CN107986993B

CN107986993B - Compound with thickening effect, lubricating grease and preparation method thereof

Info

Publication number: CN107986993B
Application number: CN201610957879.8A
Authority: CN
Inventors: 孙洪伟; 何懿峰; 段庆华; 郑会; 白文娟; 李华; 刘中其; 姜靓; 姚立丹; 杨海宁
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2016-10-27
Filing date: 2016-10-27
Publication date: 2020-06-16
Anticipated expiration: 2036-10-27
Also published as: CN107986993A

Abstract

The invention relates to the field of lubricants, and discloses a compound with a thickening effect, lubricating grease and preparation methods of the compound and the lubricating grease. The compound is shown as a formula I. The preparation method of the compound comprises the following steps: the calcium salt of a hydroxy fatty acid is reacted with a polyisocyanate, an amine and optionally further isocyanate to give a compound having one or more-NHCONH-structures. The lubricating grease disclosed by the invention contains at least one compound. The method for preparing the lubricating grease comprises the following steps: reacting a calcium salt of a hydroxy fatty acid with a polyisocyanate, an amine and optionally further isocyanate to obtain a compound having one or more groups of-NHCONH-structure; the resulting product is refined and then mixed with the balance base oil and optional additives. The invention provides lubricating grease prepared by the method. The compound provided by the invention has excellent comprehensive performance, and can simultaneously improve various performances of the lubricating grease.

Description

Compound with thickening effect, lubricating grease and preparation method thereof

Technical Field

The invention relates to the field of lubricants, in particular to a compound with a thickening effect, lubricating grease and a preparation method of the compound and the lubricating grease.

Background

The anhydrous calcium-based lubricating grease, particularly the 12-calcium hydroxystearate soap-based lubricating grease, is used in many industries due to good comprehensive performance, but has the defect of low dropping point, most of which is about 160 ℃, so that the application range of the anhydrous calcium-based lubricating grease is limited. The thickening agent in the urea-based lubricating grease is named because the molecular structure of the thickening agent contains-NH-CO-NH-urea functional group structures, and can be divided into diurea (the most common), triuret, tetrauret, hexauret, octauret and the like according to the number of urea functional groups, and the thickening agent has the defects of poor mechanical stability and poor sensitivity to metal additives.

CN1600843A discloses a preparation method for preparing polyurea-lithium based grease, comprising: respectively melting C8-C24 organic amine and isocyanate in base oil, mixing, reacting, adding at least one C10-C20 fatty acid after the reaction is finished, adding a lithium hydroxide aqueous solution after the acid is melted, reacting, heating to 190-220 ℃, preserving heat, cooling, and homogenizing, wherein the method enables ureido and lithium-based lubricating grease to be generated by the simultaneous reaction in one kettle. However, the product obtained by the mechanical mixing method is a mixture of the urea-based grease and the lithium-based grease, and the overall performance (especially the high-temperature performance, the mechanical stability and the sensitivity to metal additives) of the mixed grease is not high, so that the grease with high-temperature performance, mechanical stability and sensitivity to metal additives can be prepared in the same reaction kettle, and the method has more important practical significance.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a compound with thickening effect, which can simultaneously improve the high-temperature performance, the mechanical stability and the sensitivity to metal additives of lubricating grease, the lubricating grease and preparation methods thereof.

In order to achieve the above object, in a first aspect, the present invention provides a compound having a thickening effect, the compound having a structural formula represented by formula I:

wherein R is¹Is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl; r²Is a substituted or unsubstituted arylene, substituted or unsubstituted alkylene, or substituted or unsubstituted cycloalkylene; r³Is a group having one or more-NHCONH-structures.

In a second aspect, the present invention provides a process for the preparation of a compound according to the first aspect, which process comprises:

in the selective presence of a catalyst, the structural formula is shown in the specification

With a polyisocyanate, an amine and optionally further isocyanate to give a compound having one or more-NHCONH-structures.

In a third aspect, the present invention provides a grease comprising a base oil and a thickener, wherein the thickener is provided by at least one compound according to the first aspect.

In a fourth aspect, the present invention provides a method of preparing a grease comprising:

(1) in the selective presence of a catalyst, the structural formula is shown in the specification

With a polyisocyanate, an amine and optionally further isocyanates to give a compound having one or more groups of the structure-NHCONH-;

(2) refining the product obtained in the step (1), and mixing with the balance of base oil and optional additives.

In a fifth aspect, the present invention provides a grease prepared by the method of the fourth aspect.

The compound provided by the invention chemically combines the calcium soap-based grease and the polyurea grease by virtue of hydroxyl, has excellent comprehensive performance, can simultaneously improve the high-temperature performance, the mechanical stability and the sensitivity to metal additives of the lubricating grease, can obtain the lubricating grease with the performance superior to that of the calcium soap-based lubricating grease and/or the carbamido lubricating grease by using the compound as a thickening agent, and can be widely applied to various industries.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is an ESI mass spectrum of a compound obtained according to one embodiment of the present invention.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In a first aspect, the present invention provides a thickening compound having a structural formula as shown in formula I:

In the present invention, the group used for substitution is at least one of hydroxyl, halogen and carboxyl.

