阅读说明：本技术 一种四脲稠化剂及其在润滑脂的应用与润滑脂的制备方法 (Tetraurea thickening agent, application of tetraurea thickening agent in lubricating grease and preparation method of lubricating grease ) 是由 王晓波 徐状 赵改青 王卓群 于 2021-01-22 设计创作，主要内容包括：本发明提供了一种四脲稠化剂及其在润滑脂的应用与润滑脂的制备方法,涉及轴承润滑材料技术领域。所述的四脲润滑脂包含的各组分及其质量百分数为：基础油72.5～89.5%,具有极压作用的稠化剂10～25%,防锈剂0.5～2.5%。所述的具有极压作用的稠化剂是以2,2-二氨基二苯二硫醚、R-NH-2和二苯基甲烷-4,4’-二异氰酸酯为原料合成,其中R为碳原子数8-18的烷基。利用该稠化剂制备的四脲润滑脂不需添加极压剂,且具有优良的极压性能,可显著减少目前四脲润滑脂技术中的添加剂种类和用量,防止添加极压剂对四脲润滑脂胶体安定性和储存安定性的破坏作用。本发明提供的四脲润滑脂可广泛应用于轴承润滑材料领域。(The invention provides a tetraurea thickening agent, application thereof in lubricating grease and a preparation method of the lubricating grease, and relates to the technical field of bearing lubricating materials. The tetraurea lubricating grease comprises the following components in percentage by mass: 72.5-89.5% of base oil, 10-25% of thickening agent with extreme pressure effect and 0.5-2.5% of antirust agent. The thickener with extreme pressure effect is 2, 2-diamino diphenyl disulfide and R-NH 2 And diphenylmethane-4, 4' -diisocyanate as raw materials, wherein R is alkyl with 8-18 carbon atoms. The tetraurea lubricating grease prepared by the thickening agent does not need to be added with an extreme pressure agent, has excellent extreme pressure performance, can obviously reduce the types and the use amounts of additives in the prior tetraurea lubricating grease technology, and prevents the additive extreme pressure agent from damaging the stability and the storage stability of the tetraurea lubricating grease colloid. The tetraurea lubricating grease provided by the invention can be widely applied to the field of bearing lubricating materials.)

1. The tetraurea thickening agent is characterized by comprising 2, 2-diaminodiphenyl disulfide and R-NH₂And diphenylmethane-4, 4' -diisocyanate as raw materials, wherein R-NH is₂Wherein R is alkyl with 8-18 carbon atoms.

2. According to the rightThe tetraurea thickener according to claim 1, wherein 2, 2-diaminodiphenyl disulfide, R-NH₂And diphenylmethane-4, 4' -diisocyanate in a molar ratio of 1:2: 2.

3. The tetraurea thickener according to claim 1, wherein the tetraurea thickener has a chemical formula shown below.

。

4. The lubricating grease of claim 1, which comprises the following components in percentage by mass: 72.5-89.5% of base oil, 10-25% of tetraurea thickening agent and 0.5-2.5% of antirust agent.

5. The lubricating grease of claim 4, wherein the base oil is one or a mixture of mineral oil, synthetic ester base oil, poly-alpha-olefin base oil and alkyl naphthalene, and the kinematic viscosity of the base oil at 40 ℃ is 20-500 mm²/s。

6. The tetraurea lubricating grease of claim 5, wherein the rust inhibitor is one or more of barium petroleum sulfonate, barium dinonylnaphthalene sulfonate, fatty acid amine, benzotriazole and derivatives thereof.

7. The method of preparing a grease according to claim 4, comprising the steps of:

(1) A5L reactor was initially charged with part of the base oil, 2, 2-diaminodiphenyl disulfide and R-NH₂Heating and stirring; adding the rest base oil into a dissolving kettle, then adding diphenylmethane-4, 4' -diisocyanate, heating and stirring;

(2) adding the mixture in the dissolving kettle into a reaction kettle, heating to 90-110 ℃, and keeping the temperature for 60-120 min;

(3) after the reaction is finished, heating to 170-220 ℃, keeping the temperature for 30-100 min, cooling to 80 ℃, adding an antirust agent, homogenizing, filtering and degassing.

