CN103627496B - A kind of Composite calcium naphthenate base lubricating grease and preparation method thereof - Google Patents

Abstract

The invention provides a kind of Composite calcium naphthenate base lubricating grease and preparation method thereof.With lubricating grease weight for benchmark, this lubricating grease comprises following component: 1) non-newtonian fluid calcium naphthenate 10%-70%; 2) the calcium salt 1%-10% of higher fatty acid; 3) the calcium salt 1%-15% of small molecules mineral acid or lipid acid; 4) lubricating base oil 10%-80%.Described lubricating grease have employed petroleum naphthenic acid calcium or synthesis calcium naphthenate is raw material, simultaneously containing composite calcium viscosifying agent.This lubricating grease has excellent water resistant sprayability and water resistant drenches leachability, also has the performances such as excellent adhesivity, extreme pressure anti-wear, colloid stability, high dropping point, heat-resistant quality, non-corrosibility simultaneously.

Description

A kind of composite calcium naphthenate-based lubricating grease and preparation method thereof

technical field

The invention relates to a lubricant, specifically a high-basic value complex calcium naphthenate-based lubricating grease and a preparation method thereof.

Background technique

High base value calcium naphthenate has good cleaning and dispersibility, good acid neutralization ability and excellent diffusivity. It can be used as a detergent for lubricating oil and widely used as an additive for internal combustion engine lubricating oil. Its technical development is mainly It is to make it highly alkaline, that is, to disperse calcium carbonate into diluent oil with surface active calcium cyclic acid to form a colloidal dispersion system. Calcium naphthenate with high base value is mostly an acidic component extracted from distillate oil obtained by distillation of crude oil. It is obtained through high alkalinization techniques such as reaction with Ca(OH) ₂ and carbonation. Related patents related to preparation include CN 1465560 wait.

The lubricating grease produced by using calcium sulfonate with high alkalinity as raw material has excellent high and low temperature performance, mechanical stability, colloidal stability, oxidation stability, water resistance, corrosion resistance, rust resistance and wear resistance. Since it was put into the market, It has aroused widespread concern in the lubricating grease industry at home and abroad. However, although the high-basic value calcium sulfonate-based grease has excellent comprehensive properties, the high price of the raw material high-basic calcium sulfonate and the complicated preparation process lead to It has not been popularized rapidly. At the same time, as people's requirements for environmental protection are getting higher and higher, the pollution of the environment by the sulfonation process that must be passed through the production process of high-basic calcium sulfonate is also increasingly concerned by people. Finding a kind of lubricating grease that performance is similar to high alkali value complex calcium sulfonate but can avoid above-mentioned problem becomes the big problem that people are facing at present.

Contents of the invention

The invention provides a compound calcium naphthenate-based lubricating grease. The lubricating grease uses calcium naphthenate with a high basic value as a raw material and simultaneously contains a compound calcium thickener.

The present invention also provides a preparation method of the above lubricating grease.

The composite calcium naphthenate-based grease provided by the invention is based on the grease weight and comprises the following components:

1) Non-Newtonian calcium naphthenate 10%-70%, preferably 20%-60%, most preferably 30%-55%;

2) Higher fatty acid calcium salt 1%-10%, preferably 2%-6%, most preferably 2.2%-4.5%;

3) Calcium salt of small molecular inorganic acid and/or small molecular fatty acid 1%-15%, preferably 2%-10%, most preferably 3%-8%;

4) Lubricating base oil 10%-80%, preferably 20%-70%, most preferably 30%-60%.

The non-Newtonian calcium naphthenate has a characteristic absorption peak of crystalline calcium carbonate at 873cm ^- 1-886cm ^-1 of the infrared spectrogram, and the total base number is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g . The non-Newtonian calcium naphthenate is obtained by converting Newtonian calcium naphthenate through a converting agent. The Newtonian calcium naphthenate contains amorphous calcium carbonate, and characteristic absorption peaks appear at 860cm ^-1 -865cm ^-1 in the infrared spectrum. The Newtonian calcium naphthenate is petroleum calcium naphthenate or synthetic calcium naphthenate, and its total base value is 250mgKOH/g-450mgKOH/g, preferably 300mgKOH/g-400mgKOH/g, converted into non-Newtonian naphthenate After adding calcium acid, its base value remains unchanged.

Said higher fatty acid is a straight chain fatty acid or hydroxy fatty acid with carbon number of 8-20, preferably 10-16, such as lauric acid, palmitic acid, stearic acid, 12-hydroxystearic acid, eicosyl carboxylic acid One or more mixtures, preferably 12-hydroxystearic acid.