Preferably, R¹Is alkyl (or straight-chain alkyl) of C1-C10(C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10). More preferably, R¹Is a linear alkyl group of C3-C10(C3, C4, C5, C6, C7, C8, C9 or C10).

Preferably, R²Alkylene groups (or linear alkylene groups) that are C1-C20(C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, or C20). More preferably, R²Is a linear alkylene group of C8-C15(C8, C9, C10, C11, C12, C13, C14 or C15).

Preferably, R³Has the structural formula

Wherein R is^3’Is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, or a substituted or unsubstituted cycloalkylene group, R is a group having 6 to 30 (preferably 6 to 20) carbon atoms⁴Is substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl,Substituted or unsubstituted aryl, or a group having one or more-NHCONH-structures.

More preferably, R^3’Is composed of

(the end connected to the fatty acid chain may be any one of the above-mentioned ends),

or-CH₂-(CH₂)₄-CH₂-. More preferably, R⁴Is a linear alkyl group of C6-C20, or a group with one or more-NHCONH-structures.

In the present invention, the group having one or more (e.g., 2, 3, 4, 5, 6 or 8) -NHCONH-structure (particularly R)⁴) And may be any of a variety of conventional monourea functional groups or multi-urea functional groups. It will be understood by those skilled in the art that the "group having one or more-NHCONH-structures" referred to in the present invention means that-NHCONH-may have one or more, and the groups on both sides of-NHCONH-as described above, selected from the group consisting of substituted or unsubstituted aryl (ene), substituted or unsubstituted alkyl (ene), and substituted or unsubstituted cycloalkyl (ene) may each be the same or different.

More preferably, R³The groups on both sides of the meso-NHCONH-structure may each be independently selected from:

or-CH₂-(CH₂)_0-16-CH₂-。

According to a most preferred embodiment of the invention, the compound has the formula:

(wherein, R³As previously mentioned), for example, specific examples may be:

in a second aspect, the present invention provides a process for preparing a compound of the first aspect, comprising:

(R¹And R²As previously described, the same applies below) with a polyisocyanate, an amine and optionally further isocyanate to give a compound having one or more-NHCONH-structures.

According to the second aspect of the present invention, the calcium salt of a hydroxy fatty acid can be obtained by various conventional methods, for example, by subjecting a hydroxy fatty acid to saponification with a calcium source. According to a preferred embodiment, the preparation of the calcium salt of a hydroxy fatty acid comprises: has a structural formula of

The hydroxy fatty acid(s) and a calcium source(s) which may be at least one of calcium oxide, calcium hydroxide and calcium alkoxide (e.g., methoxy compound, ethoxy compound, etc.), with the aid of water as a solvent, are mixed to carry out a saponification reaction, and the product obtained from the saponification reaction is optionally dehydrated by heating. The alkoxy compound may have the formula Ca²⁺(OR^-)₂Wherein, R can be C1-C10 alkyl, preferably C2-C6 alkyl, such as methyl, ethyl, n-propyl, n-butyl, tert-butyl, n-pentyl or tert-pentyl.

It will be appreciated by those skilled in the art that the saponification reaction may be carried out in a reaction medium which is not particularly critical and may be a conventional organic solvent (e.g., the various base oils used in greases) such as mineral oil, synthetic oil, vegetable oil or mixtures thereof.

More preferably, the preparation method of the calcium salt of hydroxy fatty acid comprises: mixing hydroxy fatty acid, reaction medium and calcium source at 70-120 deg.c for saponification, and optionally heating to 100-150 deg.c for dewatering. Further preferably, the preparation method of the calcium salt of hydroxy fatty acid comprises: mixing hydroxy fatty acid, reaction medium and calcium source at the temperature of 100-110 ℃ for saponification, and optionally heating and dehydrating at the temperature of 115-150 ℃. The saponification reaction time may be 60-180 min. Elevated temperature dehydration is an optional step and one skilled in the art will appreciate that elevated temperature dehydration is not required if saponification is carried out at a higher temperature and the saponified material is substantially free of water. The time for heating and dehydrating can be 5-30 min.

In the above preferred embodiment, the molar ratio of the hydroxy fatty acid and the calcium source is not particularly limited, but the amount of the calcium source (in terms of calcium element) may be controlled to be higher (e.g., 1 to 10 mol% higher) than that of the hydroxy fatty acid, and for example, the molar ratio of the hydroxy fatty acid and the calcium source may be 1 to 2: 1. the reaction medium may be used in an amount of 0.3 to 10kg per mole of the calcium source (in terms of elemental calcium).

In the above preferred embodiment, the calcium source may be at least one of an oxide, a hydroxide and an alkoxide compound of calcium, for example, calcium oxide, calcium hydroxide (calcium hydroxide monohydrate), calcium alkoxide (e.g., calcium methoxide, calcium ethoxide, etc.), and the like.

According to a second aspect of the invention, the catalyst is a selectively used substance to accelerate the reaction. The catalyst can be various substances capable of promoting the reaction of hydroxyl provided by hydroxy fatty acid and isocyanate, and preferably, the catalyst is at least one of organic amine (such as amine of C1-C20), carbonate, hydroxide of alkali metal, boron trifluoride and organic metal. More preferably, the catalyst is at least one of methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, boron trifluoride and organotin.

