A composite barium-based thickener and preparation method thereof

Abstract

The present invention provides a composite barium-based thickener and a preparation method thereof, and belongs to the field of lubrication technology. The present invention obtains a composite barium-based thickener by mixing component A with azelaic acid, sebacic acid and modified porous micro-carbon spheres; mixing barium hydroxide, 12-hydroxystearic acid and mineral base oil for saponification, gradually heating up and adding component A, and maintaining a constant temperature. The thickener prepared by the present invention has complex chemical fibers, strong adsorption capacity for base oil, significantly improves the dropping point of grease, has good lubricity and extreme pressure resistance, and has a simple, convenient and fast process for refining with base oil.

Description

Technical Field

[0001] The invention belongs to the technical field of lubrication, and in particular relates to a composite barium-based thickener and a preparation method thereof. Background Art

[0002] Lubricating oil generally consists of two parts: base oil and additives. Base oil is the main component of lubricating oil and determines the basic properties of lubricating oil. Additives can make up for and improve the deficiencies in the performance of base oil and give it some new properties. They are an important part of lubricating oil. Since lubricating oil itself is easy to drip and does not have sealing functions, its use is limited. Based on this, grease came into being. Grease is mainly made of base oil and thickener. The thickener is dispersed in the base oil and forms a structural skeleton, and the base oil is adsorbed and fixed in the structural skeleton, thereby forming a semi-solid grease with plasticity. At room temperature and static state, it is like a solid, can maintain its shape without flowing, can adhere to metal without slipping, at high temperature or when subjected to external forces exceeding a certain limit, it can flow like a liquid, and even the thickener has the power to increase the dropping point of the grease and improve its anti-wear ability.

[0003] Currently, thickeners have problems such as short storage time, the dropping point of the prepared grease cannot meet the requirements, short service life, and poor effect of mixing and refining with base oil. Summary of the invention

[0004] In view of this, the object of the present invention is to provide a composite barium-based thickener and a preparation method thereof. The prepared thickener has good mixing and refining effect with base oil, high dropping point, and convenient storage and mixing.

[0005] In order to achieve the above object, the present invention provides the following technical solutions:

[0006] The present invention provides a composite barium-based thickener, which is composed of the following raw materials in parts by weight:

[0007] 20-40 parts of barium hydroxide, 20-30 parts of 12-hydroxystearic acid, 4-8 parts of azelaic acid, 4-8 parts of sebacic acid, 1-2 parts of modified porous micro-carbon spheres, and 5-10 parts of mineral base oil.

[0008] Preferably, the preparation method of the modified porous micro-carbon spheres is: the porous micro-carbon spheres are dispersed in an oleic acid solution by ultrasonication, and then the modified porous micro-carbon spheres are obtained after centrifugation, washing and drying; the particle size of the porous micro-carbon spheres is 50-150 nm.

[0009] Preferably, the concentration of the oleic acid solution is 2-5%.

[0010] The present invention also provides a method for preparing a composite barium-based thickener, comprising the following steps:

[0011] Weigh the raw materials according to the mass parts;

[0012] A component A is obtained by mixing azelaic acid, sebacic acid and modified porous micro-carbon spheres;

[0013] The barium hydroxide, 12-hydroxystearic acid and mineral base oil are mixed and saponified, and then the temperature is gradually increased and component A is added, and the temperature is maintained constant to obtain a composite barium-based thickener.

[0014] Preferably, the saponification temperature is 140-160° C., the saponification time is 1-3 h, and the saponification is carried out in a reaction kettle.

[0015] Preferably, the method of adding component A is to add 1 / 3 of component A for every 10°C increase in temperature.

[0016] Preferably, the heating rate is 1-3°C / min.

[0017] Preferably, the constant temperature is maintained for 3-6 hours and the constant temperature is 170-190°C.

[0018] Application of the composite barium-based thickener of the present invention in the preparation of lubricating grease.

[0019] Preferably, the thickener is added in an amount of 20-30% of the lubricating grease.

[0020] Beneficial technical effects: The present invention obtains a composite barium-based thickener by mixing component A with azelaic acid, sebacic acid and modified porous micro-carbon spheres; mixing barium hydroxide, 12-hydroxystearic acid and mineral base oil, gradually heating up and adding component A, and maintaining a constant temperature. The thickener prepared by the present invention has complex chemical fibers, strong adsorption capacity for base oil, significantly improves the dropping point of grease, has good lubricity and extreme pressure resistance, and has a simple, convenient and fast process for refining with base oil. DETAILED DESCRIPTION

[0021] The present invention provides a composite barium-based thickener, which is composed of the following raw materials in parts by weight:

[0022] 20-40 parts of barium hydroxide, 20-30 parts of 12-hydroxystearic acid, 4-8 parts of azelaic acid, 4-8 parts of sebacic acid, 1-2 parts of modified porous micro-carbon spheres and 5-10 parts of mineral base oil.