The molecular weight of said small molecular inorganic acid or fatty acid is less than or equal to 150, which can be one or more of acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, boric acid, phosphoric acid, sulfuric acid, etc. mixtures, preferably boric acid and/or phosphoric acid.

The lubricating base oil can be mineral oil, synthetic oil, vegetable oil or their mixtures, and the kinematic viscosity at 100°C is 4mm ² /s-60mm ² /s, preferably 10mm ² /s-30mm ² /s. The synthetic oil can be polyalphaolefin oil (PAO), ester oil, alkyl silicone oil, Fischer-Tropsch synthetic oil, etc.

The lubricating grease of the present invention may also contain various additives, such as antioxidants, antiwear agents, antirust agents and the like. Among them, the antioxidant is preferably aromatic amine antioxidant, accounting for 0.1%-5% of the total weight of the grease, preferably 0.2%-1%, which can be diphenylamine, phenyl-α-naphthylamine, diisooctyldiphenylamine Or their mixture, preferably diisooctyl diphenylamine. Antiwear agents can be zinc dithiodialkyl phosphate, molybdenum dithiodialkyl carbamate, lead dithiodialkyl carbamate, triphenyl thiophosphate, organic molybdenum complexes, sulfurized olefins , molybdenum disulfide, polytetrafluoroethylene, molybdenum thiophosphate, chlorinated paraffin, antimony dibutyldithiocarbamate, tungsten disulfide, selenium disulfide, graphite fluoride, calcium carbonate and zinc oxide; rust inhibitor Examples may be barium petroleum sulfonate, sodium petroleum sulfonate, benzothiazole, benzotriazole, zinc naphthenate and alkenylsuccinic acid.

The preparation method of described composite calcium naphthenate-based grease comprises:

(1) Mix and heat Newtonian calcium naphthenate, part of the base oil and conversion agent to thicken the material;

(2) Add lime or calcium hydroxide, add higher fatty acid and small molecule inorganic acid or fatty acid respectively, heat up and dehydrate;

(3) Raise the temperature to 200°C-220°C for constant temperature refining, cool down, add the remaining base oil, and add necessary additives to obtain the finished product.

Specifically, in step (1), Newtonian calcium naphthenate and part of the base oil are mixed and heated to 50°C-90°C, preferably kept at a constant temperature for 10 minutes to 30 minutes, and the required conversion agents are sequentially added for reaction. It is preferable to stir for about 10 minutes after adding each time to make the reaction fully, and to heat up after adding all the conversion agents, preferably at a constant temperature of 60°C-100°C for 0.5-3 hours to make the material thicken.

The Newtonian calcium naphthenate is petroleum calcium naphthenate or synthetic calcium naphthenate, and its total base value is 250 mgKOH/g-450 mgKOH/g, preferably 300 mgKOH/g-400 mgKOH/g.

The conversion agent is selected from C1-C5 fatty alcohols, fatty acids, fatty ketones, fatty aldehydes, fatty amines, naphthenic amines, cycloalkanols, ethers, and boric acid, calcium carbonate, phosphonic acid, carbon dioxide, phenol, aromatic alcohols, One or more of aromatic amines, C8-C20 alkylbenzenesulfonic acid, C16-C62 naphthenic acid, water, etc., preferably dodecylbenzenesulfonic acid, methanol, isopropanol, butanol, C20-C40 One or more of naphthenic acid, acetic acid and water. The addition amount of conversion agent is 2%-30% of the weight of Newtonian calcium naphthenate, preferably 6%-22%.

In step (2), add lime or calcium hydroxide suspension at 85°C-100°C, add higher fatty acid at 75°C-100°C, stir for 5-20 minutes, add small molecule acid, stir 5 minutes-20 minutes, heat up to 105°C-120°C, preferably keep for 30 minutes-60 minutes, dehydrate, cool to 90°C-105°C;

Said higher fatty acid is a straight chain fatty acid or hydroxy fatty acid with carbon number of 8-20, preferably 10-16, such as lauric acid, palmitic acid, stearic acid, 12-hydroxystearic acid, eicosyl carboxylic acid One or more mixtures, preferably 12-hydroxystearic acid.

The said small molecular inorganic acid or fatty acid has a molecular weight less than or equal to 150, which can be one or more of acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, boric acid, phosphoric acid, sulfuric acid, etc. mixtures, preferably boric acid and/or phosphoric acid.