According to the second aspect of the present invention, the amount of the catalyst used is not particularly limited, and may be, for example, 0.5 to 10% by weight based on the weight of the hydroxy fatty acid.

According to the second aspect of the invention, the molar ratio of isocyanate (polyisocyanate) to hydroxyl groups provided by the calcium salt of a hydroxy fatty acid is generally from 0.5 to 2.5: 1. the calcium salt of a hydroxy fatty acid may be reacted with the isocyanate (polyisocyanate) at a temperature of 90-150 ℃ for a time of 0.5-5 h.

In one embodiment of the second aspect of the invention, the calcium salt of a hydroxy fatty acid is reacted with a polyisocyanate, an amine and optionally further isocyanate to give a compound having one or more groups of the structure-NHCONH-. Wherein the other isocyanate refers to isocyanate used additionally, and may be monoisocyanate (structural formula may be R)⁴-N ═ C ═ O (where R is⁴Substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl, as described above), such as phenyl isocyanate, tolyl isocyanate, chlorophenyl isocyanate, etc., and may also be a polyisocyanate (such as a diisocyanate (the structure may be O ═ C ═ N-R)^3’-N＝C＝O，R^3’Is a substituted or unsubstituted arylene, substituted or unsubstituted alkylene, or substituted or unsubstituted cycloalkylene group, R^3’The number of carbon atoms of (a) is preferably 6 to 30, as described above), and may be at least one of diphenylmethane diisocyanate, tolylene diisocyanate, 1, 6-hexamethylene diisocyanate, dicyclohexylmethyl diisocyanate, and m-xylylene diisocyanate), which can be selected by those skilled in the art according to the number of-NHCONH-structures. The amines may also be monoamines (of the formula R)⁵-NH₂Wherein R is⁵Can be C8-C24 alkyl, C8-C24 cycloalkyl or C6-C10 aryl, and is preferably selected from aniline, m-chloroaniline, p-toluidine, n-octylamine, dodecylamine (or laurylamine), tetradecylamine, hexadecylamine and octadecylamineAt least one), also diamines (formula NH)₂-R⁶-NH₂，R⁶May be C2-C12 alkylene or C6-C14 arylene, and is preferably at least one of ethylenediamine, propylenediamine, 1, 6-hexamethylenediamine (or hexamethylenediamine), p-phenylenediamine, o-phenylenediamine, and 4, 4' -biphenyldiamine). In the present invention, after reacting a polyisocyanate with the hydroxyl group provided by the calcium salt of a hydroxy fatty acid, the skilled person is fully aware of how to obtain a compound having one or more-NHCONH-structures by reacting a polyisocyanate (e.g. a diisocyanate) with an amine (e.g. a diamine). Specifically, the method comprises the following steps:

when preparing a compound having one-NHCONH-structure, the method of the second aspect may comprise: reacting a calcium salt of a hydroxy fatty acid with a diisocyanate and a monoamine, in that order, in the selective presence of a catalyst. The diisocyanate and monoamine may be used independently in an amount of 0.5 to 1.5mol per mol of the calcium salt of the hydroxy fatty acid (in terms of hydroxyl group).

When preparing a compound having two-NHCONH-structures, the method of the second aspect may comprise: reacting the calcium salt of a hydroxy fatty acid with a diisocyanate, a diamine, and a monoisocyanate in sequence in the selective presence of a catalyst. The diisocyanate, diamine and monoisocyanate may be used in an amount of 0.5 to 1.5mol, respectively, per mol of the calcium salt of a hydroxy fatty acid (in terms of hydroxyl group).

When preparing a compound having three-NHCONH-structures, the method of the second aspect may comprise: reacting a calcium salt of a hydroxy fatty acid with a first portion of a diisocyanate, a diamine, a second portion of a diisocyanate, and a monoamine, in that order, in the selective presence of a catalyst. The amounts of the first partial diisocyanate, the diamine, the second partial diisocyanate and the monoamine may be each independently 0.5 to 1.5mol per mol of the calcium salt of the hydroxy fatty acid (in terms of hydroxyl group). Wherein the first portion of diisocyanate and the second portion of diisocyanate may be the same or different.

When preparing a compound having a four-NHCONH-structure, the method of the second aspect may comprise: reacting a calcium salt of a hydroxy fatty acid with a first portion of a diisocyanate, a first portion of a diamine, a second portion of a diisocyanate, a second portion of a diamine, and a monoisocyanate, in that order, in the selective presence of a catalyst. The first partial diisocyanate, the first partial diamine, the second partial diisocyanate, the second partial diamine, and the monoisocyanate may be used in amounts of 0.5 to 1.5mol, respectively, per mol of the calcium salt of the hydroxy fatty acid (in terms of hydroxyl groups). Wherein the first portion of diisocyanate and the second portion of diisocyanate may be the same or different, as are the first portion of diamine and the second portion of diamine.

Compounds having six, eight, or even multiple-NHCONH-structures can be obtained in the same manner as above, and are not described in detail here.

In a third aspect, the present invention provides a grease comprising a base oil and a thickener provided by at least one of the compounds described above.