8. The preparation method according to claim 7, wherein the reaction temperature of the reaction kettle in the step (1) is 95-110 ℃, and the stirring time is 60 min.

9. The method according to claim 8, wherein in the step (1), the temperature of the dissolution tank is 80 ℃ and the time is 40 min.

Technical Field

The invention relates to the technical field of lubricating materials, in particular to a tetraurea thickening agent, application thereof in lubricating grease and a preparation method of the lubricating grease.

Background

The lubricating grease is a semi-fluid lubricating material and consists of base oil, a thickening agent and a functional additive. The thickener for urea-based greases is an organic compound containing urea groups, and is classified into a diurea grease, a tetraurea grease, a hexaurea grease, and the like, depending on the number of urea groups in the compound. The carbamido lubricating grease is widely applied to the harsh lubrication field of high-temperature heavy-load working conditions such as metallurgy, automobile and the like due to the good oxidation resistance and thermal stability. The diurea lubricating grease is relatively mature in preparation technology and becomes the most widely applied one of the carbamido lubricating greases, but the diurea lubricating grease is easy to have the phenomena of reduced penetration and hardening in the service process under the high-temperature working condition, so that the lubricating property of the diurea lubricating grease is reduced, and equipment failure or damage is caused. Tetraurea grease has become a hot point of research for urea grease due to its excellent high temperature properties.

The extreme pressure performance is the key performance of the tetraurea lubricating grease applied to heavy load working conditions, however, the main effect of the currently commonly used tetraurea thickener is only to thicken base oil to form semi-fluid lubricating grease, and the extreme pressure performance of the tetraurea lubricating grease cannot be improved. The method for improving the extreme pressure performance of the tetraurea lubricating grease mainly comprises the steps of adding a large amount of extreme pressure agents, wherein the patent CN105586135A improves the extreme pressure performance of the tetraurea lubricating grease by adding the extreme pressure agents such as dithiodialkyl compounds, molybdenum disulfide and calcium carbonate; patent CN105586130B improves the extreme pressure performance of tetraurea grease by adding extreme pressure agents such as dithiodialkyl compound, polytetrafluoroethylene and graphite fluoride. The extreme pressure performance of the tetraurea lubricating grease can be obviously improved by adding the extreme pressure agent, but the added extreme pressure agent is easy to damage the colloid stability and the storage stability of the tetraurea lubricating grease, and is not beneficial to maintaining the original performance of the tetraurea lubricating grease.

Therefore, the development of a tetraurea thickener having an extreme pressure effect has become an important approach to solve the above problems.

Disclosure of Invention

The invention aims to provide a tetraurea thickening agent, application of the tetraurea thickening agent in lubricating grease and a preparation method of the lubricating grease, and solves the technical problems that the tetraurea thickening agent does not have extreme pressure performance and needs to be additionally added when the tetraurea thickening agent is applied to the lubricating grease in the prior art.

The invention is realized by the following steps:

a thickening agent with extreme pressure effect is synthesized by using 2, 2-diaminodiphenyl disulfide, R-NH2 and diphenylmethane-4, 4' -diisocyanate as raw materials, wherein R in the R-NH2 is alkyl with 8-18 carbon atoms.

Further, the molar ratio of a2, 2-diaminodiphenyl disulfide, R-NH2 and diphenylmethane-4, 4' -diisocyanate was 1:2: 2.

Further, the chemical formula of the tetraurea thickening agent is as follows.

The lubricating grease containing the tetraurea thickening agent comprises the following components in percentage by mass: 72.5-89.5% of base oil, 10-25% of thickening agent with extreme pressure effect and 0.5-2.5% of antirust agent.

Further, the base oil is one or a mixture of a plurality of mineral oil, synthetic ester base oil, poly-alpha-olefin base oil and alkyl naphthalene, and the kinematic viscosity of the base oil at 40 ℃ is 20-500 mm²/s。

Further, the antirust agent is one or more of barium petroleum sulfonate, barium dinonylnaphthalene sulfonate, fatty acid amine and benzotriazole derivatives.