The amount of H+ total substances of higher fatty acids and small molecular acids is equal to the amount of OH- total substances contained in calcium hydroxide, and the amount of calcium hydroxide can also be excessive by 1%-10%.

In step (3), heat up the product of step (2), preferably at a constant temperature of 100°C-120°C for 10-20 minutes, and finally heat up to 200°C-220°C for 5 minutes-10 minutes; cool to 150 °C-160°C, add the remaining amount of lubricating base oil, wait for the temperature to cool down to 100°C-120°C, add necessary additives, stir, circulate, filter, homogenize, and degas to obtain the finished product.

The lubricating grease of the present invention has good extreme pressure and anti-wear properties and super long lubrication life, and at the same time, it also has excellent adhesion, water resistance, colloidal stability, high dropping point, thermal stability, corrosion resistance, and salt spray resistance sexual performance. The preparation process of the product is simple, and the product quality is stable.

Description of drawings

Fig. 1 is the infrared spectrogram of the lubricating grease prepared in embodiment 1. It can be seen from the figure that the characteristic absorption peaks of crystalline calcium carbonate appear at 873cm ^-1 -886cm ^-1 .

Detailed ways

1, the calculation method of each component content in the embodiment is as follows:

Non-Newtonian calcium naphthenate %= (ultra-high base value or high base value calcium naphthenate raw material mass + total mass of converting agent)/total mass of lubricating grease; converting agent naphthenic acid, acetic acid, dodecylbenzenesulfonate Acid, methanol, butanol, etc. are included in the content of non-Newtonian calcium naphthenate.

The content of the calcium salt of higher fatty acid and the calcium salt of small molecular inorganic acid or fatty acid is calculated according to the amount of the added higher fatty acid and small molecular inorganic acid or fatty acid reacting completely with calcium hydroxide to generate calcium salt.

2. In the examples, the ultra-high base value and high base value calcium naphthenate raw materials are purchased from Xinjiang Lande Fine Petrochemical Co., Ltd., and can also be disclosed according to CN101885677A (a preparation method of high base calcium naphthenate) method of preparation.

3. In the comparative example, the raw material of high alkali value calcium sulfonate was purchased from Jinzhou Huifa Tianhe Chemical Co., Ltd.

Example 1

Raw material components: ultra-high base number calcium naphthenate (total base number 400mgKOH/g, 30kg); 150BS (30kg); C16-C50 naphthenic acid (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (1.8kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (18kg).

Add 30kg of ultra-high alkalinity calcium naphthenate with a total base number of 400mgKOH/g and 30kg of 100°C kinematic viscosity of ^31mm2 / s HVI150BS lubricating base oil, stir, heat up to 50°C, keep the temperature for 10 minutes; add 2.8kg of naphthenic acid, control the temperature at about 50°C, stir for 10 minutes; add 0.56kg of acetic acid and 4 times the weight of acetic acid Aqueous solution, stirred 10 minutes; Be warming up to 60 ℃, constant temperature 90 minutes, material thickening; Add 1.8kgCa (OH) ₂ and the suspension liquid diluted with 4 times of water, stir 10 minutes; Add 2kg12-hydroxystearic acid, Stir for 10 minutes; add 2.32kg of boric acid and dissolve with 3 times hot water, heat up to 110°C with stirring, keep for 60 minutes, dehydrate, keep the temperature at 120°C for 20 minutes, and heat up to 200°C for 5 minutes. Then, be cooled to 160 DEG C, add 100 DEG C of 100 DEG C kinematic viscosity and be the ^HVI500SN lubricating base oil of 11mm / s, circulation filtration, homogenization, degassing obtain finished product. The test results are shown in Table 1. The infrared spectrum of the product is shown in Figure 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 38.5% of non-Newtonian calcium naphthenate; 55.4% of lubricating base oil; 2.4% of calcium 12-hydroxystearate; and 3.7% of calcium borate.

Example 2

Raw material components: super high base number calcium naphthenate (total base number 420mgKOH/g, 30kg); 150BS (30kg); C16-C50 naphthenic acid (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (1.8kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (18kg).

Prepare ultra-high base value calcium naphthenate-based grease by the method of example 1, the difference is that the total base value of the ultra-high base value calcium naphthenate used is 420mgKOH/g, and the performance data of the obtained grease finished product are shown in Table 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 38.5% of non-Newtonian calcium naphthenate; 55.4% of lubricating base oil; 2.4% of calcium 12-hydroxystearate; and 3.7% of calcium borate.

