JP2015512468A - Bearing lubricant for grinding equipment - Google Patents

Abstract

The present invention relates to a method for lubricating a bearing of a solid fuel grinder, for example a coal grinder. This method involves supplying a bearing with a lubricating composition designed to have superior performance compared to conventional coal grinder bearing lubricants. The present invention further provides a bearing lubricant for a coal pulverizer and the use of the bearing lubricant in the coal pulverizer to increase the service life and / or durability of the bearing of the coal pulverizer. The present invention further provides additive compositions for use in bearing lubricants for coal grinders, and the use of additive compositions to enhance service life and / or bearing lubricant performance.

Description

(Field of Invention)
The present invention relates to a method for lubricating a bearing of a solid fuel grinder, for example a coal grinder. This method involves supplying a bearing with a lubricating composition designed to have superior performance compared to conventional coal grinder bearing lubricants. The present invention further provides a bearing lubricant for a coal pulverizer and the use of the bearing lubricant in the coal pulverizer to increase the service life and / or durability of the bearing of the coal pulverizer. The present invention further provides additive compositions for use in bearing lubricants for coal grinders, and the use of additive compositions to enhance service life and / or bearing lubricant performance.

(Background of the Invention)
It is well known that pulverizers reduce the particle size of the solid fuel and allow it to burn in the furnace. Crushers are used to reduce the solid fuel to a specific particle size by combining some of the impacts, wear and crushing. Several types of crushing mills can be used to crush solid fuel (eg, coal) into granules of a size suitable for burning in a furnace. These can include ball tube mills, impact mills, attrition mills, ball race mills, and ring roll mills or ball mills. Most typically, however, ball mills with integrated classifiers are used to pulverize, move, dry, and directly burn pulverized fuel carried by an air stream. There is a continuing need to increase the load on the mill and improve the roll life of the bearings of these grinders.

  In addition to increasing the load on the mill, another factor that deteriorates the roll life of the bearing includes, for example, solid fuel dust that flows into and mixes with the bearing and lubricant, for example, coal dust. Typically, a crusher has an interface between a rotatable assembly that is exposed to atmospheric conditions and a fixed shaft, and different pressures on the assembly produce coal dust, for example containing bearings. Flow into assembly. As coal enters the interface, the shaft extends toward the journal assembly, rotates relative to the journal assembly, and mixes with the lubricant and journal bearing, thereby degrading the roll life of the journal bearing.

  Some approaches include complex mechanical seals and expensive new devices designed to reduce dust penetration. However, these solutions do not help current devices that are already in use.

  Therefore, existing equipment without the need for expensive repairs and modifications by extending the roll life of bearings in these crushers, promoting increased loading on the mill, and preventing damage due to contamination in the bearings There remains a need for methods and lubricant and additive packages that can be used more effectively.

(Summary of the Invention)
The present invention provides a method of lubricating a solid fuel grinder bearing. This method involved supplying a bearing with a lubricating composition designed to have superior performance compared to a conventional solid fuel grinder bearing lubricant. The lubricating composition is designed to increase dust retention, in other words, the lubricant is used in the harsh conditions found in mills, including those associated with large amounts of dust in the mill's environment. Designed to perform better and / or better than conventional lubricants and perform better in lubricants. The present invention further provides the use of bearing lubricants for crushers and bearing lubricants in crushers to increase the service life and / or durability of the crusher bearings. The present invention further provides additive compositions for use in bearing lubricants for crushers, and the use of additive compositions to enhance service life and / or bearing lubricant performance. In certain embodiments, the solid fuel grinder described herein is a coal grinder.

  The lubricating composition of the present invention comprises (a) an oil having a viscosity that acts as a lubricant, (b) a phosphorus-containing compound, and (c) a nitrogen-containing dispersant, and the phosphorus-containing compound and the nitrogen-containing dispersant are combined together. And enables good performance in the bearing lubricant of the crusher. In certain embodiments, the composition further comprises (d) a sulfur-containing compound.

  In certain embodiments, the present invention deals with mineral-based oil lubricants. In other embodiments, the present invention deals with synthetic base oil lubricants.

  The present invention provides various phosphorus-containing compounds including alkyl phosphites, phosphate esters, amine salts of phosphate esters, or some combination thereof. In certain embodiments, the phosphorus-containing compound comprises an alkyl phosphite.

  The present invention relates to a Mannich dispersant comprising a reaction product of a polyetheramine, a borated succinimide dispersant, a non-borated succinimide dispersant, (i) a dialkylamine, (ii) an aldehyde and (iii) a hydrocarbyl-substituted phenol, and various Various nitrogen-containing dispersants are provided, including any combination of the following nitrogen-containing dispersants. In certain embodiments, the nitrogen-containing dispersant comprises a non-borated succinimide dispersant. The present invention further provides a lubricant containing an alkyl phosphite and a non-borated succinimide dispersant.

  In any of these embodiments, the phosphorus-containing compound is 0.25% by weight in the lubricant composition, based on excluding oil (which may be referred to herein as active agent basis) or From 0.5% to 2.0% or 1.0% by weight, the nitrogen-containing dispersant may be present in the lubricant composition from 0.1% or 0.5% to 2.% by weight. Present up to 0% or 1.0% by weight.

(Detailed description of the invention)
Various features and embodiments of the invention are described below by way of non-limiting illustration.

(Crusher and lubrication method)
The grinder suitable for use with the present invention is not so limited. A grinder will generally describe a usable device for the purpose of polishing a material. More specifically, the prior art is replete with examples of the various types of apparatus that have been used to polish many different types of materials. In this respect, it will often be seen that there are discernable differences in the nature of the structure between the individual grinders. The existence of such differences can in turn be attributed to most of the various functional requirements associated with individual applications designed to use crushers. For example, in selecting a particular type of grinder to be utilized for a particular application, one of the major factors to consider is the nature of the material to be polished in the apparatus. Coal is one of the materials that needs to be polished to make it suitable for use in a particular application. Furthermore, power generation systems that burn fossil fuels represent one of the applications where it is desirable to use coal as a fuel source, and for this purpose, i.e., systems that generate power by burning coal. There is a need to grind (i.e., grind) the coal to make it suitable. Thus, in some embodiments, the grinder used with the present invention is a coal grinder.

  In one embodiment, the pulverizer of the present invention comprises a feeder for supplying solid fuel to the pulverizer, an apparatus for pulverizing the solid fuel, a distribution system for distributing the solid fuel after the pulverization, A furnace for burning solid fuel and necessary control for appropriately operating a power generation system for burning solid fuel may be provided. Of particular interest here is an apparatus for comminuting solid fuel (eg, coal).

  In one embodiment, the pulverizer of the present invention is a ball mill. The ball mill is essentially pulverized on the inside of the ball mill, a main body portion to which a polishing table is attached for rotation, a plurality of polishing rollers that cooperate with the polishing table and polish solid fuel sandwiched between them, and the inside of the ball mill. The solid fuel supply means for supplying the solid fuel and the air supply means for supplying the air necessary for operating the latter to the inside of the ball mill may be included. According to such an operation mode of the ball mill, the solid fuel entering the ball mill is pulverized by the cooperation of the polishing roller and the polishing table. After grinding, the solid fuel particles are thrown out by centrifugal force, thereby supplying the particles to the air stream entering the ball mill. The air stream containing the pulverized solid fuel particles flows through a tortuous path partially established by being located within the ball mill of a suitably supported deflector means. As the flow of air and solid fuel particles flows along the tortuous path described above, the steep bends included in the path separate coarse solid fuel particles from the air flow. These coarse solid fuel particles are then appropriately returned to the polishing table for further grinding, while the fine solid fuel particles are carried through the ball mill along the air stream and out of the ball mill with the air. Get out. Each ball mill typically also includes bearings (eg, upper and lower bearings that are associated with the polishing roller by the polishing table and / or its connection).

  Each grinder typically also has a lubrication system for supplying lubricant to its bearings (including the upper and lower bearings of the described ball mill), but with various types of grinders All the various bearings that can be found are used in this field.

  The present invention provides a lubricant composition for a bearing of a solid fuel pulverizer, and further provides a method for lubricating a bearing of a coal pulverizer by feeding the described lubricant composition to the bearing. To do. The lubricant compositions useful in the present invention are described below.

In certain embodiments, the method of the present invention includes feeding the described lubricant composition to a coal grinder. In certain embodiments, the methods of the present invention comprise feeding the described lubricant composition to a ball mill. In certain embodiments, the method of the present invention includes feeding the described lubricant composition to a ball mill coal grinder. In certain embodiments, the method of the present invention includes feeding the described lubricant composition to the upper bearings of the grinder. In certain embodiments, the method of the present invention includes feeding the described lubricant composition to a lower bearing of a grinder. In certain embodiments, the method of the present invention includes supplying the described lubricant composition to the upper and lower bearings of the grinder, or to all bearings of the grinder.
(Lubricant composition)

  The present invention comprises (a) an oil having a viscosity that acts as a lubricant, (b) a phosphorus-containing compound, and (c) a nitrogen-containing dispersant, and the phosphorus-containing compound and the nitrogen-containing dispersant work together, It includes a bearing lubricant composition that allows for good performance in the mill lubricant. The invention further comprises (a) an optional diluent that may be an oil or solvent having a viscosity that acts as a lubricant, (b) a phosphorus-containing compound, and (c) a nitrogen-containing dispersant. Also provided is an additive composition for use in a bearing lubricant for a grinder, wherein the phosphorus-containing compound and the nitrogen-containing dispersant work together to enable good performance in the mill lubricant. In certain embodiments, the composition further comprises (d) a sulfur-containing compound.

  In some embodiments, the lubricant composition is 0.01 to 5.0 weight by weight on an active agent basis (meaning no diluent oil or solvent, these components are considered undiluted). %, Or 0.25 to 5.0% by weight, or 0.5 to 5.0% by weight, or 0.5 to 4.0% by weight, 0.75 to 3.0% by weight, 0.9 to 2% 0.0% by weight, or 1-2% by weight, or 1% by weight or 2% by weight of phosphorus-containing compound. In some embodiments, the lubricant composition is 0.01-5.0 wt%, or 0.025-0.5 wt%, or 0.025-0.25 wt%, or 0, based on the total lubricant composition. Contains phosphorus-containing compound in an amount sufficient to contain 0.05-0.1% by weight phosphorus.

