituted vinylene (T4) are It is identified in the peak region of Table 1 below. Secondly, integrate the regions of each said peak (individually A1, A2, A3, and A4). Third, the quantity of each type of olefin (individually Q1, Q2, Q3, and Q4) as moles is calculated (individually as A1 / 2, A2 / 2, A3 / 2, and A4). Fourth, the total quantity (Qt) of all olefins as moles is calculated as the sum of all four types (Qt = Q1 + Q2 + Q3 + Q4). Finally, based on the total molar quantity of all olefins, the molar concentrations of each type of olefins (individually C1, C2, C3, and C4, mol%) are calculated (in each case Ci = 100 * Qi / Qt).

Carbon-13 NMR ( ¹³ C-NMR) is used to determine the stereoregularity of the PAOs of the present invention. Carbon-13 NMR is (m, m) -triad (ie, meso, meso), (m, r )-(Ie meso, racemic) and (r, r)-(ie racemic, racemic) can be used to determine the concentration of the triad, represented by the triad. The concentration of these triads defines whether the polymer is isotactic, atactic or syndiotactic. In the present disclosure, the concentration of (m, m) -triads in mole% is reported as the isotacticity of the PAO material. The spectra for the PAO samples are obtained in the following manner. Approximately 100-1000 mg of PAO sample is dissolved in 2-3 mL of chloroform-d for ¹³ C-NMR analysis. The sample is operated with a 60 second delay and a 90 ° pulse with at least 512 transitions. Stereoregularity was calculated using peaks around 35 ppm (CH ₂ peak by branch point). Analysis of the spectra is described in Kim, I .; Zhou, J.-M .; and Chung, H. Journal of Polymer Science: Part A: Polymer Chemistry 2000, 38 1687-1697. The calculation of stereoregularity is mm * 100 / (mm + mr + rr) for the mole percentage of (m, m) -triad and mr * 100 / (mm for the mole percentage of (m, r) -triad + mr + rr) and rr * 100 / (mm + mr + rr) for the mole percentage of (r, r) -triad. (m, m) -triad corresponds to 35.5-34.55 ppm, (m, r) -triad corresponds to 34.55-34.1 ppm, and (r, r) -triad corresponds to 34.1-33.2 ppm.

II. Sulfur-containing compounds useful for base stocks

The present disclosure relates to sulfur containing compounds, which are useful in base stock compositions due to their increased thermal and oxidative stability. In particular, thiol compounds using acid catalysts to bond mainly sulfur atoms to the more substituted carbon atoms of the double bonds of uPAO instead of to sulfur atoms to avoid the formation of oxidatively unstable tertiary CH bonds. And sulfur-containing compounds that can be selectively synthesized from non-hydrogenated PAO (uPAO). Thus, provided herein are compounds having the formula (F-I):

Where

R ¹ is a C ₁ -C ₅₀₀₀ alkyl group;

R ² is (i) a C ₄ -C ₃₀ linear alkyl group or (ii) C ₄ -C ₅₀₀₀ branched alkyl having the formula (F-II):

;

;

Wherein in each case R ⁵ and R ⁶ are each independently hydrogen or a C ₁ -C ₃₀ linear alkyl group, n is a positive integer, provided that at least one of all R ⁵ and R ⁶ is C ₁ -C ₃₀ linear An alkyl group; R ⁷ is hydrogen or a C ₁ -C ₃₀ linear alkyl group;

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.

In one embodiment, R ³ may be hydrogen, for example when uPAO used during synthesis is vinylidene olefin.

Alternatively, R ³ is a 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, a 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 groups, C ₁ -C ₂₀₀ alkyl groups, C ₁ -C ₁₀₀ alkyl groups, C ₁ -C ₅₀ alkyl groups, C ₁ -C ₃₀ alkyl groups, or C ₁ -C ₁₀ alkyl groups. Alkyl groups may be linear 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, 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 groups, C ₁ -C ₂₀₀ alkyl groups, C ₁ -C ₁₀₀ alkyl groups, C ₁ -C ₅₀ alkyl groups, C ₁ -C ₃₀ alkyl groups, or C ₁ -C ₁₀ alkyl groups.

In certain stars, R ² is each independently C ₄ -C ₃₀ linear alkyl group, C ₄ -C ₂₄ linear alkyl group, C ₄ -C ₂₀ linear alkyl group, C ₄ -C ₁₈ linear alkyl group or It may be a C ₄ -C ₁₆ linear alkyl group.

In other embodiments, R ¹ can be a C ₁ -C ₁₀₀ linear alkyl group, a C ₁ -C ₅₀ linear alkyl group, a C ₁ -C ₃₀ linear alkyl group or a C ₁ -C ₁₀ linear alkyl group, and R ² is C ₄ -C ₃₀ linear alkyl group, C ₄ -C ₂₄ linear alkyl group, C ₄ -C ₂₀ linear alkyl group, C ₄ -C ₁₈ linear alkyl group, C ₄ -C ₁₆ linear alkyl group or C ₁ -C ₁₄ linear It may be an alkyl group.

In certain stars, R ¹ or R ² may be a C ₄ -C ₅₀₀₀ branched alkyl group represented by the above formula (F-II) in which n is greater than one (1) and at least 50% of R ⁵ (eg, At least 60%, 70%, 80%, 90%, or even 95%) is hydrogen and at least 50% (eg, at least 60%, 70%, 80%, 90%, or even 95%) of R ⁶ ) Is independently a C ₁ -C ₃₀ linear alkyl group. In certain stars, at least a portion of R ⁵ and at least a portion of R ⁶ are alkyl groups, of which at least 80% of R ⁵ alkyl groups are C ₁ -C ₄ linear alkyl groups and at least 80% of R ⁶ are C ₄ -C ₃₀ linear alkyl groups. In certain stars, all R ⁵ are hydrogen and all R ⁶ are the same or different and are independently C ₁ -C ₃₀ linear alkyl groups. In certain stars, all R ⁵ are hydrogen and all R ⁶ are the same C ₁ -C ₃₀ linear alkyl group.

In certain Star, R ¹ or R ² include, for at least 50% (for the C ₄ -C may be an ₅₀₀₀ branched alkyl, R ⁶ of the formula (F-II), at least 60%, 70%, 80%, 90%, or even 95%) is hydrogen and at least 50% (eg, at least 60%, 70%, 80%, 90%, or even 95%) of R ⁵ are independently C ₁ − C ₃₀ linear alkyl group. In certain embodiments, at least a portion of R ⁶ and at least a portion of R ⁵ are alkyl groups, wherein at least 80% of R ⁶ alkyl groups are C ₁ -C ₄ linear alkyl groups and at least 80% of R ⁵ are C ₄ -C ₃₀ linear alkyl groups. In certain stars, all R ⁶ are hydrogen and all R ⁵ are the same or different and are independently C ₁ -C ₃₀ linear alkyl groups. In certain stars, all R ⁶ are hydrogen and all R ⁵ are the same C ₁ -C ₃₀ linear alkyl group.

Additionally or alternatively, R ⁴ is 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, a C ₁ -C ₃₀ alkyl group or C _It may be a ₁ -C ₁₀ alkyl group. Alkyl groups may be linear or branched. In particular, R ⁴ may be a C ₁ -C ₅₀ alkyl group, more particularly a C ₁ -C ₅₀ linear alkyl group or a C ₁ -C ₃₀ linear alkyl group.

Additionally or alternatively, R ⁴ can be an aromatic group. Suitable aromatic groups are optionally substituted with one or more alkyl groups, alkoxy groups or halogens (eg F, Cl, Br), hydroxyl groups, nitro groups, and heteroatoms (eg N, O, At least one phenyl group, optionally containing S). For example, the aromatic group is without limitation 4-methylphenyl, 4-methoxyphenyl, benzyl, 2-naphthyl, 1-naphthyl, pyridinyl, 2,3,4,5,6, -pentafluorophenyl, 2 , 3,5,6-tetrafluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4 -Difluorophenyl, 3,4-difluorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2- Fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorobenzyl, 4-chlorobenzyl, 3-nitrobenzyl, 4-nitrobenzyl, 2-benzyl alcohol, 4-nitrophenyl, 2-hydride 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-bromobenzyl, 3-bromobenzyl, 4-bro Benzyl, 3-fluorobenzyl, 4-fluorobenzyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-methylphenyl, 3-methylphenyl, 4- (methylsulfanyl) phenyl, 2 -Phenoxyethyl, 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 combinations thereof.