Example 3

Raw material components: ultra-high base value calcium naphthenate (total base value 400mgKOH/g, 30kg); 150BS (20kg); butanol (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (1.8kg ); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (28kg).

Super high base value composite calcium naphthenate-based lubricating grease was prepared according to the method of Example 1, except that butanol was used instead of naphthenic acid, and the amount of base oil was also changed. The performance data of the finished lubricating grease obtained are shown in Table 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 38.5% of non-Newtonian calcium naphthenate; 55.4% of lubricating base oil; 2.4% of calcium 12-hydroxystearate; and 3.7% of calcium borate.

Example 4

Raw material components: ultra-high base number calcium naphthenate (total base number 400mgKOH/g, 39kg); 150BS (20kg); dodecylbenzenesulfonic acid (2.8kg); acetic acid (0.56kg); Ca(OH ) ₂ (1.8kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (28kg); p-p-diisooctyldiphenylamine (0.2kg).

Prepare ultra-high base value composite calcium naphthenate-based lubricating grease by the method of example 1, difference is to replace naphthenic acid with dodecylbenzenesulfonic acid, the amount of base oil also changes to some extent, the lubricating grease finished product that obtains each See Table 1 for performance data.

In the lubricating grease that present embodiment obtains, take the lubricating grease weight as a benchmark, consist of: 44.2% of non-Newtonian calcium naphthenate; 50.1% of lubricating base oil; 2.2% of calcium 12-hydroxystearate; 3.3% of calcium borate; p-Diisooctyldiphenylamine 0.2%.

Example 5

Raw material components: super high base value calcium naphthenate (total base value 400mgKOH/g, 30kg); 150BS (15kg); naphthenic acid (1.8kg); butanol (1.0kg); acetic acid (0.56kg); Ca(OH) ₂ (1.8kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (7kg); p-diisooctyldiphenylamine (0.4kg).

Prepare ultra-high base value composite calcium naphthenate base grease by the method of example 1, difference is that the amount of base oil changes to some extent, thereby makes each raw material ratio take place big change, and p-diisooctyl used in addition Diphenylamine is 0.4kg, and the performance data of the finished lubricating grease obtained are shown in Table 1.

In the lubricating grease obtained in the present embodiment, based on the weight of the lubricating grease, the composition is: 54.7% of non-Newtonian calcium naphthenate; 36.1% of lubricating base oil; 3.5% of 12-hydroxy calcium stearate; 5.0% of calcium borate; 0.7% p-diisooctyl diphenylamine.

Example 6

Raw material components: ultra-high base value calcium naphthenate (total base value 400mgKOH/g, 30kg); PAO 40 (30kg); dodecylbenzenesulfonic acid (2.8kg); acetic acid (0.56kg); Ca( OH) ₂ (1.8kg); 12-Hydroxystearic Acid (2kg); Boric Acid (2.32kg); PAO 10 (18kg).

Prepare ultra-high base value complex calcium naphthenate-based grease by the method of example 1, the difference is to use dodecylbenzenesulfonic acid instead of naphthenic acid and to use fully synthetic oil polyalpha-olefin oil PAO 10 (100 ° C The kinematic viscosity is 11mm ² /s) and PAO 40 (100°C kinematic viscosity is 41mm ² /s) instead of 500SN and 150BS respectively, and the performance data of the obtained grease products are shown in Table 1.

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 38.5% of non-Newtonian calcium naphthenate; 55.4% of lubricating base oil; 2.4% of calcium 12-hydroxystearate; and 3.7% of calcium borate.

Example 7

Raw material components: high base value calcium naphthenate (total base value 320mgKOH/g, 30kg); 150BS (30kg); naphthenic acid (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (1.8kg ); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (18kg).

Prepare high base value composite calcium naphthenate-based grease by the method of example 1, the difference is that the total base value of the high base value calcium naphthenate used is 320mgKOH/g, and the performance data of the obtained lubricating grease finished product are shown in Table 1 .

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 38.5% of non-Newtonian calcium naphthenate; 55.4% of lubricating base oil; 2.4% of calcium 12-hydroxystearate; and 3.7% of calcium borate.

Example 8

Raw material components: high base value calcium naphthenate (total base value 360mgKOH/g, 30kg); 150BS (30kg); naphthenic acid (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (1.8kg ); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (18kg).