  In certain embodiments, the lubricant composition is from 0.01 wt% or 0.1 wt% or 0.25 wt% to 10 wt% or 5 wt% or 4 wt%, or 0.01 wt% or 0.1 wt% or 0.25 wt% to 5 wt%, or 0.1 to 1.0 wt%, or 0.4 wt% to 2.0 wt% or 2.5 wt%, or 0.5-2.0% by weight of a nitrogen-containing dispersant is contained on an active substance basis.

  In some embodiments, the phosphorus-containing compound and the nitrogen-containing dispersant are in the lubricant composition 1: 10-10: 1, or 1: 4-4: 1, or 1: 2-4: 1, or 1 Present in a ratio of 1-3: 1, or about 2: 1, which is a weight ratio based on what does not contain the active substance. In certain embodiments, the phosphorus-containing compound and the nitrogen-containing dispersant are 0.5: 1 to 4: 1, and / or about 0.5: 1, 1: 1, 1.2 in the lubricant composition. Present in a ratio of up to 1, 2: 1 or 4: 1, which is a weight ratio based on an oil free basis.

(Oil having viscosity that works as a lubricant)
One component of the composition of the present invention is an oil having a viscosity that acts as a lubricant and may be present in a major amount for the lubricant composition, or a concentrate and / or additive composition. May be present in an amount to produce a concentrate.

  Suitable oils include natural and synthetic lubricating oils and mixtures thereof. In a fully formulated lubricant, the oil with viscosity that acts as a lubricant is generally present in a major amount (ie, greater than 50% by weight). Typically, the oil having a viscosity that acts as a lubricant is present in an amount of from 75 to 95%, often more than 80% by weight of the total composition. The base oil component generally constitutes 100 parts by weight (pbw) of the total composition, and the pbw range of the other components is given using the base oil 100 pbw under consideration. In other embodiments, the pbw range of the various ingredients including the base oil is given so that the sum of the pbw of all ingredients is 100, so the pbw value is comparable to the weight percent value. The pbw ranges given for the various components described below may be made in either manner, but in most embodiments should be read as comparable to weight percent values.

  Oils with viscosities that act as lubricants are natural and synthetic oils, oils derived from hydrocracking, hydrogenation and hydrofinishing, unrefined oils, refined oils and refined oils, or these May be included. Unrefined oils are oils that are obtained directly from natural or synthetic sources, generally with little (or little) further purification processing. Refined oils are similar to unrefined oils, except that they have been further processed in one or more refining steps to enhance one or more properties. Purification techniques are known in the art and include solvent extraction, secondary distillation, acid or base extraction, filtration, percolation and the like. Rerefined oils, also known as reclaimed or reprocessed oils, are obtained by a process similar to that used to obtain refined oils, often to remove used additives and oil breakdown products Further processing by technology.

  Natural oils useful as oils with viscosity that act as lubricants include animal oils, vegetable oils (eg, castor oil, lard oil), mineral lubricating oils, eg, liquid petroleum, paraffinic, naphthenic, or paraffinic and naphthenic Mixed paraffinic naphthenic solvent-treated or acid-treated mineral lubricants and oils derived from coal or shale, or mixtures thereof.

  Synthetic oils having a viscosity that acts as a lubricant include hydrocarbon oils such as polymerized olefins and interpolymerized olefins (eg, polybutylene, polypropylene, propylene isobutylene copolymers); poly (1-hexene), poly ( 1-octene), poly (1-decene) and mixtures thereof; alkyl-benzenes (eg dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene); polyphenyls (eg biphenyl) , Terphenyl, alkylated polyphenyl); alkylated biphenyl ethers and alkylated biphenyl sulfides, and derivatives, analogs and homologues thereof, or mixtures thereof. In some embodiments, the oil having a viscosity that acts as a lubricant for use in the present invention is a synthetic oil comprising polymerized polyisobutylene, and in some embodiments, the oil having a viscosity that acts as a lubricant for use in the present invention is , A synthetic oil containing polymerized polyisobutylene and polyalphaolefin.

  Other synthetic oils having a viscosity acting as a lubricant include polyol esters other than hydrocarbyl protected polyoxyalkylene polyols as disclosed herein, dicarboxylic acid esters, liquid esters of phosphorus-containing acids (e.g., phosphorus Tricresyl acid, trioctyl phosphate and decanophosphonic acid diethyl ester), or tetrahydrofuran polymers. Synthetic oils having a viscosity that serve as conventional lubricants further include oils made by the Fischer-Tropsch reaction, and may typically be hydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodiment, an oil having a viscosity that acts as a lubricant may be prepared by Fischer-Tropsch gas-liquid synthesis procedures and other gas-liquid oils.

  Oils with viscosities that act as lubricants may be further defined as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines. The five base oil groups are: Group I (sulfur content> 0.03% by weight, and / or saturates <90% by weight, viscosity index 80-120); Group II (sulfur content ≦ 0.03% by weight and saturates ≧ 90% by weight, Viscosity index 80-120); Group III (sulfur content ≦ 0.03% by weight and saturates ≧ 90% by weight, viscosity index ≧ 120); Group IV (all polyalphaolefins or PAOs, for example PAO-2) , PAO-4, PAO-5, PAO-6, PAO-7 or PAO-8); and Group V. Oils having a viscosity that act as lubricants include API Group I, Group II, Group III, Group IV, Group V oils, or mixtures thereof. In one embodiment, the oil having a viscosity that acts as a lubricant is an API Group I, Group II, Group III, Group IV oil, or a mixture thereof. Alternatively, the oil having a viscosity that acts as a lubricant is often an API Group II, Group III or Group IV oil, or a mixture thereof.

  In certain embodiments, the oil component that serves as a lubricant of the present invention comprises a Group II or Group III base oil, or a combination thereof. These are classifications established by the API (American Petroleum Institute). Group III oils contain <0.03% sulfur and> 90% saturates and have a viscosity index> 120. Group II oils have a viscosity index of 80-120 and contain <0.03% sulfur and> 90% saturates. This oil can also be derived from the hydroisomerization of waxes such as slack wax or wax synthesized by Fischer-Tropsch. Such “gas-liquid” oils are typically characterized as Group III.

  The compositions of the present invention may comprise an amount of a Group I base oil, as well as a Group IV and Group V base oil. Polyalphaolefins are classified as Group IV. Group V includes “everything else”. However, in certain embodiments, the oil component that serves as a lubricant of the present invention contains no more than 20 wt%, no more than 10 wt%, no more than 5 wt%, or even no more than 1 wt% Group I base oil. These limitations may also apply to Group IV or Group V base oils. In other embodiments, the oil that acts as a lubricant present in the composition of the present invention comprises at least 60 wt%, 70 wt%, 80 wt%, 90 wt%, or even 95 wt% Group II and / or Group III base oil. In some embodiments, the only oil acting as a lubricant present in the composition of the present invention is essentially only Group II and / or Group III base oils, and small amounts of other types of base oils are present. However, it is an amount that does not significantly affect the overall properties or performance of the composition.

  In certain embodiments, the composition of the present invention comprises an amount of a Group I and / or Group II base oil. In other embodiments, the composition of the present invention is such that the oil having a viscosity that acts as a lubricant is primarily a Group I and / or Group II base oil, or more essentially Group I and / or Group. A lubricating composition that is a base oil of Group II or more exclusively a Group I and / or Group II base oil.

  In certain embodiments, the composition of the present invention comprises an amount of a Group I and / or Group II base oil. In other embodiments, the composition of the present invention is such that the oil having a viscosity that acts as a lubricant is primarily a Group I and / or Group II base oil, or more essentially Group I and / or Group II. Or a base oil of Group I and / or Group II.

The various described oils having viscosities that act as lubricants may be used alone or in combination. An oil having a viscosity that acts as a lubricant ranges from about 70% to 99% by weight of the lubricant, in another embodiment, from about 75% to about 98%, in another embodiment, about 88%. Used in the range of weight percent to about 97 weight percent.
(Phosphorus-containing compound)

  Compositions useful in the present invention include a phosphorus-containing compound.

  In certain embodiments, the phosphorus-containing compound is a phosphite. Suitable phosphites include those having at least one hydrocarbyl group containing 4 or more, or 8 or more, or 12 or more than 12 carbon atoms. Typical ranges for the number of carbon atoms in the hydrocarbyl group include 8-30, or 10-24, or 12-22, or 14-20, or 16-18. The phosphite may be a mono-hydrocarbyl substituted phosphite, a di-hydrocarbyl substituted phosphite, or a tri-hydrocarbyl substituted phosphite.

  In one embodiment, the phosphite does not contain sulfur, i.e., the phosphite is not a thiophosphite.

によってあらわされてもよく、式中、Ｒ^３、Ｒ^４およびＲ^５の少なくとも１つは、少なくとも４個の炭素原子を含有するヒドロカルビル基であってもよく、その他は、水素またはヒドロカルビル基であってもよい。一実施形態では、Ｒ^３、Ｒ^４およびＲ^５は、全部がヒドロカルビル基である。ヒドロカルビル基は、アルキル、シクロアルキル、アリール、非環状またはこれらの混合物であってもよい。３個の基Ｒ^３、Ｒ^４およびＲ^５基をすべて含む式では、この化合物は、トリ−ヒドロカルビル置換ホスファイトであってもよく、すなわち、Ｒ^３、Ｒ^４およびＲ^５は、すべてヒドロカルビル基である。 A phosphite having at least one hydrocarbyl group containing 4 or more than 4 carbon atoms can be represented by the following formula:

Wherein at least one of R ³ , R ⁴ and R ⁵ may be a hydrocarbyl group containing at least 4 carbon atoms, and the other is hydrogen or a hydrocarbyl group. May be. In one embodiment, R ³ , R ⁴ and R ⁵ are all hydrocarbyl groups. The hydrocarbyl group may be alkyl, cycloalkyl, aryl, acyclic or a mixture thereof. In formulas containing all ^three groups R ³ , R ⁴ and R ⁵ , the compound may be a tri-hydrocarbyl substituted phosphite, ie R ³ , R ⁴ and R ⁵ are all hydrocarbyl groups. It is.