[0023] The raw materials are preferably prepared in parts by weight: 25-35 parts of barium hydroxide, 22-28 parts of 12-hydroxystearic acid, 5-7 parts of azelaic acid, 5-7 parts of sebacic acid, 1.2-1.6 parts of modified porous micro-carbon spheres and 6-8 parts of mineral base oil; further preferably, they are prepared in parts by weight: 30 parts of barium hydroxide, 25 parts of 12-hydroxystearic acid, 6 parts of azelaic acid, 6 parts of sebacic acid, 1.5 parts of modified porous micro-carbon spheres and 7 parts of mineral base oil.

[0024] In the present invention, the barium hydroxide is preferably barium hydroxide powder or barium hydroxide aqueous solution; more preferably barium hydroxide powder.

[0025] When the present invention uses barium hydroxide powder, attention should be paid to increasing the reaction time and the stirring frequency during mixing to achieve sufficient reaction; when using barium hydroxide aqueous solution, attention should be paid to draining due to the large amount of water generated by the saponification reaction.

[0026] In the present invention, the preparation method of the modified porous micro-carbon spheres is preferably: the porous micro-carbon spheres are dispersed in an oleic acid solution by ultrasonication, and then the modified porous micro-carbon spheres are obtained after centrifugation, washing and drying; the particle size of the porous micro-carbon spheres is preferably 50-150nm, more preferably 80-120nm, and further preferably 100nm; the concentration of the oleic acid solution is preferably 2-5%, more preferably 3-4%.

[0027] The porous micro-carbon spheres used in the present invention have abundant surface area and can achieve the function of oil storage. The porous micro-carbon spheres are modified by surfactants to have stronger lipophilicity.

[0028] The present invention also provides a method for preparing a composite barium-based thickener, comprising the following steps:

[0029] Weigh the raw materials according to the mass parts;

[0030] A component A is obtained by mixing azelaic acid, sebacic acid and modified porous micro-carbon spheres;

[0031] The barium hydroxide, 12-hydroxystearic acid and mineral base oil are mixed and saponified, and then the temperature is gradually increased and component A is added, and the temperature is maintained constant to obtain a composite barium-based thickener.

[0032] First, raw materials are weighed according to the mass parts; azelaic acid, sebacic acid and modified porous micro-carbon spheres are mixed to obtain component A.

[0033] The present invention firstly mixes the dibasic acid and the modified porous micro-carbon spheres and fully disperses them, the dibasic acid is adsorbed on the surface of the modified porous micro-carbon spheres, and then participates in the saponification reaction to form a special network structure.

[0034] Secondly, barium hydroxide, 12-hydroxystearic acid and mineral base oil are mixed and saponified, and then the temperature is gradually increased and component A is added, and the temperature is kept constant to obtain a composite barium-based thickener.

[0035] In the present invention, the saponification temperature is preferably 140-160°C, more preferably 145-155°C; the saponification time is preferably 1-3h, more preferably 1.5-2.5h; and the saponification is carried out in a reaction kettle.

[0036] In the present invention, the method of adding component A is preferably to add 1 / 3 of component A for every 10°C increase in temperature. The porous micro-carbon spheres of component A of the present invention are loaded with dibasic acid on their surfaces, and the dibasic acid is saponified with barium hydroxide to produce new synthetic fibers. The porous micro-carbon spheres form a network of saponified fibers, and a variety of different saponified fibers form fiber networks of various morphologies. Such fiber networks have a strong adsorption force on base oils. The porous micro-carbon spheres are fully dispersed in the base oil to improve both the lubrication performance and the extreme pressure resistance. At the same time, the good thermal conductivity will not cause local high temperatures in the components.

[0037] In the present invention, the heating rate is preferably 1-3°C / min, more preferably 2°C / min.

[0038] In the present invention, the time for maintaining the constant temperature is preferably 3-6 hours, more preferably 4-5 hours.

[0039] Application of the composite barium-based thickener of the present invention in the preparation of lubricating grease.

[0040] In the present invention, the amount of the thickener added is preferably 20-30% of the amount of the lubricating grease, and more preferably 25%.

[0041] In order to better understand the present invention, the content of the present invention is further explained below in conjunction with the embodiments, but the content of the present invention is not limited to the following embodiments.