The preparation method of the grease containing the tetraurea thickener comprises the following steps:

(1) firstly, adding part of base oil, 2, 2-diaminodiphenyl disulfide and R-NH2 into a 5L reaction kettle, heating and stirring; adding the rest base oil into a dissolving kettle, then adding diphenylmethane-4, 4' -diisocyanate, heating and stirring;

(2) adding the mixture in the dissolving kettle into a reaction kettle, heating to 90-110 ℃, and keeping the temperature for 60-120 min;

(3) after the reaction is finished, heating to 170-220 ℃, keeping the temperature for 30-100 min, cooling to 80 ℃, adding an antirust agent, homogenizing, filtering and degassing.

Further, the reaction temperature of the reaction kettle in the step (1) is 95-110 ℃, and the stirring time is 60 min.

Further, in the step (1), the reaction temperature of the dissolution kettle is 80 ℃ and the time is 40 min.

The invention has the beneficial effects that: the tetraurea thickening agent prepared by the invention has good extreme pressure performance, when the tetraurea thickening agent is applied to lubricating grease, no extra extreme pressure agent is needed to be added, the type and the using amount of the extreme pressure agent used in the tetraurea lubricating grease can be obviously reduced, and the damage effect of the added extreme pressure agent on the stability and the storage stability of the tetraurea lubricating grease colloid is prevented.

Detailed Description

Example 1

1020g of mineral oil MVI500, 255g of 500N are firstly added into a 5L reaction kettle, 86.8g of 2, 2-diaminodiphenyl disulfide and 188.4g of octadecylamine are then added, the reaction kettle is started to heat and stir, and the temperature is increased to 105 ℃ and the stirring is carried out for 60 min. 1020g of MVI500 and 255g of 500N are added into a dissolving kettle, then 174.6g of diphenylmethane-4, 4' -diisocyanate is added, stirring and heating are started, and the temperature is increased to 80 ℃ and stirring is carried out for 40 min. Adding the mixture in the dissolving kettle into a reaction kettle, and keeping the temperature at 105 ℃ for reaction for 70 min. And after the reaction is finished, continuously heating to 170 ℃, refining at constant temperature for 100min, adding 30g of barium dinonylnaphthalenesulfonate serving as an antirust agent when the temperature is reduced to 80 ℃, and homogenizing, filtering and degassing to obtain the finished lubricating grease.

Wherein the MVI500, 500N base oil has a kinematic viscosity of 2/s of 20-500 mm at 40 ℃.

The chemical formula of the prepared tetraurea lubricating grease thickener is shown as the chemical formula I.

Example 2

600g of mineral oil MVI500, 675g of 150BS and 225g of alkylnaphthalene-5 are initially introduced into a 5L reaction vessel, then 158.8g of 2, 2-diaminodiphenyl disulfide, 203.4g of octadecylamine and 67.8g of octylamine are added, the reaction vessel is started to heat and stir, the temperature is raised to 95 ℃ and stirring is carried out for 60 min. 525g of base oil MVI500 and 225g of alkyl naphthalene-5 are added into a dissolving kettle, 320.1g of diphenylmethane-4, 4' -diisocyanate is added, stirring and heating are started, and the temperature is increased to 80 ℃ and stirring is carried out for 40 min. And adding the mixture in the dissolving kettle into a reaction kettle, heating to 100 ℃, keeping the temperature constant, and reacting for 90 min. After the reaction is finished, continuously heating to 190 ℃, refining at constant temperature for 60min, adding 10g of rust inhibitor dinonyl naphthalene sulfonic acid barium and 5g of benzotriazole derivatives when cooling to 80 ℃, and homogenizing, filtering and degassing to obtain the finished product of the lubricating grease.

Wherein the kinematic viscosity of the base oil MVI500, 150BS and alkyl naphthalene-5 at 40 ℃ is 20-500 mm 2/s. The mass ratio of the octadecylamine to the octylamine is 3: 1.