Prepare high-basic value composite calcium naphthenate-based grease by the method of example 1, the difference is that the total base value of the high-basic value calcium naphthenate used is 360mgKOH/g, and the performance data of the finished lubricating grease obtained are shown in Table 1 .

In the lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, the composition is: 38.5% of non-Newtonian calcium naphthenate; 55.4% of lubricating base oil; 2.4% of calcium 12-hydroxystearate; and 3.7% of calcium borate.

Example 9

Raw material components: ultra-high base number calcium naphthenate (total base number 400mgKOH/g, 30kg); 150BS (15kg); naphthenic acid (1.8kg); methanol (1.0kg); acetic acid (0.56kg); Ca (OH) ₂ (1.8kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); 500SN (33kg).

Prepare ultra-high base value composite calcium naphthenate-based grease by the method of Example 1, the difference is that the conversion agent has increased methanol, and the amount of base oil has also changed.

The lubricating grease obtained in this embodiment, based on the weight of the lubricating grease, consists of: 38.4% non-Newtonian calcium naphthenate; 55.4% lubricating base oil; 2.5% calcium 12-hydroxystearate; 3.7% calcium borate.

Example 10

Raw material components: high base value calcium naphthenate (total base value 360mgKOH/g, 30kg); 150BS (15kg); dodecylbenzenesulfonic acid (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (5.2kg); 12-hydroxystearic acid (2kg); boric acid (2.32kg); phosphoric acid (3kg); 500SN (33kg);

Prepare high base value composite calcium naphthenate-based grease according to the method of Example 9, the difference is that dodecylbenzenesulfonic acid is used instead of naphthenic acid, and phosphoric acid is added to the small molecule acid, and the performance data of the finished grease product are obtained. See Table 1.

In the lubricating grease that present embodiment obtains, take the lubricating grease weight as a benchmark, consist of: 36.5% of non-Newtonian calcium naphthenate; 52.5% of lubricating base oil; 2.3% of 12-hydroxy calcium stearate; 3.3% of calcium borate; Calcium phosphate 5.2%; p-diisooctyl diphenylamine 0.2%.

Example 11

Raw material components: high base value calcium naphthenate (total base value 360mgKOH/g, 30kg); 150BS (30kg); naphthenic acid (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (3kg) ; 12-hydroxystearic acid (2kg); boric acid (2.32kg); acetic acid (2kg); 500SN (18kg); p-diisooctyldiphenylamine (0.2kg).

Prepare high base value complex calcium naphthenate-based lubricating grease according to the method of Example 9, the difference is that acetic acid is added, and the performance data of the finished lubricating grease obtained are shown in Table 1.

In the lubricating grease obtained in the present embodiment, based on the weight of the lubricating grease, the composition is: 37.3% of non-Newtonian calcium naphthenate; 53.6% of lubricating base oil; 2.4% of calcium 12-hydroxystearate; 3.5% of calcium borate; Calcium acetate 3.0%; p-diisooctyldiphenylamine 0.2%.

comparative example

Raw material components: high base value calcium sulfonate (320mgKOH/g, 30kg); 150BS (30kg); dodecylbenzenesulfonic acid (2.8kg); acetic acid (0.56kg); Ca(OH) ₂ (1.8kg) ; 12-Hydroxystearic Acid (2kg); Boric Acid (2.32kg); 500SN (18kg).

Prepare high-basic calcium sulfonate-based grease by the method of example 1, the difference is that Newtonian calcium naphthenate is replaced with high-basic calcium sulfonate in the reactant, and the performance data of the finished lubricating grease obtained are shown in Table 1.

In the lubricating grease obtained in this example, based on the weight of the lubricating grease, the composition is: 38.5% of non-Newtonian calcium sulfonate; 55.4% of lubricating base oil; 2.4% of 12-hydroxy calcium stearate; and 3.7% of calcium borate.

Table 1 Performance data of each grease sample

Continuation

It can be seen from Table 1 that the performance of the grease prepared by using high-basic naphthenic acid as raw material is better than that of the grease prepared by using high-basic calcium sulfonate, especially in terms of water resistance and adhesion Unique advantages, this is an unexpected result.

Claims (16)

1. a Composite calcium naphthenate base lubricating grease, with lubricating grease weight for benchmark, comprises following component:

1) non-newtonian fluid calcium naphthenate 10%-70%; 2) the calcium salt 1%-10% of higher fatty acid; 3) the calcium salt 1%-15% of small molecules acid; 4) lubricating base oil 10%-80%, said small molecules acid is mineral acid or lipid acid.