[0042] Example 1

[0043] 1) Pre-preparation of porous micro-carbon spheres: porous micro-carbon spheres with a particle size of 100 nm are dispersed in a 2% oleic acid solution by ultrasonication, and then centrifuged, washed and dried to obtain modified porous micro-carbon spheres.

[0044] 2) Weigh the raw materials:

[0045] Weigh 30 parts of barium hydroxide, 25 parts of 12-hydroxystearic acid, 6 parts of azelaic acid, 6 parts of sebacic acid, 1.5 parts of modified porous microcarbon spheres and 7 parts of mineral base oil.

[0046] 3) Preparation of component A:

[0047] Azelaic acid, sebacic acid and modified porous micro-carbon spheres were placed in a high-speed mixer and mixed for 3 hours to obtain component A.

[0048] 4) Preparation of composite barium-based thickener:

[0049] Barium hydroxide, 12-hydroxystearic acid and mineral base oil are placed in a reactor and mixed. The mixture is kept at a constant temperature of 150°C for 2 hours. After the constant temperature is completed, a stirring rate of 20 r / min is maintained. The mixture is then heated to 160°C at a heating rate of 2°C / min, 1 / 3 of component A is added, the mixture is then heated to 170°C at a heating rate of 2°C / min, 1 / 3 of component A is added, and finally the mixture is heated to 180°C at a heating rate of 2°C / min, the remaining 1 / 3 of component A is added, and the temperature is maintained for 5 hours to obtain a composite barium-based thickener.

[0050] Example 2

[0051] 1) Pre-preparation of porous micro-carbon spheres: Porous micro-carbon spheres with a particle size of 50 nm are dispersed in a 3% oleic acid solution by ultrasonic dispersion, and then centrifuged, washed and dried to obtain modified porous micro-carbon spheres.

[0052] 2) Weigh the raw materials:

[0053] Weigh 20 parts of barium hydroxide, 20 parts of 12-hydroxystearic acid, 4 parts of azelaic acid, 4 parts of sebacic acid, 1 part of modified porous microcarbon spheres and 5 parts of mineral base oil.

[0054] 3) Preparation of component A:

[0055] Azelaic acid, sebacic acid and modified porous micro-carbon spheres were placed in a high-speed mixer and mixed for 3 hours to obtain component A.

[0056] 4) Preparation of composite barium-based thickener:

[0057] Barium hydroxide, 12-hydroxystearic acid and mineral base oil are placed in a reactor and mixed. The mixture is kept at a constant temperature at 140°C for 1 hour. After the constant temperature is completed, a stirring rate of 20 r / min is maintained. The mixture is then heated to 150°C at a heating rate of 1°C / min, 1 / 3 of component A is added, the mixture is then heated to 160°C at a heating rate of 1°C / min, 1 / 3 of component A is added, and finally the mixture is heated to 170°C at a heating rate of 1°C / min, the remaining 1 / 3 of component A is added, and the temperature is maintained for 3 hours to obtain a composite barium-based thickener.

[0058] Example 3

[0059] 1) Pre-preparation of porous micro-carbon spheres: porous micro-carbon spheres with a particle size of 150 nm are dispersed in a 5% oleic acid solution by ultrasonic dispersion, and then centrifuged, washed and dried to obtain modified porous micro-carbon spheres.

[0060] 2) Weigh the raw materials:

[0061] Weigh 40 parts of barium hydroxide, 30 parts of 12-hydroxystearic acid, 8 parts of azelaic acid, 8 parts of sebacic acid, 2 parts of modified porous microcarbon spheres and 10 parts of mineral base oil.

[0062] 3) Preparation of component A:

[0063] Azelaic acid, sebacic acid and modified porous micro-carbon spheres were placed in a high-speed mixer and mixed for 3 hours to obtain component A.

[0064] 4) Preparation of composite barium-based thickener:

[0065] Barium hydroxide, 12-hydroxystearic acid and mineral base oil are placed in a reactor and mixed. The mixture is kept at a constant temperature of 160°C for 3 hours. After the constant temperature is completed, a stirring rate of 20 r / min is maintained. The mixture is then heated to 170°C at a heating rate of 3°C / min, 1 / 3 of component A is added, the mixture is then heated to 180°C at a heating rate of 3°C / min, 1 / 3 of component A is added, and finally the mixture is heated to 190°C at a heating rate of 3°C / min, the remaining 1 / 3 of component A is added, and the temperature is maintained for 6 hours to obtain a composite barium-based thickener.