An alkyl group may be straight or branched, typically linear and saturated or unsaturated, and typically saturated. Examples of alkyl groups for R ³ , R ⁴ and R ⁵ include octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonadecyl, eicosyl or these A mixture is mentioned.

式中、Ｒ^３およびＲ^４は、独立して、水素、または典型的には４〜４０個、または６〜３０個、または６〜１８個、または８〜１８個の炭素原子を含有する炭化水素であってもよく、但し、少なくとも１つは炭化水素基であり、Ｒ^５、Ｒ^６、Ｒ^７およびＲ^８は、独立して、水素またはヒドロカルビル基であってもよく、但し、少なくとも１つはヒドロカルビル基である。Ｒ^３および／またはＲ^４の炭化水素基は、直鎖、分枝鎖または環状であってもよい。 In certain embodiments, the phosphorus-containing compound is an amine salt of a phosphate hydrocarbon ester (ie, an amine salt of a phosphate ester of phosphoric acid). The amine salt of the phosphate hydrocarbon ester may be derived from an amine salt of phosphoric acid. The amine salt of phosphate hydrocarbon ester may be represented by the following formula:

In which R ³ and R ⁴ are independently hydrogen or carbonized typically containing 4 to 40, or 6 to 30, or 6 to 18, or 8 to 18 carbon atoms. ^{May be} hydrogen, provided that at least one is a hydrocarbon group and R ⁵ , R ⁶ , R ⁷ and R ⁸ may independently be hydrogen or a hydrocarbyl group, provided that at least 1 One is a hydrocarbyl group. The hydrocarbon group for R ³ and / or R ⁴ may be linear, branched or cyclic.

Examples of the hydrocarbon group of R ³ and / or R ⁴ include a linear or branched alkyl group, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl , Dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl. Further examples include 2-ethylhexyl, 4-methyl-2-pentyl and isopropyl.

Examples of cyclic hydrocarbon groups for R ³ and / or R ⁴ include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, dimethylcyclopentyl, methyl-cyclopentyl, dimethylcyclopentyl, methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, Mention may be made of methylethylcyclohexyl, diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethylcycloheptyl and diethylcycloheptyl.

  In one embodiment, the phosphate may be an amine salt of a mixture of monoalkyl phosphate ester and dialkyl phosphate ester. The monoalkyl group and dialkyl group may be linear or branched.

  The amine salt of the phosphate hydrocarbon ester may be derived from an amine (eg, primary amine, secondary amine, tertiary amine, or mixtures thereof). The amine may be aliphatic or cyclic, aromatic or non-aromatic, typically aliphatic. In one embodiment, the amine comprises an aliphatic amine, such as a tertiary aliphatic primary amine.

  Examples of suitable primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, bis- (2-ethylhexyl) amine, octylamine and dodecylamine, and n-octylamine, n-decylamine, n-dodecylamine , Aliphatic amines such as n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleylamine. Other useful aliphatic amines include commercially available aliphatic amines, such as “Armeen®” amines (products available from Akzo Chemicals, Chicago, Ill.), Such as Armeen C, Armeen O, Armen OL. , Armeen T, Armeen HT, Armeen S and Armeen SD, the letter notation being related to aliphatic groups (eg coco, oleyl, tallow or stearyl groups).

  Examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine, N-methyl-1-amino-cyclohexane, Armeen (registered) 2C and ethyl amylamine. Secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.

  Examples of tertiary amines include tri-n-butylamine, tri-n-octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine and dimethyloleylamine (Armeen® DMOD).

  In one embodiment, the amine is in the form of a mixture. Examples of suitable mixtures of amines include (i) tertiary alkyl primary amines containing 11 to 14 carbon atoms, (ii) tertiary alkyl primary amines containing 14 to 18 carbon atoms, or (iii) And tertiary alkyl primary amines containing 18 to 22 carbon atoms. Other examples of tertiary alkyl primary amines include tert-butylamine, tert-hexylamine, tert-octylamine (eg, 1,1-dimethylhexylamine), tert-decylamine (eg, 1,1-dimethyloctylamine). ), Tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine and tert-octacosanylamine.

In one embodiment, a useful mixture of amines is “Primene® 81R” or “Primene® JMT”. Primene® 81R and Primene® JMT (both manufactured and sold by Rohm & Haas) are C ₁₁ -C ₁₄ tertiary alkyl primary amine and C ₁₈ -C ₂₂ tertiary alkyl, respectively. It is a mixture of primary amines.

  Amine salts of phosphate hydrocarbon esters may be prepared as described in US Pat. No. 6,468,946. Column 10, lines 15-63 describes phosphate esters that produce an amine salt of a phosphate hydrocarbon ester by reaction of a phosphorus compound followed by reaction with an amine. Column 10, lines 64-12, line 23 reacts between phosphorus pentoxide and an alcohol (having 4-13 carbon atoms) and then an amine (typically Primene). (Registered trademark) 81-R) is described as a preparation example for producing an amine salt of a phosphoric acid hydrocarbon ester.

式中、Ｒ^２６およびＲ^２７は、独立して、分枝鎖または直鎖のアルキル基である。Ｒ^２６およびＲ^２７は、約３〜約３０個、好ましくは、約４〜約２５個、さらに好ましくは、約５〜約２０個、最も好ましくは、約６〜約１９個の炭素原子を含む。Ｒ^２３、Ｒ^２４およびＲ^２５は、上に記載したとおりである。 Suitable phosphorus-containing compounds also include hydrocarbyl amine salts of dialkyldithiophosphoric acids. An example of a hydrocarbylamine salt of a dialkyldithiophosphoric acid is represented by the following formula:

In the formula, R ²⁶ and R ²⁷ are each independently a branched or straight chain alkyl group. R ²⁶ and R ²⁷ contain about 3 to about 30, preferably about 4 to about 25, more preferably about 5 to about 20, and most preferably about 6 to about 19 carbon atoms. . R ²³ , R ²⁴ and R ²⁵ are as described above.

  In certain embodiments, hydrocarbylamine salts of dialkyldithiophosphoric acid include, but are not limited to, the reaction product (s) of diheptyldithiophosphoric acid or dioctyldithiophosphoric acid or dinonyldithiophosphoric acid and ethylenediamine, morpholine, or Primene 81R, Or a mixture thereof.

The phosphorus-containing compound is 0.01% to 5%, or 0.1% to 3%, or 0.2% to 1.5%, or 0.25% by weight of the composition described. May be present at ˜1 wt%, or 0.5 wt% ˜1 wt%.
(Nitrogen-containing dispersant)

  The compositions useful in the present invention comprise a nitrogen-containing dispersant, and in one embodiment are hydrocarbyl-substituted nitrogen-containing additives. Suitable hydrocarbyl-substituted nitrogen containing additives for use in the present invention include additives sometimes referred to as ashless dispersants. Dispersants are generally well known in the lubricant and fuel arts (although many of these additives are called fuel detergents when used in fuel applications). Suitable materials primarily include those known as ashless dispersants and polymeric dispersants. Ashless dispersants are referred to as ashless dispersants because they do not contain metal when supplied and do not normally contribute to sulfate ash when added to a lubricant. However, ashless dispersants may, of course, interact with surrounding metals when added to lubricants containing metal-containing species. Ashless type dispersants are characterized by polar groups that connect to hydrocarbon chains of relatively high molecular weight. Examples of such materials include succinimide dispersants, Mannich dispersants, and borated derivatives thereof.

  Mannich dispersants, sometimes called Mannich base dispersants or Mannich detergents, are reaction products of hydrocarbyl-substituted phenols, aldehydes and amines or ammonia. The hydrocarbyl substituent of the hydrocarbyl-substituted phenol may have 10 to 400, 30 to 180, 10 or 40 to 110 carbon atoms. This hydrocarbyl substituent may be derived from olefins or polyolefins such as 1-decene and is commercially available.

  For example, polyolefins capable of generating hydrocarbyl substituents can be prepared by polymerizing olefin monomers by well-known polymerization methods, which are also commercially available. Olefin monomers include monoolefins having 2 to 10 carbon atoms, such as monoolefins including ethylene, propylene, 1-butene, isobutylene and 1-decene. A particularly useful monoolefin source is a C4 refining stream having a butene content of 35 to 75% by weight and an isobutene content of 30 to 60% by weight. Useful olefin monomers also include diolefins such as isoprene and 1,3-butadiene. The olefin monomer may be a mixture of two or more monoolefins, two or more diolefins, or one or more monoolefins and one or more than one. A mixture of diolefins may also be included. Useful polyolefins include polyisobutylene having a number average molecular weight of 140 to 5000, in other cases 400 to 2500, and in further cases 140 or 500 to 1500. The polyisobutylene may have a vinylidene double bond content of 5 to 69%, in the second case 50 to 69%, and in the third case 50 to 95%. The polyolefin may be a homopolymer prepared from one olefin monomer or a copolymer prepared from a mixture of two or more olefin monomers. In addition, the hydrocarbyl substituent source can be a mixture of two or more homopolymers, a mixture of two or more copolymers, one or more homopolymers and one or one. A mixture of more than one type of copolymer. The above statements regarding suitable hydrocarbyl groups or polyolefin groups are applicable to the hydrocarbyl substituents of the succinimide dispersants described in detail below.

  The hydrocarbyl-substituted phenol used to prepare the Mannich dispersant is prepared by alkylating the phenol with an olefin or polyolefin as described above, such as polyisobutylene or polypropylene, using well-known alkylation methods. Can do.

  The aldehyde used to make the Mannich dispersant may have 1 to 10 carbon atoms and is generally formaldehyde or a reactive equivalent thereof, such as formalin or paraformaldehyde.