In the present invention, the object of the present invention can be achieved by using the above-mentioned compound as a thickener for grease, wherein the contents of the base oil and the thickener can be selected conventionally. Preferably, the base oil is present in an amount of 50 to 95 wt.%, more preferably 60 to 90 wt.%, most preferably 70 to 85 wt.%, based on the total weight of the grease. Preferably, the thickener is present in an amount of from 0.5 to 30 wt.%, more preferably from 1 to 25 wt.%, most preferably from 3 to 20 wt.%, based on the total weight of the grease.

The base oil may be various oils commonly used in the art, for example, at least one of mineral oil, synthetic oil, and vegetable oil. The kinematic viscosity of the base oil at 100 ℃ (measured with reference to GB/T265-1988) may be 2-100mm²/s。

The grease may further contain additives, and the content and kind of the additives are not particularly limited. The additive may be present in an amount of up to 20 wt.%, preferably from 0.5 to 15 wt.%, most preferably from 1 to 10 wt.%, based on the total weight of the grease.

The additive can be at least one of an antioxidant, an extreme pressure antiwear agent and a rust inhibitor, wherein the antioxidant is preferably an aromatic amine antioxidant, and can be at least one of diphenylamine, phenyl- α -naphthylamine and diisooctyldiphenylamine, and the diisooctyldiphenylamine is preferred, and the content of the antioxidant can be 0.01-5 wt%, and is preferably 0.1-2.5 wt% based on the total weight of the lubricating grease.

The extreme pressure antiwear agent may be at least one of zinc dialkyldithiophosphate, molybdenum dialkyldithiocarbamate, lead dialkyldithiocarbamate, triphenyl thiophosphate, an organic molybdenum complex, an olefin sulfide, molybdenum disulfide, polytetrafluoroethylene, molybdenum thiophosphate, chlorinated paraffin, antimony dibutyldithiocarbamate, tungsten disulfide, selenium disulfide, graphite fluoride, calcium carbonate, and zinc oxide. The extreme pressure antiwear agent may be present in an amount of from 0.5 to 12 wt.%, preferably from 0.8 to 8 wt.%, based on the total weight of the grease.

The rust inhibitor can be at least one of barium petroleum sulfonate, sodium petroleum sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenyl succinic acid. The rust inhibitor may be contained in an amount of 0.01 to 4.5% by weight, preferably 0.1 to 2% by weight, based on the total weight of the grease.

The greases of the present invention may be prepared in a conventional manner, for example, by mixing the thickener with a portion of the base oil and refining, and then mixing with the balance of the base oil and optional additives. The refining (constant temperature refining) conditions are not particularly limited, and can be carried out under conventional conditions. Preferably, the refining conditions include: the temperature is 140 ℃ and 230 ℃ (especially 140 ℃ and 180 ℃) and the time is 5-20 min.

According to the method for preparing the lubricating grease, the step (1) is a step for preparing the thickening agent (namely the compound of the invention), so the saponification reaction mode and conditions, the temperature-rising dehydration condition, and the selection or the using amount of the catalyst, the isocyanate and the amine in the step (1) are the same as those in the previous step, and are not repeated. In addition, the types and amounts of the base oil and additives can also be referred to the above.

As described above, in the step (1), the calcium salt of a hydroxy fatty acid can be obtained by various conventional methods, for example, by subjecting a hydroxy fatty acid to saponification with a calcium source. According to a preferred embodiment, the preparation of the calcium salt of a hydroxy fatty acid comprises:

has a structural formula of

The hydroxy fatty acid, part of the base oil (reaction medium) and a calcium source are mixed to carry out saponification, and then the product obtained from the saponification is selectively dehydrated by heating, wherein the calcium source is at least one of calcium oxide, calcium hydroxide and calcium alkoxide. More preferably, the preparation method of the calcium salt of hydroxy fatty acid comprises: mixing hydroxy fatty acid, part of base oil and calcium source at 70-120 deg.C for saponification, and optionally heating to dewater at 150 deg.C and 100 deg.C. Further preferably, the preparation method of the calcium salt of hydroxy fatty acid comprises: mixing hydroxy fatty acid, part of base oil and calcium source at the temperature of 100-110 ℃ for saponification, and optionally heating and dehydrating at the temperature of 115-150 ℃.

In the step (2), the refining (constant temperature refining) conditions are not particularly required, and may be performed under conventional conditions. Preferably, the refining conditions include: the temperature is 140 ℃ and 230 ℃ (especially 140 ℃ and 180 ℃) and the time is 5-20 min.

As will be understood by those skilled in the art, the sum of the amount of the part of the base oil and the amount of the remaining base oil is the total amount of the base oil used, and in the present invention, the weight ratio of the part of the base oil to the remaining base oil is preferably 1: 0.1-5.

After mixing with the balance of base oil and optional additives, filtration, homogenization, degassing and the like can also be carried out in a conventional manner to obtain a finished grease.

In a fifth aspect, the present invention also provides a grease prepared by the method of the fourth aspect. The lubricating grease prepared by the method has excellent comprehensive performance.