Examples of compounds of formula (F-I) are shown in Table II below.

Compounds of formula (F-I) described herein may have various levels of stereo-regularity. For example, each compound of formula (F-I) may be substantially atactic, isotactic, or syndiotactic. However, the compounds may be mixtures of different molecules, each of which may be atactic, isotactic, or syndiotactic. While not intending to be bound to a particular theory, position-regulated molecules, particularly isotactic, include compounds of formula (FI) described herein due to the regular distribution of pendant groups, especially longer ones. It is believed that there is a tendency to contribute to the increased performance of the base stock (eg, electrohydraulic lubrication performance). 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 of the compounds of formula (FI) described herein It is preferred that about 90 mol%, or even about 95 mol% is site-regular. At least about 50 mole%, or at least about 60 mole%, or at least about 70 mole%, or at least about 75 mole%, or at least about 80 mole%, or at least about 90 of the compounds of formula (FI) described herein More preferably, mole%, or even about 95 mole%, is isotactic.

III. Process for producing sulfur containing compound

Provided herein are methods of preparing compounds of formula (FI). In particular, the method comprises reacting an olefin containing material comprising HS-R ⁴ (ie thiol) with a compound having the formula (F-Ia) in the presence of an acid catalyst:

.

.

Wherein R ¹ _, R ² , R ³ and R ⁴ are As described above in connection with formula (FI).

As described above, under radically initiated conditions, the synthesis of S-PAO according to Scheme A follows the addition of anti-markovniccove, which introduces tertiary C-H bonds in addition to sulfur atoms. Such tertiary C-H bonds tend to be oxidatively degraded, which may lower the oxidative stability of S-PAO. It was unexpectedly found that oxidation-stable enhanced sulfur atoms can be introduced through the process described herein without introducing oxidatively labile tertiary C-H bonds simultaneously. Indeed, compounds of formula (FI) having increased thermal and oxidative stability (S-PAO) are capable of combining thiol compounds and uPAO under acid catalyzed conditions such that sulfur atoms bind to more highly substituted carbon atoms of a double bond from a uPAO oligomer. Can be prepared by reaction.

Thus, advantageously, the methods described herein have a high selectivity to produce compounds whose structure corresponds to formula (F-I). 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 about 99 mol% of the prepared compound Corresponds to formula (FI). 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 prepared compound Has a structure corresponding to formula (FI). Theoretically, although this reaction has a selectivity of less than 90 mol%, the product mixture can nevertheless be purified to obtain a final product with the desired product of purity higher than 90 mol%. In some instances, the valence of the formed S-PAO compound has a sulfur atom bonded to a primary or secondary carbon derived from uPAO.

In various aspects, R ³ can be hydrogen. In some examples, the olefin containing material comprises at least about 1.0 wt%, at least about 10 wt%, at least about 20 based on the total weight of the olefin containing material of at least one olefin compound of formula (F-Ia), wherein R ³ is hydrogen. 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 wt% , 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) in which R ³ is hydrogen in an amount of at least about 75% by weight. Additionally or alternatively, the olefin containing material may contain about 1.0% to about 100%, about 1.0% to about 99%, 1.0% to about 90% by weight of the compound of formula (F-Ia) wherein R ³ is hydrogen Wt%, about 20 wt% to about 90 wt%, about 40 wt% to about 90 wt%, about 50 wt% to about 90 wt%, about 60 wt% to about 90 wt%, about 75 wt% to about 90 Weight percent or from about 80 weight percent to about 90 weight percent.

Alternatively, R ³ is a 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, a 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 groups, C ₁ -C ₂₀₀ alkyl groups, C ₁ -C ₁₀₀ alkyl groups, C ₁ -C ₅₀ alkyl groups, C ₁ -C ₃₀ alkyl groups, or C ₁ -C ₁₀ alkyl groups. In some examples, the olefin containing material comprises at least about 1.0 compound 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. Wt%, at least about 10 wt%, at least about 20 wt%, at least about 25 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%, at least about 80%, at least about 90%, at least about 99%, or about 100% by weight. In particular, the olefin containing material may comprise a compound of formula (F-Ia) in which R ³ is an alkyl group (eg, a C ₁ -C ₁₀₀ alkyl group) in an amount of at least about 50% by weight. Additionally or alternatively, the olefin containing material may contain from about 1.0% to about 100%, 1.0% by weight of a compound of Formula (F-Ia) wherein R ³ is an alkyl group (eg, a C ₁ -C ₁₀₀ alkyl group) % To about 99%, 1.0% to about 90%, about 10% to about 60%, about 10% to about 50%, about 10% to about 40%, or about 10% by weight To about 25% by weight.

In some embodiments, the olefin containing material may comprise a mixture of compounds of formula (F-Ia). For example, the olefin containing material may comprise (i) at least one olefin compound of formula (F-Ia) wherein R ³ is hydrogen; And (ii) a mixture of one or more compounds of formula (F-Ia) wherein R ³ is 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 olefin compounds of Formula (F-Ia) wherein R ³ is hydrogen; And (ii) from about 1.0% to about 99% by weight of a mixture of one or more olefin compounds of formula (F-Ia) wherein R ³ is an alkyl group (eg, a C ₁ -C ₁₀₀ alkyl group). Can be. In particular, the olefin containing material may comprise (i) about 50% to about 90% or about 75% to about 90% by weight of at least one olefin compound of formula (F-Ia) wherein R ³ is hydrogen; And (ii) from about 10 wt% to about 50 wt% or from about 10 wt% to about 25 wt% of Formula (F-Ia), wherein R ³ is an alkyl group (eg, a C ₁ -C ₁₀₀ alkyl group) It may include a mixture of one or more olefin compounds of.

Olefin-containing materials used in this process include PAO (mPAO, cPAO, and mixtures thereof) dimers (C ₄ -C ₁₀₀ ), trimers (C ₆ -C ₁₀₀ ), tetramers (C ₈ -C ₁₀₀ ), Dimers, hexamers, 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.

PAO dimers (eg, mPAO, cPAO) can be any dimer with terminal C═C double bonds prepared using metallocenes or other single-site catalysts. Dimers can be alpha-olefins (eg, C ₂ -C ₃₀ alpha-olefins), for example 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octa Or combinations of decene or alpha-olefins. In particular, the olefin containing material in the methods provided herein can be prepared by oligomerization of C ₁ -C ₁₀₀ alpha-olefins in the presence of a metallocene compound. Metallocene-catalyzed alpha-olefin oligomerization methods are described in US Pat. Nos. 5,688,887 and 6,043,401 and WO 2007/011973, each of which is incorporated herein by reference in its entirety, feeds, metals Reference is made to the details of the Rosene catalyst, preparation conditions and characterization of the product.

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%, 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 can be prepared using conventional catalysts to form olefin containing materials having formula (F-Ib). Examples of suitable conventional catalysts include without limitation Lewis acid compounds such as BF ₃ , AlCl ₃ , aluminum trialkyl, or combinations thereof. When using conventional catalysts, the final olefin containing material tends to be a mixture of olefin compounds having highly variable R ¹ , R ² and R ³ . At least one of R ¹ , R ² and R ³ may be alkyl having a carbon backbone chain having a plurality of pendant groups attached thereto, many of which are short chain alkyl such as methyl, ethyl and the like. The distribution of such pendant groups on the backbone chain can be random. Such non-hydrogenated cPAOs obtained using conventional catalysts can typically be atactic. Methods for preparing cPAO are described, for example, in US Pat. No. 3,149,178; 3,382,291; 3,742,082; 3,769,363; 3,780,128; 3,780,128; No. 4,172,855; And 4,956,122; Shubkin, RL (Ed.) (1992) Synthetic Lubricants and High-Performance Functional Fluids (Chemical Industries) New York: Marcel Dekker Inc, each of which is incorporated herein by reference in its entirety.