  The amine used to make the Mannich dispersant may be a monoamine or polyamine, including the materials described below for succinimide dispersants, including alkanolamines having one or more hydroxyl groups. Including. Useful amines include ethanolamine, diethanolamine, methylamine, dimethylamine, ethylenediamine, dimethylaminopropylamine, diethylenetriamine and 2- (2-aminoethylamino) ethanol. Mannich dispersants can be prepared by reacting hydrocarbyl substituted phenols, aldehydes and amines as described in US Pat. No. 5,697,988. In one embodiment, the Mannich reaction product is prepared from an alkylphenol derived from polyisobutylene, formaldehyde, and an amine that is a primary monoamine, secondary monoamine or alkylenediamine, in particular ethylenediamine or dimethylamine. In one embodiment, the alkylphenol is prepared from a high vinylidene polyisobutene having, for example, greater than 50% (ie, percent of polyisobutylene molecules having vinylidene end groups), greater than 70%, or greater than 75% terminal vinylidene groups. May be. The above description regarding amines is also applicable to the description of amines used in preparing the succinimide dispersants described below.

  In one embodiment, the Mannich dispersant comprises a hydrocarbyl substituted phenol, formaldehyde or a reactive equivalent of formaldehyde and a reaction product of a primary or secondary amine. In one embodiment, the Mannich dispersant comprises a polyisobutene-substituted phenol, formaldehyde or a reactive equivalent of formaldehyde and a reaction product of dimethylamine.

  As used herein, the term “hydrocarbyl substituent” or “hydrocarbyl group” is used in its ordinary sense, which is well-known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly connected to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include hydrocarbon substituents (including aliphatic, alicyclic and aromatic substituents); substituted hydrocarbon substituents, ie, the main hydrocarbon character of the substituent in terms of the present invention Substituents containing non-hydrocarbon groups that do not change the ring; and hetero substituents, i.e., substituents that similarly have the main hydrocarbon character but contain other than carbon in the ring or chain. A more detailed definition of the term “hydrocarbyl substituent” or “hydrocarbyl group” is found in published application US2010 / 0197536, paragraphs [0137] to [0141].

式中、各Ｒ^１は、独立して、アルキル基、頻繁には、ポリイソブチレン前駆体に由来する分子量（Ｍ_ｎ）が５００〜５０００のポリイソブチレン基であり、Ｒ^２は、アルキレン基、一般的にはエチレン（Ｃ_２Ｈ_４）基である。このような分子は、一般的に、アルケニルアシル化剤とポリアミンの反応から誘導され、この２種類の部分の多種多様な結合は、上に示す単純なイミド構造以外にも可能であり、種々のアミドおよび四級アンモニウム塩を含む。上の構造では、アミン部分は、アルキレンポリアミンとして示されるが、上に記載し、以下に記載するものを含む他の脂肪族および芳香族のモノアミンおよびポリアミンを使用してもよい。さらに、種々の環状結合を含み、イミド構造に対するＲ^１基の種々の結合態様が可能である。アミンの窒素原子に対するアシル化剤のカルボニル基の比率は、１：０．５〜１：３、他の場合には、１：１〜１：２．７５、または１：１．５〜１：２．５であってもよい。スクシンイミド分散剤は、米国特許第４，２３４，４３５号および第３，１７２，８９２号およびＥＰ ０３５５８９５号にさらに完全に記載される。 Another suitable hydrocarbyl-substituted nitrogen-containing additive is a succinimide dispersant, sometimes referred to as a succinimide fuel detergent. In one embodiment, the succinimide dispersant is a condensation product of a hydrocarbyl substituted succinic anhydride or reactive equivalent thereof (eg, an anhydride, ester or acid halide) and an amine, eg, a polyethylene polyamine. Succinimide dispersants may typically be considered as various chemical structures, generally including:

Wherein each R ¹ is independently an alkyl group, frequently a polyisobutylene group having a molecular weight (M _n ) derived from a polyisobutylene precursor of 500 to 5000, R ² is an alkylene group, Specifically, it is an ethylene (C ₂ H ₄ ) group. Such molecules are generally derived from the reaction of an alkenyl acylating agent with a polyamine, and a wide variety of linkages between the two moieties are possible besides the simple imide structure shown above, Including amides and quaternary ammonium salts. In the above structure, the amine moiety is shown as an alkylene polyamine, but other aliphatic and aromatic monoamines and polyamines may be used, including those described above and described below. In addition, various linkages of the R ¹ group to the imide structure are possible, including various cyclic bonds. The ratio of the carbonyl group of the acylating agent to the nitrogen atom of the amine is 1: 0.5 to 1: 3, in other cases 1: 1 to 1: 2.75, or 1: 1.5 to 1: It may be 2.5. Succinimide dispersants are more fully described in US Pat. Nos. 4,234,435 and 3,172,892 and EP 0355895.

  Succinimide dispersants may be further described as being prepared from hydrocarbyl-substituted succinic acylating agents, which acylating agents may be by the so-called “chlorine” route or by the so-called “thermal” route or “direct alkylation”. It is prepared similarly by the route. These routes are described in detail in paragraphs 0014-0017 of published application US2005-0202981. A direct alkylation or low chlorine route is also described in US Pat. No. 6,077,909. See column 6, line 13 to column 7, line 62 and column 9, line 10 to column 10, line 11. An exemplary thermal process or direct alkylation process involves heating the polyolefin, typically at 180-250 ° C., with maleic anhydride under an inert atmosphere. Either reactant may be in excess. If maleic anhydride is present in excess, this excess may be removed by distillation after the reaction. These reactions may use high vinylidene polyisobutylene as the polyolefin, ie use more than 50%, 70%, or 75% terminal vinylidene groups (in some embodiments, alpha vinylidene end groups). May be. In certain embodiments, succinimide dispersants may be prepared by a direct alkylation route. Other embodiments may include a mixture of direct alkylation and chlorine pathway dispersants.

  These optional additives may be post-treated with any of a variety of agents to impart desired properties. Such post-treatments include urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, nitrile, epoxide, boron compounds such as boric acid, phosphorus compounds, Or reaction with these mixtures is mentioned. References regarding such treatments are listed in US Pat. No. 4,654,403.

  Further suitable hydrocarbyl substituted nitrogen-containing additives include acylated amines, hydrocarbyl substituted amines, or mixtures thereof.

Suitable acylated amines include the reaction product of one or more carboxylic acylating agents and one or more amines. Carboxylic acylating agents include those described above, including C _8-30 fatty acids, C _14-20 iso fatty acids, C _18-44 dimer acids, addition dicarboxylic acids, trimer acids, addition tricarboxylic acids and hydrocarbyl substitutions. Examples include acylating agents for carboxylic acids. Dimer acids are disclosed in U.S. Pat. Nos. 2,482,760, 2,482,761, 2,731,481, 2,793,219, 2,964,545, and 2,978. 468, 3,157,681, and 3,256,304. Suitable amines may be any of those described above, and in certain embodiments may be polyamines, such as alkylene polyamines or condensed polyamines. Acylated amines, intermediates thereof and methods for their preparation are described in US Pat. Nos. 3,219,666; 4,234,435; 4,952,328; 4,938,881; 957,649; 4,904,401; and 5,053,152.

  The hydrocarbyl substituted nitrogen containing additive may further be a hydrocarbyl substituted amine. These hydrocarbyl substituted amines are well known to those skilled in the art. These amines are described in U.S. Pat. Nos. 3,275,554; 3,438,757; 3,454,555; 3,565,804; 3,755,433; , 822, 289. Typically, hydrocarbyl substituted amines are prepared by reacting olefins and olefin polymers, including the above polyalkenes and their halogenated derivatives, with amines (monoamines or polyamines). The amine may be any amine described herein, and in certain embodiments is an alkylene polyamine.

  Examples of hydrocarbyl substituted amines include ethylene polyamines such as diethylenetriamine; poly (propylene) amine; N, N-dimethyl-N-poly (ethylene / propylene) amine (monomer ratio 50:50 mol); polybuteneamine; N, N-di (hydroxyethyl) -N-polybuteneamine; N- (2-hydroxypropyl) -N-polybuteneamine; N-polybutene-aniline; N-polybutenemorpholine; N-poly (butene) ethylenediamine; Poly (propylene) trimethylenediamine; N-poly (butene) diethylenetriamine; N ′, N′-poly (butene) tetraethylenepentamine; N, N-dimethyl-N′-poly (propylene) -1,3-propylene Examples include diamines.

  In certain embodiments, the hydrocarbyl-substituted nitrogen-containing additive described above is borated. Any of the additives described herein may be borated and generally prepared by reaction of the additive with a boron-containing compound, such as boric acid.

  In one embodiment, the boron compound is a borated dispersant. Typically, the borated dispersant contains from about 0.1% to about 5%, or from about 0.5% to about 4%, or from 0.7% to about 3% by weight boron. contains. In one embodiment, the borated dispersant is a borated acylated amine, such as a borated succinimide dispersant. Borated dispersants are disclosed in U.S. Pat. Nos. 3,000,916; 3,087,936; 3,254,025; 3,282,955; 3,313,727; , 491,025; 3,533,945; 3,666,662; and 4,925,983. In one embodiment, the boron compound is an alkali metal borate or a mixture of alkali and alkaline earth metal borates. These metal borates are generally hydrated particulate metal borates that are known in the art. Alkali metal borates include alkali metal and alkaline earth metal borate mixtures. These metal borates are commercially available. Representative patents disclosing suitable alkali and alkali metal and alkaline earth metal borates and methods for their production include US Pat. Nos. 3,997,454; 3,819,521; 853,772; 3,907,601; 3,997,454; and 4,089,790.

  The hydrocarbyl-substituted nitrogen-containing additive described above can also be post-treated by reaction with various optional agents other than the borated agent. In particular, urea, thiourea, dimercaptothiadiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon-substituted succinic anhydride, nitrile, epoxide and phosphorus compounds. References detailing such treatment are listed in US Pat. No. 4,654,403.

  The amine used in the preparation of the hydrocarbyl-substituted nitrogen-containing additive described above may be a polyamine. Suitable polyamines include aliphatic, alicyclic, heterocyclic and aromatic polyamines. Examples of polyamines include alkylene polyamines, hydroxy-containing polyamines, aryl polyamines and heterocyclic polyamines.