The present invention will be described in detail below by way of examples. 12-Hydroxystearic acid was purchased from Weining chemical company, Inc., of Tongliao.

Example 1

The raw material components are as follows: 12-hydroxystearic acid (8 kg); calcium hydroxide (0.99 kg); diphenylmethane diisocyanate (MDI, 6.66 kg); n-octylamine (3.44 kg); tripropylamine (1 kg); 500SN (120 kg).

(a) Preparation of the thickening agent: 80kg of 500SN base oil (kinematic viscosity at 100 ℃ of 11 mm) is added into a reaction kettle with the capacity of 200L and the functions of heating, stirring, circulating and cooling²And/s, purchased from Yanshan petrochemical company, China), 8kg of 12-hydroxystearic acid, stirring, heating to 80 ℃ to obtain a homogeneous system, slowly adding 0.99kg of calcium hydroxide and 3kg of water, heating to 100 ℃ to saponify for 2h, heating to 115 ℃, adding 6.66kg of MDI and 1kg of catalyst (tripropylamine), reacting for 30min, adding 3.44kg of n-octylamine, reacting for 30min, using the obtained product as a thickening agent in the step (b), dissolving the product in petroleum ether, filtering, washing the filter residue 3 times with petroleum ether, and testing the filter residue by Fourier cyclotron resonance mass spectrometry (FT-ICR MS) (ESI is an ion source)^-The sample is dissolved in toluene/methanol (volume ratio is 1:1) solvent, the concentration is 0.01mg/mL, 1 wt% ammonia water is added to promote ionization, the same is shown below), the obtained ESI mass spectrum is shown in figure 1, the strongest peak is a carboxylate anion peak which can be seen at 678, and the structure of the thickening agent is obtained by combining further hydrogen spectrum analysis and carbon spectrum analysis as follows:

(b) and (b) heating the product obtained in the step (a) to 170 ℃, keeping the temperature for 5min, adding 40kg of 500SN base oil, stirring, cooling, homogenizing, filtering, degassing, and taking out of the kettle to obtain the mono-urea carboxylic acid soap-based lubricating grease. According to the material feeding amount, the composition of the lubricating grease can be calculated as follows: 86.6 weight percent of base oil and 13.4 weight percent of thickening agent;

(c) the physical and chemical properties of the grease were analyzed and the results are shown in table 1.

Example 2

The raw material components comprise 12-hydroxystearic acid (10kg), calcium hydroxide (1.23kg), diphenylmethane diisocyanate (MDI, 8.33kg), hexamethylene diamine (3.87kg), dibutyltin (0.5kg), phenyl isocyanate (3.96kg), poly α -olefin PAO10(200kg) and diisodecyl sebacate (DDS, 80 kg).

(a) Preparation of the thickening agent: 100kg of PAO10 base oil (kinematic viscosity of 10mm at 100 ℃) was added to a reaction kettle with heating, stirring, circulation and cooling capacity of 500L²And/s, purchased from exxon meifu corporation) and 10kg of 12-hydroxystearic acid, stirring, heating to 95 ℃ to form a homogeneous system, slowly adding 1.23kg of calcium hydroxide and 5kg of water, heating to 100 ℃ to saponify for 1h, heating to 150 ℃, adding 100kg of PAO10, cooling to 90 ℃, adding 8.33kg of MDI and 0.5kg of catalyst (dibutyltin), reacting for 60min, adding 3.87kg of hexamethylenediamine, reacting for 60min, adding 3.96kg of phenylisocyanate, reacting for 30min, taking the obtained product as a thickening agent for the step (b), dissolving the product in petroleum ether, filtering, washing the filter residue with petroleum ether for 3 times, testing the filter residue by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and analyzing the obtained ESI mass spectrum by combining a further hydrogen spectrum and a carbon spectrum to obtain the structure of the thickening agent as follows:

(b) heating the product obtained in the step (a) to 200 ℃, keeping the temperature for 5min, adding 80kg of DDS (with the kinematic viscosity of 6.8mm at 100 ℃), and adding²And/s, purchased from lubricant oil division, Chongqing Yibei, China), stirring, cooling to 100 ℃, and grinding to obtain the calcium diurea carboxylate-based lubricating grease. According toThe material feeding amount can be calculated, and the lubricating grease comprises the following components: 91.3 wt% of base oil and 8.7 wt% of thickening agent;

Example 3

The raw material components are as follows: 12-hydroxystearic acid (10 kg); calcium oxide (0.93 kg); diphenylmethane diisocyanate (MDI, 8.33 kg); ethylenediamine (2 kg); tolylene diisocyanate (TDI, 5.8 kg); octadecylamine (8.97 kg); potassium carbonate (0.1 kg); methyl silicone oil (70 kg); 150BS (30 kg).