PAO lubricant compositions found to have little double bond isomerization resulted in a different class of high viscosity index PAO (HVI-PAO), which is also contemplated for use herein. In a class of HVI-PAO, the reduced chromium catalyst reacts with alpha-olefin monomers. Such PAOs are U.S. Patent number 4,827,073; 4,827,064; No. 4,967,032; 4,926,004; And 4,914,254, each of which is incorporated herein by reference in its entirety.

As described herein, R ⁴ is an alkyl group (eg, C ₁ -C ₅₀₀ alkyl group, C ₁ -C ₃₀₀ alkyl group, C ₁ -C ₁₀₀ alkyl group, C ₁ -C ₅₀ alkyl group, etc. ) Or aromatic groups. 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. . Other exemplary aliphatic thiols useful in the present disclosure include, for example, methanethiol (m-mercaptan), ethanethiol (e-mercaptan), 1-propanethiol (nP mercaptan), 2-propanethiol (2C3 mer) Captan), 1-butanethiol, (n-butyl mercaptan), tert-butyl mercaptan, 1-pentane thiol (pentyl mercaptan), 1-hexanethiol, 1-peptane thiol (heptyl mercaptan), 1-octane Thiols, 1-nonanethiol, 1-decanethiol, 1-dodecanethiol, 1-hexadecanethiol, 1-octadecanethiol, cyclohexanethiol, 2,4,4-trimethyl-2-pentanethiol and the like or these It includes a combination of.

Exemplary aromatic thiols are, for example, thiophenol, 4-methylbenzenethiol, 4-methoxythiophenol, benzyl mercaptan, 4-mercaptopyridine, 2-mercaptopyrimidine, 1-naphthalenethiol, 2-naphthalene Thiols and the like. Other exemplary aromatic thiols useful in the present disclosure are, 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- Difluorothiophenol, 2-bromothiophenol, 3-bromothiophenol, 4-bromothiophenol, 2-chlorothiophenol, 3-chlorothiophenol, 4-chlorothiophenol, 2-fluorothio Phenol, 3-fluorothiophenol, 4-fluorothiophenol, 2-chlorobenzenemethanethiol, 4-chlorobenzenemethanethiol, (3-nitrobenzyl) mercaptan, (4-nitrobenzyl) mercaptan, 2- Mercaptobenyl alcohol, 4-nitrothiophenol, 2-mercaptophenol, 3-mercaptophenol, 4-mercaptophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2- ( Trifluoromethyl) benzenethiol, 4-bromo-2-fluoro Benzyl mercaptan, 4-chloro-2-fluorobenzyl mercaptan, 3,4-difluorobenzyl mercaptan, 3,5-difluorobenzyl mercaptan, 2-bromobenzyl mercaptan, 3-bromo Benzyl 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-ethoxythiolphenol, 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-dimethylthio Phenol, 2-ethylbenzenethiol, 2-phenylethanethiol, 1,2-benzenedimethanethiol, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 2-isopropylbenzenethiol, 4- Isopropylbenzenethiol, 4- (dimethylamino) thiophenol, 1-naphthalenethiol, 2-naphthalenethiol, 2,4,6-trimethylbene Jyl mercaptan, 4-tert-butylbenzyl mercaptan, 4-tert-butylbenzenethiol, tert-dodecyl mercaptan, triphenylmethanethiol, 9-fluorenylmethylthiol, 9-mercaptofluorene, or the like, or these It includes a combination of.

Suitable acid catalysts that can be used in the methods described herein to prepare compounds having formula (FI) include, for example, Lewis acids. Lewis acid catalysts useful in the coupling reaction include metal and metalloid halides commonly used as Friedel-Krafts catalysts. Suitable examples include AlCl ₃ , BF ₃ , AlBr ₃ , TiCl ₃ , and TiCl ₄ as such or in combination with quantum promoters. Other examples include solid Lewis acid catalysts such as synthetic or natural zeolites; Acid clays; Polymeric acid resins; Amorphous solid catalysts such as silica-alumina; And heteropolyacids such as tungsten zirconate, tungsten molybdate, tungsten vanadate, phosphotungstate and molybdo tungsutovanadogermanate (eg, WO _x / ZrO ₂ and WO _x / MoO ₃ ). In addition to these catalysts, acidic ionic liquids can also be used as catalysts for coupling reactions. Among the different catalysts, polymeric acid resins such as Amberlyst 15, Amberst 36 are most preferred. Typically, the amount of acid catalyst used is from 0.1 to 30% by weight, and preferably from 0.2 to 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, acidic clays, polymeric acidic resins, silica-alumina, mineral acids and combinations thereof. Examples of suitable mineral acids include, without limitation, 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 It includes.

Reaction conditions for the methods described herein, such as temperature, pressure and contact time, may also be quite variable and any suitable combination of these conditions may be applied herein. The reaction temperature may range from about 25 ° C to about 250 ° C, and preferably from about 30 ° C to about 200 ° C, more preferably from about 60 ° C to about 150 ° C. The reaction may be carried out at atmospheric pressure and the contact time may vary from approximately a few seconds or minutes to several hours or more. The reactants may be added to the reaction mixture or combined in any order. The stirring time applied may range from 0.5 to 48 hours, preferably 1 to 36 hours, and more preferably 2 to 24 hours.

In another embodiment, prepared herein by reacting HS-R ⁴ (ie, thiol) with an olefin containing material comprising a compound having the formula (F-Ia) as described herein in the presence of an acid catalyst Also provided herein are compounds having Formula (FI) as described herein.

IV. Lubricant and Base Stock Compositions

The present disclosure provides lubricants useful as engine oils and in other applications that are characterized by good stability, solubility and dispersibility characteristics. The lubricating oil is the main part comprising one or more compounds corresponding to the structure of formula (F-1) as described herein and also optionally other components such as group I, II and / or III mineral oil base stocks. , GTL, Group IV (eg, PAO), Group V (eg, esters, alkylated aromatics, PAG) and combinations thereof, based on high quality base stocks. The lubricant base stock can be any oil boiling in the lubricant boiling range, typically from about 100 to about 450 ° C. In this specification and claims, the terms base oil (s) and base stock (s) are used interchangeably.

The viscosity-temperature relationship of lubricants is one of the key criteria that must be considered when selecting lubricants for specific applications. Viscosity index (VI) is an experimental, dimensionless number which means the rate of change of viscosity of an oil within a predetermined temperature range. Fluids that exhibit relatively large changes in viscosity with temperature have a low viscosity index. The low VI oil will thin at high temperatures, for example faster than the high VI oil. In general, high VI oils are more preferred because they have higher viscosity at higher temperatures, which translates into better or thicker lubrication film and better protection of the contacting machine components.

In another aspect, if the oil operating temperature is reduced, the viscosity of the high VI oil will not increase as much as the viscosity of the low VI oil. This is advantageous because excessively high viscosity of low VI oil will reduce the efficiency of the work machine. High VI (HVI) oils therefore have performance advantages in both high and low temperature operations. VI is determined according to ASTM method D 2270-93 [1998]. VI relates to kinematic viscosity measured at 40 ° C. and 100 ° C. using ASTM method D 445-01.

IV.A. Lubricant base stock

A wide variety of lubricants are known in the art. Lubricants useful in the present disclosure are both natural and synthetic oils. Natural and synthetic oils (or mixtures thereof) can be used crude, purified or refined (the latter also reclaimed or reprocessed oils). Crude oil is obtained directly from natural or synthetic sources and used without further purification. These include shale oils obtained directly from the distillation operation, petroleum obtained directly from the primary distillation, and ester oils obtained directly from the esterification process. Refined oils are similar to the oils described for the crude oil except that the refined oil is subjected to one or more refining steps to improve at least one lubricant 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 exudation. Refined oils use oils previously used as feedstock but are obtained in a similar process as refined oils.