The alkylene polyamine is represented by the following formula:
_{(H) (R 5) N-} ( alkylene _{-N) n - (R 5)} (R 5)
Wherein n has an average value of 1 or from about 2 to about 10, or up to about 7, or up to about 5, and the number of “alkylene” groups is 1, or about 2 to about 10, or about 6 Up to or up to about 4 carbon atoms. Each R ₅ is independently hydrogen or is an aliphatic or hydroxy-substituted aliphatic group containing up to about 30 carbon atoms.

  Examples of such alkylene polyamines include methylene polyamine, ethylene polyamine, butylene polyamine, propylene polyamine, and pentylene polyamine. Also included are higher homologs and related heterocyclic amines such as piperazine and N-aminoalkyl substituted piperazines. Specific examples of such polyamines include ethylenediamine, diethylenetriamine (DETA), triethylenetetramine (TETA), tris- (2-aminoethyl) amine, propylenediamine, trimethylenediamine, tripropylenetetramine, tetraethylenepentamine, hexa Ethyleneheptamine, pentaethylenehexamine and the like.

  Higher homologues obtained by condensing two or more of the above-mentioned alkylene amines are likewise useful as mixtures of two or more of the above-mentioned polyamines.

  Ethylene polyamines such as those described above are useful. Such polyamines are described in Kirk Othmer's “Encyclopedia of Chemical Technology”, 2nd edition, Vol. 7, pages 22-37, Interscience Publishers, New York (1965) headline section of Ethylene Amine. Such polyamines are most conveniently prepared by reaction of ethylene dichloride with ammonia or by reaction of ethyleneimine with a ring-opening reagent (eg, water, ammonia, etc.). These reactions result in the formation of complex mixtures of polyalkylene polyamines containing cyclic condensation products, such as the piperazine described above. Ethylene polyamine mixtures are also useful.

  Another useful type of polyamine mixture is obtained from the above-described stripping of polyamine mixtures and remains as a residue, often referred to as "polyamine bottom". In general, alkylene polyamine bottoms can be characterized by a material having a boiling point of less than about 200 ° C. of less than 2%, usually less than 1% (wt%). A typical sample of such an ethylene polyamine bottom, obtained from the Dow Chemical Company (Freeport, TX) and called “E-100”, has a specific gravity of 1.0168 at 15.6 ° C. and a weight percent of nitrogen. The viscosity at 33.15 and 40 ° C. is 121 centistokes. Gas chromatographic analysis of such a sample shows about 0.93% “light fraction” (most likely DETA), 0.72% TETA, 21.74% tetraethylenepentamine and 76.61% Of pentaethylenehexamine and higher (based on weight). These alkylene polyamine bottoms contain cyclic condensation products such as piperazine and higher homologues such as diethylenetriamine, triethylenetetramine and the like. These alkylene polyamine bottoms may simply be reacted with an acylating agent, or they may be used with other amines, polyamines, or mixtures thereof.

  Another useful polyamine is a condensation reaction between at least one hydroxy compound and at least one primary or secondary amino group containing at least one polyamine reactant. Hydroxy compounds are in some cases polyhydric alcohols and polyamines. Polyhydric alcohols are described above. In certain embodiments, the hydroxy compound is a polyvalent amine. Multivalent amines include any of the monoamines described above reacted with alkylene oxides having 2 to about 20 or up to about 4 carbon atoms (eg, ethylene oxide, propylene oxide, butylene oxide, etc.). Examples of polyvalent amines include tri- (hydroxypropyl) amine, tris- (hydroxymethyl) aminomethane, 2-amino-2-methyl-1,3-propanediol, N, N, N ′, N′— Tetrakis (2-hydroxypropyl) ethylenediamine and N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine and, in some embodiments, tris (hydroxymethyl) aminomethane (THAM).

  In another embodiment, the polyamine is a hydroxy-containing polyamine. Hydroxy-containing polyamine analogs of hydroxy monoamines, particularly alkoxylated alkylene polyamines (eg, N, N- (diethanol) ethylenediamine) may be used. Such polyamines may be made by reacting the alkylene polyamines described above with one or more alkylene oxides described above. Reacting similar alkylene oxide-alkanolamine reaction products, such as the primary, secondary or tertiary alkanolamines described above, with ethylene, propylene or higher epoxides in a molar ratio of 1: 1 to 1: 2. May be used. The ratio and temperature of the reactants for carrying out such a reaction are known to those skilled in the art.

  Specific examples of alkoxylated alkylenepolyamines include N- (2-hydroxyethyl) ethylenediamine, N, N-bis (2-hydroxyethyl) ethylenediamine, 1- (2-hydroxyethyl) piperazine, mono (hydroxypropyl) substituted tetra Examples include ethylenepentamine and N- (3-hydroxybutyl) tetraethylenediamine. Higher homologues obtained by condensation of hydroxy-containing polyamines with amino or hydroxy groups as indicated above are also useful. Condensation with an amino group results in a higher amine with condensation with a hydroxy group while removing ammonia and a product containing an ether linkage with removal of water. Mixtures of any two or more than two polyamines described above are also useful.

  In another embodiment, the amine is a heterocyclic polyamine. Heterocyclic polyamines include aziridine, azetidine, azolidine, pyridine, pyrrole, indole, piperidine, imidazole, piperazine, isoindole, purine, morpholine, thiomorpholine, N-aminoalkyl morpholine, N-aminoalkylthiomorpholine, N-aminoalkyl And piperazine, N, N'-diaminoalkylpiperazine, azepine, azocine, azonin, azesin, and the respective tetra-, di- and perhydro derivatives of the above and mixtures of these two or more heterocyclic amines. It is done. In certain embodiments, the heterocyclic amine is a saturated 5-membered and 6-membered heterocyclic amine containing only nitrogen, oxygen and / or sulfur in the heterocycle, in particular piperidine, piperazine, thiomorpholine, morpholine, Such as pyrrolidine. Piperidine, aminoalkyl substituted piperidine, piperazine, aminoalkyl substituted piperazine, morpholine, aminoalkyl substituted morpholine, pyrrolidine and aminoalkyl substituted pyrrolidine. Usually, the aminoalkyl substituent is substituted on the nitrogen atom that forms part of the heterocycle. Specific examples of such heterocyclic amines include N-aminopropylmorpholine, N-aminoethylpiperazine and N, N'-diaminoethylpiperazine. Hydroxy heterocyclic polyamines are also useful. Examples include N- (2-hydroxyethyl) cyclohexylamine, 3-hydroxycyclopentylamine, para-hydroxyaniline, N-hydroxyethylpiperazine and the like.

The amine used in the preparation of the hydrocarbyl-substituted nitrogen-containing additive described above has at least four aromatic groups, at least one —NH ₂ functional group, and at least two secondary amino groups or tertiary. An amine having an amino group may be used.

式中、独立して、それぞれの変数は、以下のように定義されてもよい。Ｒ^１は、水素またはＣ_１〜５アルキル基（典型的には水素）であってもよく；Ｒ^２は、水素またはＣ_１〜５アルキル基（典型的には水素）であってもよく；Ｕは、脂肪族基、脂環式基または芳香族基であってもよく、但し、Ｕが脂肪族である場合、脂肪族基は、１〜５個、または１〜２個の炭素原子を含有する直鎖または分枝鎖のアルキレン基であってもよく、ｗは、１〜１０、または１〜４、または１〜２（典型的には１）であってもよい。 Suitable amines having at least three aromatic groups, at least one —NH ₂ functional group, and at least two secondary or tertiary amino groups may be represented by the following formula: ,

In the formula, independently, each variable may be defined as follows. R ¹ may be hydrogen or a C _1-5 alkyl group (typically hydrogen); R ² may be hydrogen or a C _1-5 alkyl group (typically hydrogen); U may be an aliphatic group, an alicyclic group or an aromatic group, provided that when U is aliphatic, the aliphatic group contains 1 to 5 or 1 to 2 carbon atoms. It may be a linear or branched alkylene group containing, and w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

式中、独立して、それぞれの変数は、以下のように定義されてもよい。Ｒ^１は、水素またはＣ_１〜５アルキル基（典型的には水素）であってもよく；Ｒ^２は、水素またはＣ_１〜５アルキル基（典型的には水素）であってもよく；Ｕは、脂肪族基、脂環式基または芳香族基であってもよく、但し、Ｕが脂肪族である場合、脂肪族基は、１〜５個、または１〜２個の炭素原子を含有する直鎖または分枝鎖のアルキレン基であってもよく、ｗは、１〜１０、または１〜４、または１〜２（典型的には１）であってもよい。 Suitable amines having at least three aromatic groups, at least one —NH ₂ functional group, and at least two secondary or tertiary amino groups may be represented by the following formula: ,

In the formula, independently, each variable may be defined as follows. R ¹ may be hydrogen or a C _1-5 alkyl group (typically hydrogen); R ² may be hydrogen or a C _1-5 alkyl group (typically hydrogen); U may be an aliphatic group, an alicyclic group or an aromatic group, provided that when U is aliphatic, the aliphatic group contains 1 to 5 or 1 to 2 carbon atoms. It may be a linear or branched alkylene group containing, and w may be 1 to 10, or 1 to 4, or 1 to 2 (typically 1).

式中、それぞれの変数Ｕ、Ｒ^１およびＲ^２は、上に記載したのと同じであり、ｗは、０〜９または０〜３または０〜１（典型的には０）である。 Alternatively, the amine may be represented by the following formula:

Wherein each variable U, R ¹ and R ² is the same as described above and w is 0-9 or 0-3 or 0-1 (typically 0).

のいずれかによってあらわされてもよい。 Examples of suitable amines having at least 3 aromatic groups are:

It may be expressed by either of the following.

  In one embodiment, the amine having at least three aromatic groups may comprise a mixture of compounds represented by the formulas disclosed above. One skilled in the art will appreciate that these compounds may be further reacted with the aldehydes described below to produce acridine derivatives. In addition to such compounds, one skilled in the art will also appreciate that other acridine structures that react aldehydes with other benzyl groups bridged with> NH groups may also be possible. Any or all N-bridged aromatic rings can be further condensed and possibly aromatized.