(a) Preparation of the thickening agent: 70kg of methyl silicone oil (201-100) with a kinematic viscosity of 100mm at 25 ℃ is added into a reaction kettle with a volume of 200L and with heating, stirring, circulating and cooling functions²And/s, purchased from beijing china kingdom industrial and trade company limited), 10kg of 12-hydroxystearic acid, stirring, heating to 90 ℃ to obtain a homogeneous system, slowly adding 0.93kg of calcium oxide and 10kg of water, heating to 105 ℃ to saponify for 3h, heating to 120 ℃, adding 8.33kg of MDI and 0.1kg of catalyst (potassium carbonate), reacting for 2h, adding 2kg of ethylenediamine, reacting for 30min, adding 5.8kg of TDI, reacting for 30min, adding 8.97kg of octadecylamine, reacting for 30min, taking the obtained product as a thickening agent for the step (b), dissolving the product in petroleum ether, filtering, washing the filter residue with petroleum ether for 3 times, testing the filter residue by using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and analyzing the obtained mass spectrogram by combining further hydrogen spectrum and carbon spectrum to obtain the thickening agent with the following structure:

(b) heating the product obtained in the step (a) to 180 ℃, keeping the temperature for 10min, adding 30kg of 150BS (with the kinematic viscosity of 31mm at 100 ℃), and drying²And/s, available from Clarithromycin chemical company, the same below), stirring, cooling to 80 ℃, and grinding to obtain the calcium triurea carboxylate-based lubricating grease. According to the material feeding amount, the composition of the lubricating grease can be calculated as follows: 73.7 weight percent of base oil and 26.3 weight percent of thickening agent;

Example 4

The raw material components comprise 12-hydroxystearic acid (10kg), calcium hydroxide (1.23kg), 1, 6-hexamethylene diisocyanate (HDI, 5.6kg), laurylamine (6.17kg), potassium hydroxide (KOH, 0.1kg), zinc butyl octyl dithiophosphate (T202, 2kg), zinc naphthenate (T704, 2kg), molybdenum oxygen sulfide of dibutyl dithiocarbamate (T351, 2kg), molybdenum disulfide (3kg), phenyl- α -naphthylamine (1kg), poly α -olefin PAO6(60kg) and 150BS (20 kg).

(a) Preparation of the thickening agent: 60kg of PAO6 oil (kinematic viscosity 5.9mm at 100 ℃) was added to a reaction kettle with heating, stirring, circulation and cooling, the volume of which was 150L²(s) from exxonmobil corporation) and 10kg of 12-hydroxystearic acid, stirring, heating to 85 ℃ to obtain a homogeneous system, slowly adding 1.23kg of calcium hydroxide and 3kg of water, heating to 110 ℃ to saponify for 2h, adding 5.6kg of HDI and 0.1kg of catalyst (KOH), reacting for 30min, adding 6.17kg of laurylamine, reacting for 40min to obtain a product, using the product as a thickening agent in the step (b), dissolving the product in petroleum ether, filtering, washing the residue 3 times with petroleum ether, testing the residue by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), and analyzing the obtained ESI mass spectrum by combining a hydrogen spectrum and a carbon spectrum to obtain the thickening agent with the following structure:

(b) heating the product obtained in the step (a) to 200 ℃, keeping the temperature for 5min, adding 20kg of 150BS quenching oil, stirring and cooling, adding 2kg of T202, 2kg of T704, 2kg of T351 and 3kg of MoS in batches at 100 DEG C₂1kg of phenyl- α -naphthylamine, stirring uniformly, homogenizing, filtering, degassing and discharging from the kettle to obtain a finished product, wherein the lubricating grease comprises 71.2 wt% of base oil, 19.9 wt% of thickening agent, T2021.8 wt%, T7041.8 wt%, T3511.8 wt% and MoS according to the material feeding amount₂2.7 wt%, phenyl- α -naphthylamine 0.9 wt%;

Example 5

The raw material components are as follows: 12-hydroxystearic acid (10 kg); calcium oxide (0.44 kg); calcium hydroxide (0.65 kg); diphenylmethane diisocyanate (MDI, 8.33 kg); n-octylamine (4.3 kg); tripropylamine (1 kg); 500SN (100 kg).

(a) Preparation of the thickening agent: adding 70kg of 500SN oil and 10kg of 12-hydroxystearic acid into a reaction kettle with the capacity of 200L and the functions of heating, stirring, circulating and cooling, stirring, heating to 80 ℃ to form a uniform system, slowly adding 0.44kg of calcium oxide, 0.65kg of calcium hydroxide and 5kg of water into the reaction kettle, heating to 105 ℃ for saponification for 2 hours, heating to 115 ℃, adding 8.33kg of MDI and 1kg of catalyst (tripropylamine), reacting for 30min, and adding 4.3kg of n-octylamine, and reacting for 30 min;

(b) and (b) heating the product obtained in the step (a) to 180 ℃, keeping the temperature for 10min, adding 30kg of 500SN quenching oil, stirring and cooling, homogenizing, filtering, degassing, and taking out of the kettle to obtain the calcium monourea carboxylate-based lubricating grease. According to the material feeding amount, the composition of the lubricating grease can be calculated as follows: 81.1% of base oil and 18.9% of thickening agent;

Example 6

A grease was prepared as in example 1, except that 8kg of 12-hydroxystearic acid was replaced with 5kg of 10-hydroxydecanoic acid. The results are shown in Table 1.

Example 7

A grease was prepared as in example 1, except that 8kg of 12-hydroxystearic acid was replaced with 9.92kg of dihydroxybehenic acid, while the amounts of MDI, tripropylamine and n-octylamine used subsequently were doubled. The results are shown in Table 1.