Groups I, II, III, IV and V are a broad category of base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to generate guidelines for lubricating base oils. Group I base stocks generally have a viscosity index of 80 to 120 and contain more than 0.03% sulfur and less than 90% saturates. Group II base stocks generally have a viscosity index of 80 to 120 and contain up to 0.03% sulfur and at least 90% saturates. Group III stocks generally have a viscosity index of greater than 120 and contain up to 0.03% sulfur and more than 90% saturates. Group IV includes polyalpha-olefins (PAO). Group V base stocks include base stocks not included in Group I-IV. Table III below summarizes the characteristics of each of these five groups.

Natural oils include animal oils, vegetable oils (castor oil and lard oils, for example), and mineral oils. Animal and vegetable oils that possess the desired thermal oxidation stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils vary widely depending on their crude source, 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 vary depending on the method used for their preparation and purification, such as their distillation range and whether they are direct current or decomposition, water clarifier or solvent extraction.

Synthetic oils such as polyalpha-olefins, alkyl aromatics and synthetic esters, ie Group IV and Group V oils, including Group II and / or Group III hydrotreated or hydrocracked base stocks, are also well known base stock oils.

Synthetic oils include hydrocarbon oils such as polymerized and interpolymerized olefins (polybutyl on, polypropylene, propylene isobutylene copolymers, ethylene-olefin copolymers, and ethylene-alpha-olefin copolymers, for example). Polyalpha-olefin (PAO) oil base stocks, group IV API base stocks are commonly used synthetic hydrocarbon oils. As an example, PAOs derived from C ₈ , C ₁₀ , C ₁₂ , C ₁₄ olefins or mixtures thereof can be used. US Patent No. 4,956,122; 4,827,064; And 4,827,073, which are incorporated herein by reference in their entirety. Group IV oils, ie PAO base stocks, preferably have a viscosity index of greater than 130, more preferably greater than 135, even more preferably greater than 140.

In one particular embodiment, a lubricant base stock is provided. Lubricant base stocks may include one or more compounds of formula (F-I) as described herein. Also contemplated herein are formulated lubricant oil compositions that include one or more of the lubricant base stocks described herein.

As described herein, compounds of formula (F-I) have unexpectedly increased oxidation and thermal stability. Thus, a composition comprising a compound of Formula (FI), eg, a lubricant base stock composition provided herein, is at least about 200 minutes, at least about 300 minutes, at least about 400, measured according to ASTM standard D-2272. A rotation pressure vessel oxidation test (RPVOT) breakdown time of 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. Additionally or alternatively, a composition comprising a compound of Formula (FI), such as a lubricant base stock composition provided herein, has a RPVOT break time of about 200 to about 1000 minutes, 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.

In addition, a composition comprising a compound of Formula (FI), for example, a lubricant base stock composition provided herein, can be used in the range of about 1 to about 20 cSt, about 1 to about 15 cSt, measured according to ASTM standard D-445. , Preferably about 2 to about 20 cSt, preferably about 2 to about 10 cSt, and more preferably about 2 to about 5 cSt, having a kinematic viscosity at 100 ° C. (KV100).

Additionally or alternatively, a composition comprising a compound of Formula (FI), eg, a lubricant base stock composition provided herein, is about 5 to about 100 cSt, preferably measured in accordance with ASTM standard D-445. Kinematic viscosity at 40 ° C. of 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, and more preferably about 9 to about 25 cSt It may have (KV40).

Additionally or alternatively, a composition comprising a compound of Formula (FI), eg, a lubricant base stock composition provided herein, is from about 5 to about 200, preferably about, measured according to ASTM standard D-2270. It may have a viscosity index (VI) of 10 to about 200, preferably about 10 to about 180, preferably about 10 to about 150, and more preferably about 10 to about 130.

Additionally or alternatively, a composition comprising a compound of Formula (FI), eg, a lubricant base stock provided herein, may be about 35% or less, preferably about 30% or less, and more preferably about 25% or less It can have noack volatility. As used herein, noark volatility is determined by ASTM D-5800.

Additionally or alternatively, a composition comprising a compound of Formula (FI), eg, a lubricant base stock provided herein, may be less than about −30 ° C., less than about −40 ° C., less than about −50 ° C., about − It may have a pour point of less than 60 ° C or -70 ° C. Preferably, the compositions provided herein can have a pour point of less than about -60 ° C. The compositions provided herein can have a pour point of about -70 ° C to about -30 ° C, about -70 ° C to about -40 ° C, or about -70 ° C to about -50 ° C.

Small amounts of esters may be useful in the lubricating oils of the present disclosure. Further solubility and sealing suitability features can be ensured by the use of esters such as mono alkanol and dibasic acids and polyol esters of monocarboxylic acids. The former ester types are for example various alcohols such as butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol and the like, dicarboxylic acids such as phthalic acid, succinic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, Esters such as malonic acid, alkyl malonic acid, alkenyl malonic acid and the like. Specific examples of these types of esters are dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, isodecyl alkate, dioctyl Phthalates, didecyl phthalates, diicosyl sebacates and the like.

Particularly useful synthetic esters include one or more polyhydric alcohols, preferably steric hindrance polyols such as neopentyl polyols; For example, neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol, trimethylol propane, pentaerythritol and dipentaerythritol contain at least 4 carbon atoms. Saturated straight-chain fatty acids or the corresponding, including alkanoic acids, preferably C ₅ to C ₃₀ acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, and behenic acid Branched or unsaturated fatty acids such as oleic acid, or mixtures of any of these materials.

The ester should be used in such an amount that the improved wear and corrosion resistance provided by the lubricating oil of the present disclosure is not negatively affected.

Atypical or unusual base stocks and / or base oils include (1) one or more liquefied gas (GTL) materials, and (2) synthetic waxes, natural waxes or wax sources, mineral and / or non-mineral oil wax feedstocks. For example, diesel, slack wax (derived from solvent desalination of natural oils, mineral oils or synthetic oils; for example Fischer-Tropsch feedstock), natural waxes, and lead stocks such as diesel, lead fuel hydrocracker residues, lead raffinate , Hydrolyzate, pyrolysate, lead oil or other minerals, mineral oils or even non-petroleum-based lead materials such as lead recovered from coal liquefaction or shale oil, 20 or more, preferably 30 or more carbon numbers Hydrodewaxing, or hydroisomerization / catalyst (and / or solvent) dewaxing bases derived from linear or branched hydrocarbyl compounds having One or mixtures of the base (s) and / or base oil and base stock (s) and / or base oil (s) derived from such base stocks and / or mixtures of base oils.

GTL materials include gaseous carbon-containing compounds, hydrogen-containing compounds and / or components as feedstocks such as hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propene, butane, butylene, and A material derived from one of the butenes through synthesis, combining, conversion, rearrangement, and / or decomposition / disassembly processes. GTL base stocks and / or base oils are hydrocarbons; For example, simpler gas carbon-containing compounds, hydrogen-containing compounds and / or GTL materials of lubricating viscosity generally derived from leaded synthetic hydrocarbons which are themselves derived from components as feedstocks. The GTL base stock (s) and / or base oil (s) may be (1) to produce a reduced / low pour point tube oil, such as, for example, one of distillation and subsequent catalytic dewaxing, or solvent dewaxing. Or an oil boiling in the lubricating oil boiling range separated / fractionated from the synthesized GTL material by performing a final wax processing step comprising both; (2) synthesized wax isomers, including, for example, hydrodewaxed or hydroisomerization catalysts and / or solvent dewaxed synthesized waxes or leady hydrocarbons; (3) hydrodewaxing or hydroisomerization catalysts and / or solvent dewaxing Fischer-Tropsch (F-T) materials (ie, hydrocarbons, lead hydrocarbons, waxes and possible analogous oxygenates); Preferably de-lead F-T leaded hydrocarbons that are hydrodewaxed or hydroisomerized / post-catalyst and / or solvent-dewaxed, or de-dewaxed, F-T wax, or mixtures thereof.