Examples of suitable amines having at least 3 aromatic groups are bis [p- (p-aminoanilino) phenyl] -methane, 2- (7-amino-acridin-2-ylmethyl) -N-4- {4 - [4- (4-amino - phenylamino) - benzyl] - phenyl} - ^{benzene-1,4-diamine,} N 4 - {4- [4- (4-amino - phenylamino) - benzyl] - phenyl} 2- [4- (4-Amino-phenylamino) -cyclohexa-1,5-dienylmethyl] -benzene-1,4-diamine, N- [4- (7-amino-acridin-2-ylmethyl) -phenyl ] -Benzene-1,4-diamine, or a mixture thereof.

  In one embodiment, the amine having at least 3 aromatic groups is bis [p- (p-aminoanilino) phenyl] -methane, 2- (7-amino-acridin-2-ylmethyl) -N-4- { It may be 4- [4- (4-amino-phenylamino) -benzyl] -phenyl} -benzene-1,4-diamine or a mixture thereof.

Amines having at least three aromatic groups may be prepared by a process involving the reaction of an aldehyde and an amine (typically 4-aminodiphenylamine). The resulting amine is an alkylene-coupled amine having at least three aromatic groups, at least one —NH ₂ functional group, and at least two secondary or tertiary amino groups. May be described.

  In certain embodiments, the hydrocarbyl substituted nitrogen-containing additive is a succinimide dispersant. In some embodiments, the hydrocarbyl substituted nitrogen-containing additive is a non-borated succinimide dispersant. In certain embodiments, the succinimide dispersant is derived from an alkylarylamine, a polyethylene polyamine, or some combination thereof. In certain embodiments, the succinimide dispersant may be derived from a hydrocarbyl substituted succinic anhydride or acid (reactive equivalents thereof such as esters, acid halides, etc.), and the hydrocarbyl substituted succinic anhydride has a molecular weight Contains 500 to 3000, or 1600 to 3000, or 1000 to 2000 polyisobutylene groups.

  Suitable hydrocarbyl substituted nitrogen-containing additives also include quaternary ammonium salts, also referred to as quaternary ammonium salt detergents and / or dispersants. Examples of suitable quaternary ammonium salts include (i) imide quaternary ammonium salts, (ii) Mannich quaternary ammonium salts, (iii) polyalkene-substituted amine quaternary ammonium salts, (iv) amide quaternary ammonium salts, ( v) ester quaternary ammonium salts, (vi) polyester quaternary ammonium salts, or (vii) any combination thereof.

  These various types of quaternary ammonium salts may be prepared in any of a number of ways, but are generally prepared by reacting a non-quaternized nitrogen-containing compound with a quaternizing agent. . Each different type of quaternary ammonium salt described uses a different non-quaternized nitrogen-containing compound in its preparation, but in general, non-quaternized nitrogen-containing compounds are quaternized capable of quaternization. Contains a primary nitrogen (or a primary or secondary nitrogen atom that can be alkylated to a tertiary nitrogen and then quaternized) and a hydrocarbyl substituent. The non-quaternized compound is typically a detergent and / or dispersant itself and can provide excellent performance when converted to a quaternary ammonium salt.

  The hydrocarbyl substituent of the quaternary ammonium salt detergent and / or dispersant and / or the hydrocarbyl substituent of the non-quaternized nitrogen-containing compound prepared therefrom is not unduly limited and any It may be a hydrocarbyl substituent.

  Each of the quaternary ammonium salts described above is prepared using a quaternizing agent. Suitable quaternizing agents are not unduly limited as long as the non-quaternized precursor tertiary nitrogen can be converted to quaternized nitrogen. Suitable quaternizing agents include dialkyl sulfates, benzyl halides, hydrocarbyl substituted carbonates, hydrocarbyl epoxides, esters of certain polycarboxylic acids, or mixtures thereof. Any of these agents, including hydrocarbyl epoxides and hydrocarbyl substituted carbonates, may be used in combination with an acid (eg, acetic acid). Suitable acids include carboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and the like. For example, in certain embodiments involving amide quaternary ammonium salts, quaternizing agents (including hydrocarbyl epoxides and hydrocarbyl substituted carbonates) are used without the addition of such acids. In certain embodiments, some amount of water is present during the reaction, particularly when no acid is used.

式中、Ｒ^１５、Ｒ^１６、Ｒ^１７およびＲ^１８は、独立して、ＨまたはＣ_１〜５０ヒドロカルビル基であってもよい。適切なヒドロカルビルエポキシドの例としては、スチレンオキシド、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチルベンオキシド、Ｃ_２〜５０エポキシド、またはこれらの組み合わせが挙げられる。 In certain embodiments, the quaternizing agent may be a hydrocarbyl epoxide, as represented by the following formula:

Wherein R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may independently be H or a C _1-50 hydrocarbyl group. Examples of suitable hydrocarbyl epoxides include styrene oxide, ethylene oxide, propylene oxide, butylene oxide, stilbene oxide, _C2-50 epoxide, or combinations thereof.

  With respect to the amide quaternary ammonium salts described above, the presence of an amide group and its collision with the rest of the structure allows for a salt that is “self-chlorinated,” thus the structure also has at least one other acid group Assuming that it does not require a separate anion. For example, when preparing a non-quaternized nitrogen-containing compound using hydrocarbyl substituted succinic anhydride and similar materials, the resulting quaternary ammonium salt may have an amide group and an acid group, where the acid group is , The counter anion of the quaternized nitrogen or amide quaternary ammonium salt obtained. These materials may be described as betaines. The preparation of these quaternary ammonium salts will typically be characterized by the use of alkylene oxide quaternizing agents or similar agents without the addition of a separate acid.

  In another embodiment, the quaternizing agent may be a carboxylic acid ester or a polycarboxylic acid ester. In certain embodiments, quaternizing agents include dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.

  In certain embodiments, the quaternary ammonium salt is a quaternary made by polymerizing a condensation product of a hydrocarbyl substituted acylating agent with a compound having an oxygen or nitrogen atom capable of condensing the acylating agent. This condensation product contains at least one tertiary amino group or by further polymerizing a hydrocarbyl-substituted acylating agent and then reacting with a compound having an oxygen atom or a nitrogen atom. Quaternized polymer made. One or more tertiary amino groups on the polymer may then be quaternized using the methods described herein to obtain a quaternized polymer.

  Any of the above quaternary ammonium salts may be derived in the presence of a protic solvent. In certain embodiments, the process used to prepare these additives is substantially free of to methanol of methanol. In one embodiment, protic solvents include compounds containing one or more hydroxyl functional groups and may include water. In certain embodiments, the protic solvent is water.

  Further details regarding quaternary ammonium, examples thereof, and methods of making them can be found in US Pat. Nos. 7,951,211 and 7,906,470, US Published Application No. 2008/0113890, US Published Application No. 2012/0010112 and US Application Publication No. 2011/0315107 and International Publications WO 2010/132259, WO 2010/097624 and WO 2011/095819.

  The dispersant containing nitrogen may be a polyetheramine. In some embodiments, the polyetheramine may comprise a compound having two or more consecutive ether groups and at least one primary, secondary or tertiary amine group; Amine nitrogen has some basicity. The polyetheramines of the present invention render poly (oxyalkylene) amines soluble in conventional liquid fuels (eg, hydrocarbons boiling in the range of gasoline or diesel fuel) and blends of hydrocarbon and non-hydrocarbon fuels. A poly (oxyalkylene) amine having a sufficient number of repeating oxyalkylene units. In general, poly (oxyalkylene) amines having at least 5 oxyalkylene units are suitable for use in the present invention.

  The poly (oxyalkylene) amine includes at least two hydrocarbyl poly (oxyalkylene) -amines, hydrocarbyl poly (oxyalkylene) polyamines, hydropoly (oxyalkylene) -amines, hydropoly (oxyalkylene) polyamines, and derivative molecules. Mention may be made of poly (oxyalkylene) amine and / or polyhydric alcohol derivatives having a poly (oxyalkylene) polyamine chain.

In one embodiment, a poly (oxyalkylene) amine for use in the present invention is represented by the following formula:
R ⁶ O (A ² O) _m R ⁷ NR ⁸ R ⁹
In which R ⁶ is a hydrocarbyl group containing 1 to 50 carbon atoms, or 8 to 30 carbon atoms; A ² is 2 to 18 carbon atoms, in certain embodiments 2 to 6 An alkylene group having 1 carbon atom; m is a number from 1 to 50; and R ⁷ is an alkylene group having 2 to 18 carbon atoms, in an embodiment, 2 to 6 carbon atoms. R ⁸ and R ⁹ are independently hydrogen, a hydrocarbyl group or — [R′N (R ″)] nR ″ ′, where R ′ is an alkylene group having 2 to 6 carbon atoms R ″ and R ″ ′ are independently hydrogen or a hydrocarbyl group, and n is a number from 1 to 7.

In another embodiment, the poly (oxyalkylene) amines of the present invention may be represented by the formula:
R ¹⁰ O [CH ₂ CH (CH ₂ CH ₃ ) O] _Z CH ₂ CH ₂ CH ₂ NH ₂
Wherein R ¹⁰ is an aliphatic group or alkyl-substituted phenyl group containing 8 to 30 carbon atoms; Z is a number from 12 to 30. In yet another embodiment, the poly (oxyalkylene) amines of the present invention may be represented by the above formula, wherein R ¹⁰ is CH ₃ CH (CH ₃ ) — [CH ₂ CH (CH ₃ )] _2. CH (CH ₃ ) CH ₂ CH ₂ —, and Z is a number from 16 to 28. The poly (oxyalkylene) amine of the present invention may have a molecular weight in the range of 300 to 5,000.

  The polyetheramines of the present invention can be prepared by using the polyethers described above as intermediates and converting them to polyetheramines. The polyether intermediate can be converted to a polyetheramine by several methods. Convert polyether intermediates to polyetheramines by reductive amination with ammonia, primary amines or polyamines as described in US Pat. Nos. 5,112,364 and 5,752,991. be able to. In one embodiment, the polyether intermediate can be converted to a polyetheramine by addition reaction of the polyether to acrylonitrile to create a nitrile, which is then hydrogenated to create the polyetheramine. US Pat. No. 5,264,006 provides reaction conditions for cyanoethylation of polyether and acrylonitrile, followed by hydrogenation to make a polyetheramine. In yet another embodiment, as described in US Pat. No. 4,247,301, a polyether intermediate or poly (oxyalkylene) alcohol is converted to the corresponding poly (oxyalkylene) chloride with a suitable chlorinating agent. Convert and then replace chlorine with ammonia, primary or secondary amines, or polyamines.