2. according to lubricating grease according to claim 1, wherein with lubricating grease weight for benchmark, comprise following component:

1) non-newtonian fluid calcium naphthenate 20%-60%; 2) the calcium salt 2%-6% of higher fatty acid; 3) the calcium salt 2%-10% of small molecules mineral acid or lipid acid; 4) lubricating base oil 20%-70%.

3., according to lubricating grease according to claim 1, wherein said non-newtonian fluid calcium naphthenate is at infrared spectrum 873cm ^-1-886cm ^-1there is crystal form calcium carbonate charateristic avsorption band in place.

4., according to lubricating grease according to claim 1, wherein said non-newtonian fluid calcium naphthenate total basicnumber is 250mgKOH/g-450mgKOH/g.

5. according to lubricating grease according to claim 1, straight chain fatty acid or the hydroxy fatty acid of said higher fatty acid to be carbon number be 8-20.

6., according to lubricating grease according to claim 1, said higher fatty acid is selected from one or more mixtures in lauric acid, palmitinic acid, stearic acid, 12-oxystearic acid, eicosyl carboxylic acid.

7., according to lubricating grease according to claim 1, the molecular weight of said small molecules mineral acid or lipid acid is less than or equal to 150.

8., according to lubricating grease according to claim 1, said small molecules mineral acid is selected from the mixture of one or more in boric acid, phosphoric acid, sulfuric acid

9., according to lubricating grease according to claim 1, said small molecules lipid acid is selected from the mixture of one or more in acetic acid, oxalic acid, propionic acid, propanedioic acid, butyric acid, succinic acid.

10. one of claim 1 ~ 9 described Composite calcium naphthenate base preparation of greases method, comprising: (1) is by newton's body calcium naphthenate, part basis oil and transforming agent mixes, heating, makes material retrogradation; (2) add lime or calcium hydroxide, add higher fatty acid and small molecules mineral acid or lipid acid respectively, heat up dehydration; (3) be warmed up to 200 DEG C of-220 DEG C of constant temperature refinings, cooling, adds surplus base oil, adds necessary additive, obtains finished product.

11. according to preparation method according to claim 10, in step (1), by newton's body calcium naphthenate, part basis oil Hybrid Heating to 50 DEG C-80 DEG C, add required transforming agent successively to react, all transforming agents add rear intensification, 80 DEG C of-90 DEG C of constant temperature 60 minutes-90 minutes, make material retrogradation.

12. according to preparation method according to claim 10, in step (2), add the suspension liquid of lime or calcium hydroxide at 85 DEG C-100 DEG C, add higher fatty acid at 85 DEG C-100 DEG C, stir 5 minutes-20 minutes, add small molecules mineral acid or lipid acid, stir 5 minutes-20 minutes, be warmed up to 105 DEG C-120 DEG C, dehydration, cool to 90 DEG C-105 DEG C, the addition sequence of its Fatty Acids and small molecules acid can exchange.

13. according to preparation method according to claim 10, in step (3), heats up to the product of step (3), 100 DEG C of-120 DEG C of constant temperature 10 minutes-20 minutes, is finally warmed up to 200 DEG C-220 DEG C constant temperature 5-10 minute; Be cooled to 150 DEG C-160 DEG C, add surplus lubricating base oil, treat that temperature is cooled to 100 DEG C-120 DEG C, add necessary additive, stir, circulating filtration, homogenizing, degassed.

14. according to preparation method according to claim 10, and described newton's body calcium naphthenate is petroleum naphthenic acid calcium or synthesis calcium naphthenate, and its total basicnumber is 250mgKOH/g-450mgKOH/g.

15. according to preparation method according to claim 10, said transforming agent is selected from fatty alcohol, lipid acid, aliphatic ketone, alkanoic, aliphatic amide, cycloalkanes amine, cycloalkanol, the ether of C1-C5, and boric acid, calcium carbonate, phosphonic acids, carbonic acid gas, phenol, aromatic alcohol, aromatic amine, C8-C20 alkyl benzene sulphonate (ABS), C16-C62 naphthenic acid, one or more in water, the add-on of transforming agent is the 2%-30% of newton's body calcium naphthenate weight.

16. according to preparation method according to claim 15, said transforming agent is selected from one or more in Witco 1298 Soft Acid, methyl alcohol, Virahol, butanols, C20-C40 naphthenic acid, acetic acid and water, and the add-on of transforming agent is the 6%-22% of newton's body calcium naphthenate weight.