Base oil (s) derived from the GTL base stock (s) and / or GTL material, in particular the catalyst and / or solvent dewaxed wax or lead source, preferably base stock (s) and / or hydrodewaxed or hydroisomerized / after Or the FT material derived from the base oil (s) typically has a kinematic viscosity at 100 ° C. of 2 mm 2 / s to 50 mm 2 / s (ASTM D445). They are further characterized by having a pour point (ASTM D97) of -5 ° C to -40 ° C or less. They are also typically characterized as having a viscosity index (ASTM D2270) of 80 to 140 or more.

In addition, the GTL base stock (s) and / or base oil (s) are typically highly paraffinic (> 90% saturates) and may contain a mixture of monocycloparaffins and multicycloparaffins in combination with acyclic isoparaffins. Can be. The proportion of naphthenic (ie cycloparaffin) content in this combination varies with the catalyst and temperature used. In addition, GTL base stock (s) and / or base oil (s) typically have very low sulfur and nitrogen contents, which generally contain less than 10 ppm, more typically less than 5 ppm, each of these elements. The sulfur and nitrogen content of the GTL base stock (s) and / or base oil (s) obtained from the F-T material, in particular the F-T wax, is substantially zero. In addition, the absence of phosphorus and aromatics makes these materials particularly suitable for the formulation of low SAP products.

The terms GTL base stock and / or base oil and / or wax isomer base stock and / or base oil are blends as blends exhibiting target kinematic viscosities, including individual fractions of these materials of a wide range of viscosities recovered in the manufacturing process, and mixtures of two or more of these fractions. It is to be understood that it encompasses a mixture of one, two or more higher viscosity fractions and one or more low viscosity fractions to produce.

The GTL material from which the GTL base stock (s) and / or base oil (s) are derived is preferably an F-T material (ie hydrocarbon, lead hydrocarbon, wax).

Base oils for use in formulated lubricants useful in the present disclosure include API Group I, Group II, Group III, Group IV, 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 any of a variety of oils corresponding to group III to group VI base oils due to their exceptional volatility, stability, viscosity and cleanliness properties. A small amount of Group I stock, such as the amount used to dilute the additive for mixing in the formulated lubricant product, can be tolerated, but diluent / carrier oil for the additive used in a minimum amount, ie on an "as received" basis. It should only be maintained in quantities associated with their use. Even in the context of group II stocks, group II stocks are preferably higher quality ranges associated with the stocks, ie group II stocks having a viscosity index in the range of 100 <VI <120.

In addition, the GTL base stock (s) and / or base oil (s) are typically highly paraffinic (> 90% saturates) and may contain a mixture of monocycloparaffins and multicycloparaffins in combination with acyclic isoparaffins. Can be. The proportion of naphthenic (ie cycloparaffin) content in this combination varies with the catalyst and temperature used. In addition, GTL base stock (s) and / or base oil (s) and hydrodewaxing, or hydroisomerization / catalyst (and / or solvent) dewaxing base stock (s) and / or base oil (s) typically have very low sulfur and It has a nitrogen content, which generally contains less than 10 ppm of each of these elements, and more typically less than 5 ppm. The sulfur and nitrogen content of GTL, base stock (s) and / or base oil (s) obtained from F-T materials, in particular F-T wax, is substantially zero. In addition, the absence of phosphorus and aromatics makes this material particularly suitable for combinations of low sulfur, sulfurized ash and phosphorus (low SAP) products.

The components of the base stock of the lubricating oils of the present invention typically range from about 50% to about 99% by weight of the total composition (all ratios and percentages described herein are by weight unless otherwise specified) and more generally about 80% by weight. To about 99% by weight.

IV.B. Other additives

Formulated lubricating oils useful in the present disclosure are, without limitation, dispersants, other detergents, corrosion inhibitors, rust inhibitors, metal deactivators, other antiwear and / or extreme pressure additives, fusion inhibitors, wax modifiers, viscosity index improvers, viscosity One or more other agents including modifiers, fluid-loss additives, seal compatibility agents, other friction modifiers, lubricants, antifouling agents, colorants, antifoams, demulsifiers, emulsifiers, extenders, wetting agents, gelling agents, tackifiers, colorants, and the like. It may contain commonly used lubricant performance additives. 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. See also "" 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 lubricant compositions are not limited by the examples shown herein illustrated.

IV.C. Viscosity improver

Viscosity improvers (also called viscosity index modifiers, and VI improvers) have a limited effect on viscosity at low temperatures, but increase the viscosity of the oil composition at high temperatures that increase film thickness.

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 weights of these polymers are 10,000 to 1,000,000, more typically 20,000 to 500,000, and even more typically 50,000 to 200,000.

Examples of suitable viscosity improving agents are copolymers and polymers of methacrylate, butadiene, olefins, or alkylated styrenes. Polyisobutylene is a commonly used viscosity index improver. Other suitable viscosity index improvers are polymethacrylates (eg, copolymers of various chain length alkyl methacrylates), and some combinations thereof also serve as pour point lowering agents. Other suitable viscosity index improvers include copolymers of ethylene and propylene, hydrogenated block copolymers of styrene and isoprene, and polyacrylates (eg, copolymers of various chain length acrylates). Specific examples include styrene-isoprene or styrene-butadiene based polymers of 50,000 to 200,000 molecular weight.

The amount of viscosity modifier may range from 0 to 8% by weight, preferably 0 to 4% by weight, more preferably 0 to 2% by weight, depending on the particular viscosity modifier used based on the active ingredient.

IV.D. Antioxidant

Typical antioxidants include phenolic antioxidants, amine antioxidants and oil soluble copper complexes. A detailed description of these antioxidants and their use can be found, for example, in WO2015 / 060984 A1, the relevant parts of which are incorporated herein by reference in their entirety.

IV.E. Detergent

In addition to alkali or alkaline earth metal salicylate detergents, which are essential ingredients in the present disclosure, other detergents may also be present. While such other detergents may be present, it is preferred that the amount applied does not interfere with the synergistic effects, for example due to the presence of salicylate. Therefore, most preferably such other detergents do not apply.

If such additional detergents are present, they may include alkali and alkaline earth metal phenates, sulfonates, carboxylates, phosphonates and mixtures thereof. These supplemental detergents may have a total base (TBN) in the neutral to high overbased range, ie 0 to 500, preferably 2 to 400, more preferably 5 to 300 TBN, and they have a total of formulated lubricants It may be present in combination or separately from one another in amounts ranging from 0 to 10% by weight, preferably from 0.5 to 5% by weight (active ingredient), by weight. However, as stated previously, it is preferred that such other detergents not be present in the formulation.

Such further other detergents include, by way of example and without limitation, calcium phenate, calcium sulfonate, magnesium phenate, magnesium sulfonate and other related ingredients (including borated detergents).

IV.F. Dispersant

During engine operation, oil-insoluble oxidation by-products are produced. Dispersants help maintain these byproducts in solution, reducing their deposition on metal surfaces. Dispersants may be ashless in nature or may be ash-forming. Preferably, the dispersant is ashless. So-called ashless dispersants are organic materials that do not substantially form ash upon combustion. For example, metal-free or borated metal-free dispersants are considered ashless. In contrast, the metal-containing detergents discussed above form ash upon combustion.

Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. Polar groups typically contain at least one element of nitrogen, oxygen, or phosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

Particularly useful classes of dispersants are alkenyl succinic acid derivatives, which are typically prepared by reacting long-chain substituted alkenyl succinic compounds, generally substituted succinic anhydrides, with polyhydroxy or polyamino compounds. The long chain group constituting the lipophilic portion of the molecule that imparts solubility in oil is generally a polyisobutylene group. Many examples of this type of dispersant are well known in the literature and commercially. Exemplary patents describing such dispersants include U.S. Pat. Patent number 3,172,892; 3,219,666; 3,316,177 and 4,234,435. Another type of dispersant is U.S. Patent number 3,036,003; And 5,705,458.

Hydrocarbyl-substituted succinic acid compounds are popular dispersants. Particularly useful are succinimides, succinate esters, or succinate ester amides, preferably prepared by reacting a hydrocarbon-substituted succinic acid compound having at least 50 carbon atoms with at least one equivalent of an alkylene amine, preferably with a hydrocarbon substituent. .