式中、Ｒ^１１は、４〜３０個の炭素原子を有するヒドロカルビル基であり、Ａ^３およびＡ^４は、ビシナルアルキレン基であり、ｘとｙの合計は、少なくとも１の整数である。ヒドロカルビル基は、主に炭化水素の性質を有するが、非炭化水素置換基を有してもよく、ヘテロ原子を有してもよい炭素原子の一価の基である。ヒドロカルビル基Ｒ^１１は、４〜３０個の炭素原子、または１０〜２２個の炭素原子を含むアルキル基またはアルキレン基であってもよい。ビシナルアルキレン基Ａ^３およびＡ^４は、同じであってもよく、または異なっていてもよく、隣接する炭素原子または近くにある炭素原子に炭素窒素結合および炭素酸素結合を有するエチレン（−ＣＨ_２−）、プロピレン（−ＣＨ_２ＣＨ_２ＣＨ_２−）およびブチレン（−ＣＨ_２ＣＨ_２ＣＨ_２ＣＨ_２−）が挙げられる。アルコキシル化脂肪族アミンの例としては、ジエトキシル化タローアミン、ジエトキシル化オレイルアミン、ジエトキシル化ステアリルアミン、および大豆油脂肪酸由来のジエトキシル化アミンを挙げることができる。アルコキシル化脂肪族アミンは、ＡｋｚｏからＥｔｈｏｍｅｅｎ（登録商標）シリーズで市販されている。 The mixed alkoxylate of the present invention may further contain an alkoxylated aliphatic amine, and may contain an amine represented by the following formula:

In the formula, R ¹¹ is a hydrocarbyl group having 4 to 30 carbon atoms, A ³ and A ⁴ are vicinal alkylene groups, and the sum of x and y is an integer of at least 1. The hydrocarbyl group mainly has a hydrocarbon property, but may have a non-hydrocarbon substituent and may be a monovalent group of carbon atoms which may have a hetero atom. The hydrocarbyl group R ¹¹ may be an alkyl or alkylene group containing 4 to 30 carbon atoms, or 10 to 22 carbon atoms. The vicinal alkylene groups A ³ and A ⁴ may be the same or different and are ethylene (—CH ₂₎ having a carbon nitrogen bond and a carbon oxygen bond at adjacent or nearby carbon atoms. -), propylene _{(-CH 2 CH 2 CH 2 -} ) and butylene _{(-CH 2 CH 2 CH 2 CH} 2 -) and the like. Examples of alkoxylated aliphatic amines include diethoxylated tallow amine, diethoxylated oleylamine, diethoxylated stearylamine, and diethoxylated amines derived from soybean oil fatty acids. Alkoxylated aliphatic amines are commercially available from Akzo in the Ethomeen® series.

Nitrogen-containing compounds may be 0.01% to 5%, or 0.1% to 3%, or 0.2% to 1.5%, or 0.25% by weight of the described composition. May be present at ˜1 wt%, or 0.5 wt% ˜1 wt%.
(Sulfur-containing compounds)

  In an embodiment, the bearing lubricant of the present invention, or a method using the same, may further include (d) a sulfur-containing compound.

  Suitable sulfur-containing compounds include vulcanized olefins. Any olefin described herein for other components is also a suitable olefin from which vulcanized olefins may be prepared. In certain examples, the sulfur-containing compound is a vulcanized olefin derived from isobutylene, butylene, propylene, ethylene, or some combination thereof. In certain examples, the sulfur-containing compound is a vulcanized olefin derived from any of the natural or synthetic oils described above, or some combination thereof. For example, the vulcanized olefin may be derived from vegetable oil.

When a sulfur-containing compound is present, the sulfur-containing compound is 0.01% to 5%, or 0.1% to 3%, or 0.2% to 1.5% by weight of the composition described. %, Or 0.25 wt% to 1 wt%, or 0.5 wt% to 1 wt%.
(Additional additives)

  Optionally, the lubricating composition of the present invention comprises one or more additional additives, the one or more additional additives comprising a foam inhibitor, a demulsifier, a pour point depressant, Includes antioxidants, dispersants other than those described above, metal deactivators (eg, copper deactivators), antiwear agents other than those described above, extreme pressure agents, viscosity modifiers, or mixtures thereof It may be selected from a group. Optional additives are 50 ppm, 75 ppm, 100 ppm or 150 ppm to 5 wt%, 4 wt%, 3 wt%, 2 wt% or even 1.5 wt%, or 75 ppm to 0.5 wt%, respectively. , 100 ppm to 0.4 wt%, or 150 ppm to 0.3 wt%, the wt% values being relative to the overall lubricating oil composition. However, some optional additives, including a viscosity modifying polymer that can be selectively considered part of the base liquid, are considered to be 30% by weight, if considered separate from the base liquid, Note that many amounts may be present, including up to 40 wt%, or even up to 50 wt%. Note that the optional additives may be used alone or in mixtures thereof.

  Antifoaming agents (also known as foam inhibitors) are known in the art and include, but are not limited to, organic silicone foam inhibitors and non-silicon foam inhibitors. Examples of organosilicones include dimethyl silicone and polysiloxane. Examples of non-silicon foam inhibitors include, but are not limited to, polyethers, polyacrylates, and mixtures thereof, and copolymers of ethyl acrylate, 2-ethylhexyl acrylate and optionally vinyl acetate. In certain embodiments, the antifoaming agent is a polyacrylate. Antifoaming agents may be present in the composition from 0.001 to 0.012 pbw, or 0.004 pbw or even 0.001 to 0.003 pbw.

  Demulsifiers are known in the art and include, but are not limited to, propylene oxide, ethylene oxide, polyoxyalkylene alcohols, alkylamines, amino alcohols, diamines or polyamine derivatives that are subsequently reacted with ethylene oxide or substituted ethylene oxide. Or mixtures thereof. Examples of demulsifiers include polyethylene glycol, polyethylene oxide, polypropylene oxide, (ethylene oxide-propylene oxide) polymers, and mixtures thereof. In certain embodiments, the demulsifier is a polyether. The demulsifier may be present in the composition in an amount of 0.002 to 0.012 pbw.

  Pour point depressants are known in the art and include, but are not limited to, maleic anhydride-styrene copolymers, polymethacrylates; polyacrylates; polyacrylamides; condensation products of haloparaffin waxes and aromatic compounds; vinyl carboxylates Polymers; and dialkyl fumarate, fatty acid vinyl esters, ethylene-vinyl acetate copolymers, alkylphenol formaldehyde condensation resins, terpolymers of alkyl vinyl ethers, and mixtures thereof.

  The composition of the present invention may further contain a corrosion inhibitor other than the above-mentioned several additives. Suitable corrosion inhibitors include hydrocarbylamine salts of dialkyldithiophosphates, hydrocarbylamine salts of hydrocarbylarene sulfonic acids, aliphatic carboxylic acids or esters thereof, nitrogen-containing carboxylic esters, ammonium sulfonates, imidazolines, mono-thiophosphates or Esters, or any combination thereof; or mixtures thereof.

式中、Ｃｙは、ベンゼン環またはナフタレン環である。Ｒ^２８は、約４〜約３０個、好ましくは、約６〜約２５個、さらに好ましくは、約８〜約２０個の炭素原子を含むヒドロカルビル基である。ｚは、独立して、１、２、３または４であり、最も好ましくは、ｚは、１または２である。Ｒ^２３、Ｒ^２４およびＲ^２５は、上に記載したとおりである。 Examples of hydrocarbylamine salts of dialkyldithiophosphates of the present invention include, but are not limited to, those described above, and the reaction products of diheptyldithiophosphate or dioctyldithiophosphate or dinonyldithiophosphate with ethylenediamine, morpholine or Primene 81R, Or a mixture thereof. A suitable hydrocarbylamine salt of hydrocarbylarene sulfonic acid for use in the corrosion inhibitor package of the present invention is represented by the following formula:

In the formula, Cy is a benzene ring or a naphthalene ring. R ²⁸ is a hydrocarbyl group containing about 4 to about 30, preferably about 6 to about 25, more preferably about 8 to about 20 carbon atoms. z is independently 1, 2, 3 or 4, and most preferably z is 1 or 2. R ²³ , R ²⁴ and R ²⁵ are as described above.

  Examples of hydrocarbyl amine salts of hydrocarbyl arene sulfonic acids of the present invention include, but are not limited to, ethylenediamine salts of dinonyl naphthalene sulfonic acids.

  Examples of suitable aliphatic carboxylic acids or esters thereof include glycerol monooleate and oleic acid. Examples of suitable esters of nitrogen-containing carboxylic acids include oleyl sarcosine.

  The corrosion inhibitor may be present in the range of 0.02-0.2 pbw, 0.03-0.15 pbw, 0.04-0.12 pbw, or 0.05-0.1 pbw of the lubricating oil composition. Good. The corrosion inhibitors of the present invention may be used alone or in mixtures thereof.

  The lubricating composition of the present invention may further contain a metal deactivator. A metal deactivator is used to neutralize the catalytic effect of the metal to promote the oxidation of the lubricating oil. Suitable metal deactivators include, but are not limited to, triazole, tolyltriazole, thiadiazole, or combinations thereof and derivatives thereof. Examples include benzotriazole derivatives other than those described above, benzimidazole, 2-alkyldithiobenzimidazole, 2-alkyldithiobenzothiazole, 2- (N, N′-dialkyldithio-carbamoyl) benzothiazole, 2,5 -Bis (alkyl-dithio) -1,3,4-thiadiazole, 2,5-bis (N, N'-dialkyldithiocarbamoyl) -1,3,4-thiadiazole, 2-alkyldithio-5-mercaptothiadiazole, Or a mixture thereof. These additives may be used in an amount of 0.01 to 0.25% by weight in the entire composition.