The chemical formula of the prepared tetraurea lubricating grease thickener is a mixture of I, II and III.

Example 3

600g of mineral oil 900N, 480g of 120BS and 360g of pentaerythritol ester oil are firstly added into a 5L reaction kettle, then 121.0g of 2, 2-diaminodiphenyl disulfide and 235.3g of hexadecylamine are added, the reaction kettle is started to heat and stir, and the temperature is increased to 100 ℃ and the stirring is carried out for 60 min. 600g of base oil 900N and 360g of pentaerythritol ester oil are added into a dissolving kettle, 244.0g of diphenylmethane-4, 4' -diisocyanate is added, stirring and heating are started, and the temperature is increased to 80 ℃ and stirring is carried out for 40 min. Adding the mixture in the dissolving kettle into a reaction kettle, keeping the temperature at 90 ℃, and then preserving the temperature for reaction for 120 min. And after the reaction is finished, continuously heating to 200 ℃, refining at constant temperature for 40min, cooling to 80 ℃, adding 55g of barium petroleum sulfonate and 20g of fatty amide, and homogenizing, filtering and degassing to obtain the finished lubricating grease.

Wherein the kinematic viscosity of the 900N, 120BS and pentaerythritol ester oil at 40 ℃ is 20-500 mm 2/s.

The chemical formula of the prepared tetraurea lubricating grease thickener is shown as chemical formula IV.

Example 4

360g of poly-alpha-olefin base oil PAO10, 600g of 120BS and 240g of alkyl naphthalene-5 are firstly added into a 5L reaction kettle, then 120.9g of 2, 2-diaminodiphenyl disulfide, 58.9g of dodecylamine and 176.7g of octadecylamine are added, the reaction kettle is started to heat and stir, and the temperature is raised to 100 ℃ and the stirring is carried out for 60 min. 360g of poly-alpha-olefin base oil PAO10, 600g of 120BS and 240g of alkyl naphthalene-5 are added into a dissolving kettle, then 255.8g of diphenylmethane-4, 4' -diisocyanate is added, stirring and heating are started, and the temperature is increased to 80 ℃ and stirring is carried out for 40 min. Adding the mixture in the dissolving kettle into a reaction kettle, keeping the temperature at 110 ℃, and then preserving the temperature for reaction for 60 min. After the reaction is finished, continuously heating to 210 ℃, refining at constant temperature for 30min, cooling to 80 ℃, adding 35g of barium petroleum sulfonate and 10g of benzotriazole derivatives, homogenizing, filtering and degassing to obtain the finished product of the lubricating grease.

Wherein the kinematic viscosity of the base oil PAO10, 120BS and alkyl naphthalene-5 at 40 ℃ is 20-500 mm²And s. The mass ratio of the octadecylamine to the dodecylamine is 3: 1.

The chemical formula of the prepared tetraurea lubricating grease thickener is a mixture of I, V and VI.

The test data of the physical and chemical properties and the extreme pressure property of the tetraurea lubricating grease prepared in the four examples are shown in the following table:

test data for the tetraurea greases obtained in the examples

Test items	Example 1	Example 2	Example 3	Example 4	Comparative sample	Test method
							Penetration/0.1 mm)	246	231	214	216	286	GB/T 269
Dropping Point/. degree.C	265	232	273	241	261	GB/T 3498
							Steel mesh oil/percent	0.18	0.08	0.15	0.12	0.10	SH/T 0324
PD(four-sphere method)/N	1961	2452	2452	1961	785	SH/T 0202

Note: the comparative sample is the tetraurea lubricating grease prepared by using octadecylamine, 4 '-dicyclohexylmethane diamine and diphenylmethane-4, 4' -diisocyanate which are commonly used for preparing the tetraurea at present as raw materials, and the chemical structural formula of the tetraurea lubricating grease is shown as the following formula.

As can be seen from the test data in table 1, the tetraurea grease provided by the present invention has excellent extreme pressure properties.