Succinimide is formed by the condensation reaction between alkenyl succinic anhydride and 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.

Succinate esters are formed by condensation reactions between alkenyl succinic anhydrides and alcohols or polyols. The molar ratio can vary depending on the alcohol or polyol used. For example, condensation products of alkenyl succinic anhydride and pentaerythritol are useful dispersants.

Succinate ester amides are formed by the condensation reaction between alkenyl succinic anhydrides and alkanol amines. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine.

The molecular weight of the alkenyl succinic anhydride will typically range from 800 to 2,500. The product can be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid, and boron compounds such as borate esters or highly borated dispersants. The dispersant may be borated with 0.1 to 5 moles of boric acid per mole of dispersant reaction product.

Mannich base dispersants are prepared by the reaction of alkylphenols, formaldehyde, and amines. Process aids and catalysts such as oleic acid and sulfonic acid may also be part of the reaction mixture. The molecular weight of alkylphenols ranges from 800 to 2,500.

Typical high molecular weight aliphatic acid modified Mannich condensation products can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or HN (R) ₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenols, polybutylphenols, and other polyalkylphenols. These polyalkylphenols are phenols with high molecular weight polypropylene, polybutylene, and other polyalkylene compounds, in the presence of alkylation catalysts such as BF ₃ to provide alkyl substituents on the benzene ring of phenols having an average molecular weight of 600-100,000. It can be obtained by alkylation of.

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 the Mannich condensation product are well known and are mono- and di-amino alkanes and their substituted analogs such as ethylamine and Diethanol amines; Aromatic diamines such as phenylene diamine, diamino naphthalene; Heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine, and piperidine; Melamine and substituted analogs thereof.

Examples of alkylene polyamine reactants include ethylenediamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexamine, hexaethylene heptaamine, heptaethylene octaamine, octaethylene nonaamine, nonaethylene decamine, And such amines having a nitrogen content corresponding to decaethylene undecamine and the aforementioned alkylene polyamines of the formula H ₂ N- (Z-NH-) _n H wherein Z is divalent ethylene and n is 1 to 10. It contains a mixture of. Corresponding propylene polyamines such as propylene diamine and di-, tri-, tetra-, pentapropylene tri-, tetra-, penta- and hexaamine are also suitable reactants. Alkylene polyamines are generally obtained by the reaction of ammonia and dihalo alkanes such as dichloro alkanes. Thus alkylene polyamines obtained by reacting 1 to 10 moles of dichloroalkane having 2 to 6 carbon atoms and chlorine on different carbons with 2 to 11 moles of ammonia are suitable alkylene polyamine reactants.

Aldehyde reactants useful in the preparation of the polymeric products useful in the present disclosure include aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (β-hydroxybutyraldehyde). Formaldehyde or formaldehyde-producing reactants are preferred.

Preferred dispersants include borated and unborated succinimides, including these derivatives from mono-succinimides, leis-succinimides, and / or mixtures of mono- and bis-succinimides Hydrocarbyl succinimides are derived from hydrocarbylene groups such as 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-coupled Mannich adducts, their capped derivatives, and other related components. Such additives may be used in amounts of 0.1 to 20% by weight, preferably 0.1 to 8% by weight, more preferably 1 to 6% by weight, based on the weight of the total lubricant.

IV.G. Pour point reducer

Conventional pour point depressants (also called lubricant flow improvers) may also be present. Pour point depressants can be added to lower the minimum temperature at which the fluid can flow or be poured. Examples of suitable pour point depressants include condensation products of alkylated naphthalene polymethacrylates, polyacrylates, polyarylamides, haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and dialkylfumarates, vinyl esters and allyl vinyl ethers of fatty acids. Terpolymer of. Such additives may be used in amounts of from 0.0 to 0.5% by weight, preferably from 0 to 0.3% by weight, more preferably from 0.001 to 0.1% by weight, as received.

IV.H. Corrosion Inhibitors / Metal Deactivators

Corrosion inhibitors are used to reduce the decomposition of metallic parts that come into contact with the lubricating oil composition. Suitable corrosion inhibitors include aryl thiazines, alkyl substituted dimercapto thiadiazole thiadiazoles and mixtures thereof. Such additives are present in an amount of from 0.01 to 0.5% by weight, preferably from 0.01 to 1.5% by weight, more preferably from 0.01 to 0.2% by weight, even more preferably from 0.01 to 0.1% by weight, based on the total weight of the lubricant composition. Can be used as

IV.I. Sealing compatibility additive

Sealing compatibilizers help to cause swelling of the elastomeric seal by causing a physical change in the elastomer or a chemical reaction in the fluid. Sealing suitable agents for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (butylbenzyl phthalate, for example), and polybutenyl succinic anhydrides and sulfolane-type seal swelling agents such as Lubrizol 730-type seal swelling additives. Include. Such additives may be used in amounts of from 0.01 to 3% by weight, preferably from 0.01 to 2% by weight, as received.

IV.J. Antifoam

Antifoams may advantageously be added to the lubricant. These formulations delay the formation of stable foams. Silicones and organic polymers are typical antifoams. For example, polysiloxanes such as silicone oils or polydimethyl siloxanes provide antifoaming properties. Antifoaming agents are commercially available and can be used conventionally in small amounts with other additives such as demulsifiers; Generally the amount of these additives formulated is less than 1%, preferably 0.001 to 0.5% by weight, more preferably 0.001 to 0.2% by weight, still more preferably 0.0001 to 0.15% by weight, based on the total weight of the lubricating oil composition )to be.

IV.K. Corrosion Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces against chemical attack by water or other contaminants. One type of antirust additive is a polar compound that preferentially wets the metal surface, protecting it with an oil film. Another type of antirust additive is introduced into the water-in-oil emulsion so that only oil is in contact with the surface to adsorb water. Another type of antirust additive is chemically attached to the metal to create 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 amounts of 0.01 to 5% by weight, preferably 0.01 to 1.5% by weight, as received.

In addition to the ZDDP antiwear additives that are an essential component of the present disclosure, other antiwear additives include zinc dithiocarbamate, molybdenum dialkyldithiophosphate, molybdenum dithiocarbamate, other organo molybdenum-nitrogen complexes, sulfide olefins, and the like. May exist.

The term “organo molybdenum-nitrogen complex” encompasses the organo molybdenum-nitrogen complex described in US Pat. No. 4,889,647. This complex is the reaction product of fatty oil, diethanolamine and molybdenum sources. No special chemical structure has been designated for this complex. US Patent 4,889,647 reports infrared spectra of typical reaction products of the disclosure; This spectrum identifies the ester carbonyl band at 1740 cm ⁻¹ and the amide carbonyl band at 1620 cm ⁻¹ . Fatty oils are glyceryl esters of higher fatty acids containing at least 12 carbon atoms to 22 carbon atoms or more. Molybdenum sources are oxygen-containing compounds such as ammonium molybdate, molybdenum oxide and mixtures.

Other organo molybdenum complexes that can be used in the present disclosure include the triple-nuclear molybdenum-sulfur compounds and U.S. compounds described in EP 1 040 115 and WO 99/31113. Molybdenum complexes described in patent 4,978,464.

In the foregoing detailed description, specific embodiments of the present disclosure have been described in conjunction with preferred embodiments thereof. However, to the extent that the above description is particular to a particular embodiment or a particular use of the present disclosure, it is intended to be illustrative only and provides a concise description of the exemplary embodiment only. Accordingly, the disclosure is not limited to the particular embodiments described above, but instead the disclosure includes all alternatives, modifications, and equivalents falling within the scope of the appended claims. It will be understood that various modifications and variations of the present disclosure will be apparent to those skilled in the art and such modifications and variations are included within the spirit and scope of the present application and claims.

Example

General way

Lubricant properties of the products prepared in Examples 1 and 2 were evaluated as provided. 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). Viscosity index (VI) was measured according to ASTM standard D-2270 using kinematic viscosity measured for each product. Noark volatility of the product was measured according to ASTM standard D-5800. Pour point of the product was measured according to ASTM D5950.