  In certain embodiments, the metal deactivator is a hydrocarbyl substituted benzotriazole compound. Benzotriazole compounds containing hydrocarbyl substituents include at least one of the following ring positions 1- or 2- or 4- or 5- or 6- or 7-benzotriazole. The hydrocarbyl group contains from about 1 to about 30, preferably from about 1 to about 15, more preferably from about 1 to about 7 carbon atoms, and most preferably the metal deactivator alone 5-methylbenzotriazole, or a mixture thereof.

  The metal deactivator may be present in the range of 0.001 to 0.1 pbw, 0.01 to 0.04 pbw, or 0.015 to 0.03 pbw of the lubricating oil composition. A metal deactivator may also be present in the composition from 0.002 pbw or 0.004 pbw to 0.02 pbw. The metal deactivator may be used alone or in a mixture thereof.

  An antioxidant comprising (i) an alkylated diphenylamine and (ii) a substituted hydrocarbyl mono-sulfide may also be present. In certain embodiments, the alkylated diphenylamines of the present invention are bis-nonylated diphenylamine and bis-octylated diphenylamine. In certain embodiments, the substituted hydrocarbyl monosulfide includes n-dodecyl-2-hydroxyethyl sulfide, 1- (tert-dodecylthio) -2-propanol, or a combination thereof. In certain embodiments, the substituted hydrocarbyl monosulfide is 1- (tert-dodecylthio) -2-propanol.

  The antioxidant package may also contain sterically bulky phenol. Examples of suitable hydrocarbyl groups include, but are not limited to, 2-ethylhexyl or n-butyl ester, dodecyl or mixtures thereof. Examples of methylene bridged sterically bulky phenols include, but are not limited to, 4,4′-methylene-bis (6-tert-butyl o-cresol), 4,4′-methylene-bis (2-tert- Amyl-o-cresol), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 4,4′-methylene-bis (2,6-di-tertbutylphenol), or mixtures thereof Is mentioned.

  In certain embodiments, the compositions of the present invention are essentially free or completely free of alkylated phenols, alkaryl amines, or both, or at most 2.0% by weight, Containing at most 1.0 wt%, or even at most 0.5 wt%, the wt% value refers to the total amount of alkylated phenol and / or alkarylamine present in the overall lubricant.

The invention is further illustrated by the following examples, which describe particularly advantageous embodiments. These examples are given to illustrate the invention, but are not intended to limit the invention.
(Example set 1)

An example set of coal grinder lubricant composition is prepared. The formulation of the examples are summarized in the table below by weight percent, listing phosphorus-containing compounds and nitrogen-containing dispersants on an active substance basis.

（７）試験終了時に、実施例の潤滑剤を取り出し、保存し、ラベルを付ける。
（８）繊維製品用薬剤ですすぐことによって試験ベアリングを洗浄し、次いで、超音波浴において、トルエンを用いてベアリングを１５分間洗浄する。繊維製品用薬剤で再びすすぎ、ベアリングを乾燥させる。
（９）試験ベアリングの終了時の重量を１ミリグラムの１０分の１まで得る。
（１０）試験重量の開始時および終了時の重量から重量損失を決定し、摩耗した金属の量について、終了時の試験実施例の潤滑剤を分析する。 The lubricants of each example are tested in a procedure that mimics the harsh conditions found in mills, specifically coal mill bearings. Coal dust is added to the lubricant of this example to mimic the in-situ incorporation, measure the impact on lubricant performance, and show the ability of these examples to give acceptable performance under these conditions. This test uses a high load KRL type tester and an SNR 32008 C test bearing. This test procedure includes the following steps.
(1) Clean the new test bearing with toluene in an ultrasonic bath for 15 minutes. Rinse with textile spirit and dry the bearings.
(2) Obtain the starting weight of the test bearing to 1 / 10th of a milligram.
(3) Place the bearing on the test head of the KRL type tester.
(4) Add 0.9% by weight of coal dust to the lubricant of the example. Lubricant and coal dust are mixed well using a high speed shaker, and then the test head is filled with 30 ml of the lubricant of the example mixed with coal dust.
(5) Place the test head in the KRL type tester.
(6) Conduct the harsh conditions experienced by the crusher bearings and the test conditions outlined in Table 2 designed to mimic the mode of operation.

(7) At the end of the test, the lubricant of the example is removed, stored and labeled.
(8) Clean the test bearings by rinsing with textile agent and then rinse the bearings with toluene in an ultrasonic bath for 15 minutes. Rinse again with textile agent and dry the bearings.
(9) Obtain the weight at the end of the test bearing to 1 / 10th of 1 milligram.
(10) The weight loss is determined from the weight at the start and end of the test weight, and the lubricant of the test example at the end is analyzed for the amount of worn metal.

The results from testing the lubricants of the examples are summarized in the following table.

This result shows that the pulverizer bearing lubricant of the present invention and the method of using it can provide significant performance in the harsh conditions found in pulverizer bearings. The lubricants and methods described are particularly advantageous compared to currently marketed options for these applications.
(Example set 2)

A second example set of coal grinder lubricant composition is prepared without the addition of additional additives. The formulation of the examples are summarized in the table below by weight percent, listing phosphorus-containing compounds and nitrogen-containing dispersants on an active substance basis.

The examples in Table 4 are evaluated using the same test procedure as described above. The results are summarized in the following table.

  This result shows that the pulverizer bearing lubricant of the present invention and the method of using it can provide significant performance in the harsh conditions found in pulverizer bearings. The lubricants and methods described are particularly advantageous compared to currently marketed options for these applications.

  In particular, the inventive examples (Examples 13, 14, 15 and 18) all have better weight than the un-added lubricant (Examples 10 and 12). Note that it has a loss result. Example 16 has good weight loss results, but the amount of iron in the lubricant is too high at the end of the test. Similarly, Example 17 is moderate although it still has a high amount of iron, but has a high weight loss. In contrast, the embodiments of the present invention give a good balance of results in both areas. Furthermore, the commercial example (Example 12) with the top treated showed a marked improvement when the invention was applied to it.

  Each of the documents listed above is incorporated herein by reference. Unless stated otherwise or otherwise indicated, all stated quantities specifying quantities, reaction conditions, molecular weight, number of carbon atoms, etc. should be understood to be modified with the term “about”. is there. Unless otherwise indicated, all percentages and formulation values are on a weight basis. Unless otherwise indicated, all molecular weights are number average molecular weights. Unless otherwise indicated, each chemical or composition referred to herein may contain isomers, by-products, derivatives, and other such materials commonly understood to exist in commercial grade. It should be interpreted as a commercial grade material. However, the amount of each chemical component is present except for any solvent or diluent that may be customarily present in commercially available materials, unless otherwise indicated. It should be understood that the upper and lower limit amounts, ranges, and ratio boundary values set forth herein may be independently combined. Similarly, the range and amount of each element of the invention may be used in conjunction with the range or amount of any other element. As used herein, the expression “consisting essentially of” permits inclusion of substances that do not significantly affect the basic and new characteristics of the composition under consideration.

Claims (15)

A method of lubricating a bearing of a solid fuel crusher,
I. In the bearing,
(A) an oil having a viscosity that acts as a lubricant;
(B) a phosphorus-containing compound;
(C) a nitrogen-containing dispersant;
Optionally, further comprising (d) supplying a lubricant composition comprising a sulfur-containing compound. The method of claim 1, wherein the oil having a viscosity that serves as a lubricant comprises a mineral base oil. The method according to claim 1, wherein the oil having a viscosity acting as a lubricant comprises a synthetic base oil. 4. The method according to any one of claims 1 to 3, wherein the phosphorus-containing compound comprises an alkyl phosphite, a phosphate ester, an amine salt of a phosphate ester, or some combination thereof. The nitrogen-containing dispersant comprises a polyetheramine; a borated succinimide dispersant; a non-borated succinimide dispersant; a Mannich dispersant comprising a reaction product of a dialkylamine, an aldehyde and a hydrocarbyl-substituted phenol; or any combination thereof The method in any one of Claims 1-4. 6. A method according to any preceding claim, wherein the nitrogen-containing dispersant comprises a non-borated succinimide dispersant derived from an aromatic amine. The method according to claim 1, wherein the lubricant composition further comprises (d) a sulfur-containing compound. 9. The method according to any of claims 1 to 8, wherein the phosphorus-containing compound comprises an alkyl phosphite and the nitrogen-containing dispersant comprises a non-borated succinimide dispersant. The phosphorus-containing compound is present in the lubricant composition in an amount of 0.01 to 5.0% by weight;
The method according to claim 1, wherein the nitrogen-containing dispersant is present in the lubricant composition in an amount of 0.01 to 4.0% by weight. (A) an oil having a viscosity that acts as a lubricant;
(B) a phosphorus-containing compound;
(C) A bearing lubricant for a solid fuel grinder comprising a nitrogen-containing dispersant. 11. The bearing lubricant of claim 10, wherein the phosphorus-containing compound comprises an alkyl phosphite, a phosphate ester, an amine salt of a phosphate ester, or some combination thereof. The nitrogen-containing dispersant comprises a polyetheramine; a borated succinimide dispersant; a non-borated succinimide dispersant; a Mannich dispersant comprising a reaction product of a dialkylamine, an aldehyde and a hydrocarbyl-substituted phenol; or any combination thereof The bearing lubricant according to any one of claims 10 to 11. The phosphorus-containing compound is present in the lubricant composition in an amount of 0.01 to 5.0% by weight;
The bearing lubricant according to any one of claims 10 to 12, wherein the nitrogen-containing dispersant is present in the lubricant composition in an amount of 0.01 to 4.0% by weight. The bearing lubricant according to claim 10, wherein the bearing lubricant further comprises (d) a sulfur-containing compound. Use of a lubricant composition for increasing the service life or durability of a bearing of a solid fuel crusher, wherein the lubricant composition comprises:
(A) an oil having a viscosity that acts as a lubricant;
(B) a phosphorus-containing compound;
(C) Use comprising a nitrogen-containing dispersant.