[0066] Example 4

[0067] This embodiment provides a composite barium-based thickener, which is different from Embodiment 1 only in that step 4) is: barium hydroxide, 12-hydroxystearic acid and mineral base oil are placed in a reaction kettle and mixed, and kept at a constant temperature of 150°C for 2 hours. After the constant temperature is completed, a stirring rate of 20 r / min is maintained, and then the temperature is increased to 180°C at a heating rate of 2°C / min, and then component A is added, and the constant temperature is maintained for 5 hours to obtain the composite barium-based thickener.

[0068] Comparative Example 1

[0069] 2) Weigh the raw materials:

[0070] Weigh 30 parts of barium hydroxide, 25 parts of 12-hydroxystearic acid, 6 parts of azelaic acid, 6 parts of sebacic acid, 1.5 parts of porous micro-carbon spheres and 7 parts of mineral base oil.

[0071] 3) Preparation of component A:

[0072] Azelaic acid, sebacic acid and porous micro-carbon spheres were placed in a high-speed mixer and mixed for 3 hours to obtain component A.

[0073] 4) Preparation of composite barium-based thickener:

[0074] Barium hydroxide, 12-hydroxystearic acid and mineral base oil are placed in a reaction kettle and mixed, and the temperature is kept constant at 150°C for 2 hours. After the constant temperature is completed, the stirring rate is maintained at 20r / min, and then the temperature is increased to 160°C at a heating rate of 2°C / min, and 1 / 3 of component A is added. Then, the temperature is increased to 170°C at a heating rate of 2°C / min, and 1 / 3 of component A is added. Finally, the temperature is increased to 180°C at a heating rate of 2°C / min, and the remaining 1 / 3 of component A is added. The temperature is kept constant for 5 hours to obtain a composite barium-based thickener.

[0075] Experimental Example 1

[0076] 1. The performance of the composite barium-based thickener obtained in Examples 1-4 was tested

[0077] The complex barium-based thickeners provided in Examples 1-4 were all prepared into greases: 25 parts by mass of the complex barium-based thickeners were mixed with 75 parts by mass of base oil (mineral base oil: synthetic base oil = 3:1), refined at 240°C for 1 hour, and then the performance was tested, as shown in Table 1.

[0078] Table 1 Grease performance test table

[0079]

[0080] As shown in Table 1, the modified porous micro-carbon spheres prepared according to the method of the present invention can significantly increase the dropping point of the grease and improve the lubrication performance. The improvement in the extreme pressure resistance may be due to the improvement in the dispersion effect of the micro-carbon spheres, thereby improving the extreme pressure resistance.

[0081] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A composite barium-based thickener, characterized in that: It is composed of the following raw materials by weight: 20-40 parts of barium hydroxide, 20-30 parts of 12-hydroxystearic acid, 4-8 parts of azelaic acid, 4-8 parts of sebacic acid, 1-2 parts of modified porous microcarbon spheres and 5-10 parts of mineral base oil; The preparation method of the modified porous micro-carbon spheres is as follows: the porous micro-carbon spheres are dispersed in an oleic acid solution by ultrasonication, and then centrifuged, washed and dried to obtain the modified porous micro-carbon spheres; the particle size of the porous micro-carbon spheres is 50-150nm; The preparation method of the composite barium-based thickener comprises the following steps: Weigh the raw materials according to the mass parts; A component A is obtained by mixing azelaic acid, sebacic acid and modified porous micro-carbon spheres; The barium hydroxide, 12-hydroxystearic acid and mineral base oil are mixed and saponified, and then the temperature is gradually increased and component A is added, and the temperature is maintained constant to obtain a composite barium-based thickener.

2. The complex barium-based thickener according to claim 1, characterized in that: The concentration of the oleic acid solution is 2-5%.

3. The complex barium-based thickener according to claim 1, characterized in that: The saponification temperature is 140-160° C., the saponification time is 1-3 hours, and the saponification is carried out in a reaction kettle.

4. The complex barium-based thickener according to claim 1, characterized in that: The method of adding component A is to add 1 / 3 of component A for every 10°C increase in temperature.

5. The complex barium-based thickener according to claim 1, characterized in that: The heating rate is 1-3℃ / min.

6. The complex barium-based thickener according to claim 1, characterized in that: The constant temperature is maintained for 3-6 hours and the constant temperature is 170-190°C.

7. Use of the thickener according to claim 1 in the preparation of lubricating grease.

8. The use according to claim 7, characterized in that: The thickener is added in an amount of 20-30% of the lubricating grease mass.

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