Comparative example 1

The raw material components are as follows: 12-hydroxystearic acid (8 kg); calcium hydroxide (0.99 kg); 500SN (100 kg).

A grease was prepared as in example 1, except that MDI, tripropylamine and n-octylamine were not added. The results are shown in Table 1.

Comparative example 2

The raw material components are as follows: diphenylmethane diisocyanate (MDI, 6.66 kg); n-octylamine (6.88 kg); 500SN (100 kg).

Adding 70kg of 500SN lubricating base oil and 6.88kg of n-octylamine into a normal-pressure reaction kettle with the volume of 200L and the functions of heating, stirring, circulating and cooling, heating to 100 ℃ to form a homogeneous system, stirring for 10 minutes, adding 6.66kg of MDI, stirring for 30 minutes, then heating to 170 ℃ and keeping the temperature for 10 minutes, adding 30kg of 500SN quenching oil, stirring and cooling, homogenizing, filtering, degassing and discharging from the kettle to obtain the lubricating grease. According to the material feeding amount, the composition of the lubricating grease can be calculated as follows: 88.1 percent of base oil and 11.9 percent of thickening agent. The physical and chemical properties of the grease were analyzed and the results are shown in table 1.

Comparative example 3

The raw material components are as follows: 12-hydroxystearic acid (8 kg); calcium hydroxide (0.99 kg); diphenylmethane diisocyanate (MDI, 6.66 kg); n-octylamine (6.88 kg); 500SN (120 kg).

(a) Preparation of the thickening agent: adding 80kg of 500SN oil and 8kg of 12-hydroxystearic acid into a reaction kettle with the capacity of 200L and the functions of heating, stirring, circulating and cooling, stirring, heating to 80 ℃ to form a uniform system, slowly adding 0.99kg of calcium hydroxide and 3kg of water into the reaction kettle, heating to 100 ℃ for saponification for 2 hours, heating to 115 ℃, adding 6.66kg of MDI, stirring for 20 minutes, adding 6.88kg of n-octylamine, and reacting for 30 minutes to obtain a product serving as a thickening agent;

(b) heating the product obtained in the step (a) to 170 ℃, keeping the temperature for 5min, adding 40kg of 500SN quenching oil, stirring and cooling, homogenizing, filtering, degassing, and taking out of the kettle to obtain a finished product. According to the material feeding amount, the composition of the lubricating grease can be calculated as follows: 83.6 wt% of base oil, 16.4 wt% of thickening agent;

Comparative example 4

The polyurea-calcium-based lubricating grease is prepared according to the method disclosed in CN1600843A, and comprises the following specific steps:

Weighing 120kg of 500SN oil, dividing into three parts, respectively putting 6.88kg of n-octylamine and 6.66kg of MDI into the 500SN oil, heating and melting, mixing and reacting at 80 ℃, stirring, adding 8kg of 12-hydroxystearic acid after the reaction is completed, adding 0.99kg of calcium hydroxide after the reaction is melted and at 91 ℃, continuing to heat until the temperature reaches 180 ℃, keeping the temperature for 15min, then heating to 200 ℃, adding 500SN quenching oil, cooling to room temperature, and grinding twice.

Comparative example 5

A grease was prepared as in example 1, except that "calcium hydroxide" was replaced with "barium hydroxide" and the results of physical and chemical property analyses of the resulting grease are shown in Table 1.

Comparative example 6

A grease was prepared as in example 1, except that "calcium hydroxide" was replaced with "aluminum isopropoxide", and the results of physical and chemical property analysis of the resulting grease are shown in Table 1.

TABLE 1

From the above examples, it can be seen that the grease of the present invention has an excellent combination of properties, particularly high temperature performance, mechanical stability and susceptibility to metal-based additives. Specifically, the dropping point is higher, which indicates that the high temperature performance is better; the penetration of the working cone is small after 60 times, which indicates that the thickening capacity is strong; the difference between the working cone penetration of 60 times and 10 ten thousand times is small, which indicates that the mechanical stability is good; the corrosion resistance is qualified, which indicates that the corrosion resistance is good; the water loss is small, which indicates that the water resistance is good; the steel mesh has small oil separation, which shows that the colloid stability is good; the longer the bearing life is, the better the comprehensive performance is; after the metal additive is added, the dropping point is higher, and the difference value between the working penetration degrees of 60 times and 10 ten thousand times is small, so that the sensibility of the metal additive is good.

In particular, example 1 obtained a compound having both calcium soap and urea groups as the thickener, while comparative example 1 used a calcium soap-based compound as the thickener, comparative example 2 used a urea-based compound as the thickener, while comparative example 3 did not use a catalyst so that the thickener was a simple mixture of a calcium soap-based compound and a urea-based compound, and comparative example 4 prepared a grease with reference to the existing method of preparing a polyurea-calcium-based grease in the same pot (CN1600843A), i.e., a mechanical mixture of two greases, and it can be seen from the results of table 1 that the grease of the present invention performed far better than a simple soap-based grease, a urea-based grease, or a mixture of a soap-based grease and a urea-based grease.