In the following examples herein, unless otherwise specified, the C16 uPAO dimers used are primarily (> 95%) as vinylidene olefin isomers having <5% triple or 1,2-disubstituted olefin isomers. C16 uPAO dimers were prepared according to the method described in International Publication No. WO2007 / 011973, the entirety of which is incorporated herein by reference. Thus, the predominant C16 uPAO dimer will take one of the following forms:

In this specification and in the examples below, unless otherwise specified, the C20 uPAO dimer used was an approximate mixture of vinylidene and trisubstituted olefins having a weight ratio of vinylidene to trisubstituted olefins in the range 20/80 to 60/40. . C20 uPAO dimer is U.S. It was prepared according to the method described in Example 1 of published patent application 2013/0090277 A1, the entirety of which is incorporated herein by reference. Thus, the C20 uPAO dimer will take the following predominant form:

Example 1 Acid Catalytic Synthesis of Product I Containing Compound-I and Compound-II

C16 uPAO dimers were alkylated with 4-methylbenzenethiol by acid catalyst as shown in Scheme 1 below to form product I containing compound-I and compound-II.

Glass reactors under N ₂ atmosphere were used to form C16 uPAO dimer (242.1 g, 1.07 mol), 4-methylbenzenethiol (160.4 g, 1.29 mol) (available from Sigma-Aldrich), and Amberlyst. -15H (6.89 g, 1.7 wt.%) (Obtained from Sigma-Aldrich) was charged. The mixture was heated with stirring at 120 ° C. for 20 hours. The mixture was filtered to remove the catalyst. The filtrate was distilled under vacuum to 160 ° -205 ° C. to remove unreacted olefins and thiols. Distillation pot residue was collected as Product I containing Compound-I and Compound-II in a molar ratio of approximately 97.5 to 2.5. Lubricant properties of Product I were determined as provided above and are shown in Table IV below.

Example 2 Comparative Radical Synthesis of Comparative Product 1 Containing Compound-I and Compound-II

C16 uPAO dimers were alkylated with 4-methylbenzenethiol with a radical initiator as shown in Scheme A below to form Comparative Product 1 containing Compound-I and Compound-II.

Glass reactors under N ₂ atmosphere were used to form C16 uPAO dimer (325.0 g, 1.44 mol), 4-methylbenzenethiol (309.0 g, 2.49 mol) (available from Sigma-Aldrich) and AIBN (23.1 g, 0.17). mol) was charged. 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. Distillation pot residue was treated with decolorized carbon and filtered. The filtrate was collected as comparative product 1 containing Compound-I and Compound-II in a molar ratio of I: II of approximately 1:99. The lubricant properties of Comparative Product 1 were determined as provided above and are shown in Table V below.

Product I and comparative product 1 contain the same type of isomers of alkylated thiols, but in different proportions thereof. The nature of the catalyst and process conditions applied can control the geochemistry of the sulfur addition to the double bond. This difference in molecular structure can be confirmed by ¹ H and ¹³ C NMR.

There are a few key structural properties that can be identified by ¹ H NMR that can be used to distinguish the structure of the product. The ¹ H NMR spectra of Product I and Comparative Product 1 were determined and shown in FIGS. 1 and 2, respectively. In addition, the ¹ H NMR structural arrangement of Compound-I and Compound-II is shown in FIG. 3. As shown in FIG. 3, the molecular structure of Compound-I includes a methyl group located adjacent to an aliphatic CS bond. The methyl group was identified as a singlet peak with a chemical shift of 1.14 ppm. The carbon atom of the aliphatic CS bond does not have a hydrogen atom and is therefore not characterized by ¹ H NMR.

In contrast, the molecular structure of Compound-II includes a methylene group bonded to a sulfur atom. This was identifiable as a doublet peak with a chemical shift of 2.85 ppm. The carbon atoms adjacent to these methylene groups carry one hydrogen atom that is identifiable as a quintet peak with a chemical shift of 1.59 ppm.

The presence or absence of any of these ¹ H NMR peaks indicates that the structure of the product or base stock is a sulfur atom in which the structure of the PAO moiety is bonded to the primary carbon (ie Compound-II) or tertiary carbon (ie Compound-I) Can be used to determine whether or not to include. These identifiable markers can be used to determine the molecular structure of the base stock and to quantify the relative amounts of different molecular isomers if a blend of isomers is present.

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 small amounts of Compound-II. Normalized integration shows that the compound-I to compound-II molar ratio in this product was approximately 97.7 to 2.5.

On the other hand, the ¹ H NMR spectrum of Comparative Product 1 shown in FIG. 2 shows the doublet at 2.85 ppm and the triplet at 1.59 ppm, which is characteristic of Compound-II. However, there was no identifiable singlet peak at 1.14 ppm, meaning that the composition of Comparative Product I was almost quantitative (> 99%) Compound-II.

Example 3 Acid Catalytic Synthesis of Product II Containing Compound-III and Compound-IV

The C20 uPAO dimer was alkylated with 4-methylbenzenethiol (available from Sigma-Aldrich) by acid catalyst to form product II containing Compound-III and Compound-IV as shown in Scheme 2 below.

Glass reactors under N ₂ atmosphere were converted to 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 to form a mixture. (20.0 g, 1.31 wt%) (obtained from Sigma-Aldrich) was charged. The mixture was heated with stirring at 120 ° C. 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 thiols and then to unreacted olefins at 215 ° C. Distillation pot residue was treated with decolorized carbon (20 g) and filtered through celite. The filtrate was collected as product II containing compound-III and compound-IV. Lubricant properties of product II were determined as provided above and are shown in Table VI below.

Example 4 Acid Catalytic Synthesis of Product III Containing Compound-V and Compound-VI

C16 uPAO dimers were alkylated with 1-octanethiol by acid catalyst as shown in Scheme 3 below to form product III containing Compound-V and Compound-VI.

Glass reactors under N ₂ atmosphere were converted to C16 uPAO dimer (200.0 g, 0.89 mol), 1-octanethiol (157.0 g, 1.07 mol) (obtained from Sigma-Aldrich), and Amberlyst-15H (10.0) to form a mixture. g, 2.7 wt.%) (obtained from Sigma-Aldrich). The mixture was heated to 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. Distillation pot residue was treated with decolorized carbon and filtered through celite. The filtrate was collected as Product III containing Compound-V and Compound-VI at a molar ratio of V: VI of approximately 78:22. Lubricant properties of Product III were determined as provided above and are shown in Table VII below.

Example 5 Acid Catalytic Synthesis of Product IV Containing Compound-VII and Compound-VIII

The C20 uPAO dimer was alkylated with 1-octanethiol by acid catalyst as shown in Scheme 4 below to form product IV containing compound-VII and compound-VIII.

Glass reactors under N ₂ atmosphere were used to form a mixture of C20 uPAO dimers (887.1 g, 3.16 mol), 1-octanethiol (554.3 g, 3.79 mol) (available from Sigma-Aldrich), and Amberlyst-15H (30.1). g, 3.3 wt.%) (obtained from Sigma-Aldrich). The mixture was heated to 120 ° C. for 20 hours. Additional Amberlist-15H (15.0 g, 1.6 wt.%) Was added and the reaction was continued for 8 hours. The mixture was filtered through celite to remove the catalyst. The filtrate was distilled under vacuum at 100 ° C. to remove unreacted thiols and then at 250 ° C. to remove unreacted olefins. Distillation pot residue was treated with decolorized carbon (20 g) and filtered through celite. The filtrate was collected as product IV containing compounds VII and VIII in a molar ratio of VII: VIII of approximately 95: 5. Lubricant properties of product IV were determined as provided above and are shown in Table VIII below.

The ¹ H NMR spectrum of the product IV was determined and shown in FIG. 3. In addition, the ¹ H NMR structural arrangement of compounds VII and VIII is shown in FIG. 5. As shown in FIG. 5, the molecular structure of compound VII includes a methyl group located adjacent to an aliphatic CS bond. The methyl group was identified as a singlet peak with a chemical shift of 1.20 ppm. The carbon atoms of the aliphatic CS bonds from the PAO moiety do not have a hydrogen atom and are therefore uncharacterized by ¹ H NMR. The carbon atoms of aliphatic CS bonds from aliphatic thiol moieties have two hydrogen atoms that were recognizable as triplet peaks with a chemical shift of 2.39 ppm.

Those skilled in the art will recognize that compound VIII provides triplet peaks at approximately 2.39 ppm and also provides additional doublet peaks in the range from 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 if a blend of isomers is present.

For example, in the ¹ H NMR spectrum of product IV in FIG. 4, triplet peaks were observed at 2.39 ppm, which could mean compound VII or VIII. However, only a few corresponding doublet peaks were observed in the 2.4-2.9 ppm range. Along with the observation of a strong singlet peak at 1.40 ppm, this meant that the main structure in the product IV was Compound VII, ie, the result of the Markovnicocove addition of aliphatic thiols to the uPAO dimer. Normalization of the ¹ H NMR peak meant that Product IV was present in a molar ratio of Compound-VII to Compound-VIII of 95: 5.

Example 6-Oxidation Stability Experiment

The oxidative stability of product I and product III were compared against comparative product 1 and conventional hydrocarbon synthesis base stocks according to the method described in ASTM D2272. Common hydrocarbon synthesis base stocks tested were PAO 4 and Synesstic ™ 5 (both available from ExxonMobil Chemical Company (27111 Springwoods Village Parkway, Spring, Texas 77389, U.S.A.). Rotational pressure vessel oxidation test (RPVOT) breakdown time of each product tested is provided in FIG. 6. Aromatic moieties tend to impart enhanced oxidative stability to base stock molecules. Thus, aromatic-containing Synnestic ™ 5 has a longer RPVOT break time than aliphatic PAO 4 base stocks. In particular, both S-containing aromatic base stocks from Product I and Comparative Product 1 also have longer RPVOT break times than Synesstic ™ 5, demonstrating that S atoms can contribute to further oxidative stability to aromatic-containing base stocks. . Furthermore, the presence of sulfur atoms in other aliphatic base stock molecules can improve oxidative stability. For example, the base stock of product III has a longer RPVOT break time compared to hydrocarbon base stocks such as PAO 4.

The RPVOT break time of the base stock of product I is substantially longer than the base stock of comparative product 1, demonstrating that the positional chemistry of the sulfur atoms and the positional chemistry of the sulfur addition can strongly affect oxidative stability. The base stock of product I, which derives primarily from the addition of sulfur markovib of sulfur to PAO olefins, has enhanced oxidative stability than the base stock of comparative product 1.

All patents and patent applications. Test procedures (such as ASTM methods, UL methods, etc.) and other documents cited herein are incorporated by reference for all jurisdictions in which such incorporation is permitted to such an extent that such disclosure is inconsistent with the present disclosure.

When the lower and upper numerical limits are listed herein, any lower limit to any upper limit range is contemplated. While exemplary embodiments of the disclosure have been described in detail, it will be understood that various other modifications will be apparent to those skilled in the art without departing from the scope and spirit of the disclosure and may be readily made by those skilled in the art. Accordingly, the scope of the claims appended hereto is not intended to be limited to the embodiments and descriptions set forth herein, but rather, the claims are intended to cover the present disclosure, including all features that are treated as equivalents thereof by those skilled in the art to which this disclosure belongs. It should be construed to cover all the characteristics of the patent novelty present in the content.

The present disclosure has been described with reference to numerous embodiments and specific examples. Many variations will be suggested to those skilled in the art in light of the above description. All such obvious changes fall within all intended scope of the appended claims.

Claims (25)

Lubricant base stocks comprising compounds having the formula (FI):

Where
R ¹ is a C ₁ -C ₅₀₀₀ alkyl group;
R ² is (i) a C ₄ -C ₃₀ linear alkyl group or (ii) a C ₄ -C ₅₀₀₀ branched alkyl group having the formula (F-II):

;
Wherein in each case R ⁵ and R ⁶ are each independently hydrogen or a C ₁ -C ₃₀ linear alkyl group and n is a positive integer, provided that at least one of all R ⁵ and R ⁶ is C ₁ -C ₃₀ linear An alkyl group; R ⁷ is hydrogen or a C ₁ -C ₃₀ linear alkyl group;
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. The lubricant base stock of claim 1 wherein R ³ is hydrogen. The lubricant base stock of claim 1 wherein R ³ is a C ₁ -C ₁₀₀ alkyl group. The lubricant base stock of claim 1 wherein R ¹ is a C ₁ -C ₃₀ linear alkyl group. The lubricant base stock of claim 1 wherein R ² is a C ₄ -C ₃₀ linear alkyl group. The method of claim 5,
R ² is a branched alkyl group represented by formula (F-II), wherein the lubricant base stock meets one of the following conditions:
(i) at least 50% of R ⁵ is hydrogen and at least 50% of R ⁶ are independently a C ₁ -C ₃₀ linear alkyl group;
(ii) at least 50% of R ⁵ are independently a C ₁ -C ₃₀ linear alkyl group and at least 50% of R ⁶ is hydrogen. The lubricant base stock of claim 1, wherein at least 50 mol% of the total R ⁵ and R ⁶ are independently C ₄ -C ₃₀ linear alkyl groups. The lubricant base stock of claim 1 wherein n is from 50 to 500. 3. The lubricant base stock of claim 1 wherein n is from 2 to 50. 3. The lubricant base stock of claim 1 wherein R ¹ and R ² are the same or different and are each independently C ₁ -C ₁₀₀ linear alkyl groups. The lubricant base stock of claim 1 wherein R ¹ and R ² are the same or different and each independently a C ₁ -C ₃₀ linear alkyl group. The lubricant base stock according to claim 1 wherein R ⁴ is a C ₁ -C ₅₀ linear alkyl, preferably C ₁ -C ₃₀ linear alkyl group. The lubricant base stock of claim 1 wherein R ⁴ is an aromatic group. The lubricant base stock of claim 6 having isotacticity of at least about 60 mol%, preferably at least about 75 mol%, more preferably at least about 80 mol%. The lubricant base stock of claim 1 having a Rotational Pressure Vessel Oxidation Test (RPVOT) break time of at least about 200 minutes. A method of making the lubricant base stock of claim 1,
In the presence of an acid catalyst, a process comprising the step of reacting an olefin containing material comprising HS-R ⁴ with a compound having the formula (F-Ia):

. The method of claim 16, wherein the olefin comprises at least about 75 wt% of a compound of Formula (F-Ia) wherein R ³ is hydrogen. The method of claim 16, wherein the olefin comprises at least about 50 wt% of a compound of Formula (F-Ia) wherein R ³ is a C ₁ -C ₁₀₀ alkyl group. The compound of claim 16, wherein the olefin comprises: (i) about 50-90% by weight of a compound of Formula (F-Ia) wherein R ³ is hydrogen; And (ii) about 10-50% by weight of a mixture of compounds of Formula (F-Ia) wherein R ³ is a C ₁ -C ₁₀₀ alkyl group. The method of claim 16, wherein the olefin containing material is prepared by oligomerization of C ₁ -C ₁₀₀ alpha-olefins in the presence of a metallocene compound. The method of claim 20, wherein the olefin containing material has isotacticity of at least about 60 mol%, preferably at least about 75 mol%, more preferably at least about 80 mol%. 17. The process of claim 16, wherein the acid catalyst is selected from the group consisting of Lewis acids, acidic clays, polymeric acidic resins, heteropolyacids, acidic ionic liquids, and combinations thereof. The process according to claim 16, wherein at least about 90 mol%, preferably at least about 95 mol% of the compound produced has a structure corresponding to formula (F-1). A blended lubricant composition comprising the lubricant base stock of claim 1. The blended lubricant composition of claim 24 wherein the lubricant base stock is present in an amount from about 50% to about 99% by weight.

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