Furthermore, example 1 used 12-hydroxystearic acid to prepare a grease, while examples 6-7 used other hydroxy fatty acids, it can be seen from the performance test results that greases with better performance can be obtained with the preferred hydroxy fatty acids of the present invention. In addition, example 1 shows that greases with better performance can be obtained with the preferred calcium source of the present invention than greases made in comparative examples 5-6, in which the calcium source is replaced with barium hydroxide and aluminum isopropoxide, respectively.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A compound having thickening effect, wherein the structural formula of the compound is shown as formula I:

wherein R is¹Is hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aryl; r²Is a substituted or unsubstituted arylene, substituted or unsubstituted alkylene, or substituted or unsubstituted cycloalkylene; r³Is a group having one or more-NHCONH-structures;

the group used for substitution is at least one of hydroxyl, halogen and carboxyl.

2. The compound of claim 1, wherein R¹Is C1-C10 alkyl; and/or

R²Is C1-C20 alkylene; and/or

R³Has the structural formula

Wherein R is^3’Is a substituted or unsubstituted arylene group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted cycloalkylene group, a C6-C30 unsaturated aliphatic or aromatic aliphatic hydrocarbon group, or a mixture thereof,

R⁴Is a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a group having one or more-NHCONH-structures.

3. The compound of claim 2, wherein R¹Is a linear alkyl group of C3-C10; and/or

R²Is a linear alkylene group of C8 to C15; and/or

R^3’Is composed of

or-CH₂-(CH₂)₄-CH₂-; and/or

R⁴Is a linear alkyl group of C6-C20, or a group with one or more-NHCONH-structures.

4. The compound of any one of claims 1-3, wherein the compound has the structural formula:

5. a process for preparing a compound according to any one of claims 1 to 4, comprising:

in the presence of a catalyst, the structural formula is shown in the specification

6. The method according to claim 5, wherein the calcium salt of a hydroxy fatty acid is prepared by a method comprising:

has a structural formula of

The hydroxy fatty acid and a calcium source are mixed to carry out saponification, and then the product obtained by saponification is selectively heated and dehydrated, wherein the calcium source is at least one of calcium oxide, calcium hydroxide and calcium alkoxide.

7. The method of claim 6, wherein the calcium salt of a hydroxy fatty acid is prepared by a method comprising: mixing hydroxy fatty acid, reaction medium and calcium source at 70-120 deg.c for saponification, and optionally heating to 100-150 deg.c for dewatering.

8. The method of claim 6, wherein the calcium salt of a hydroxy fatty acid is prepared by a method comprising: mixing hydroxy fatty acid, reaction medium and calcium source at the temperature of 100-110 ℃ for saponification, and optionally heating and dehydrating at the temperature of 115-150 ℃.

9. The method of claim 5 or 6, wherein the catalyst is at least one of an organic amine, a carbonate, a hydroxide of an alkali metal, boron trifluoride, and an organic metal.

10. The method of claim 5 or 6, wherein the catalyst is at least one of methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, boron trifluoride, and organotin.

11. A grease comprising a base oil and a thickener, wherein the thickener is provided by at least one compound according to any one of claims 1 to 4.

12. The grease of claim 11, wherein the base oil is present in an amount of 50-95 wt.% and the thickener is present in an amount of 0.5-30 wt.%, based on the total weight of the grease.

13. The grease of claim 11, wherein the base oil is present in an amount of 60-90 wt.%, and the thickener is present in an amount of 1-25 wt.%, based on the total weight of the grease.

14. The grease of claim 11, wherein the base oil is present in an amount of 70-85 wt.%, and the thickener is present in an amount of 3-20 wt.%, based on the total weight of the grease.

15. A method of preparing a grease, comprising:

(1) in the presence of a catalyst, the structural formula is shown in the specification

16. The method of claim 15, wherein the calcium salt of a hydroxy fatty acid is prepared by a method comprising:

has a structural formula of

The hydroxy fatty acid, part of the base oil and a calcium source are mixed to carry out saponification, and then the product obtained from the saponification is selectively heated and dehydrated, wherein the calcium source is at least one of calcium oxide, calcium hydroxide and calcium alkoxide.

17. The method of claim 16, wherein the calcium salt of a hydroxy fatty acid is prepared by a method comprising: mixing hydroxy fatty acid, part of base oil and calcium source at 70-120 deg.C for saponification, and optionally heating to dewater at 150 deg.C and 100 deg.C.

18. The method of claim 16, wherein the calcium salt of a hydroxy fatty acid is prepared by a method comprising: mixing hydroxy fatty acid, part of base oil and calcium source at the temperature of 100-110 ℃ for saponification, and optionally heating and dehydrating at the temperature of 115-150 ℃.

19. The method of any of claims 15-18, wherein the catalyst is at least one of an organic amine, a carbonate, an alkali metal hydroxide, boron trifluoride, and an organometallic.

20. The method of any one of claims 15-18, wherein the catalyst is at least one of methylamine, ethylamine, propylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, sodium carbonate, potassium carbonate, lithium carbonate, sodium hydroxide, potassium hydroxide, boron trifluoride, and organotin.

21. A grease produced by the method of any one of claims 15-20.