CN115010751A

CN115010751A - Phosphorus-nitrogen type multifunctional additive and preparation method thereof

Info

Publication number: CN115010751A
Application number: CN202210843615.5A
Authority: CN
Inventors: 王爽; 袁小二; 王庆超; 刘西林; 徐坤; 范金凤
Original assignee: Xinxiang Richful Lube Additive Co ltd
Current assignee: Xinxiang Richful Lube Additive Co ltd
Priority date: 2022-07-18
Filing date: 2022-07-18
Publication date: 2022-09-06

Abstract

The invention provides a phosphorus-nitrogen type multifunctional additive and a preparation method thereof, and relates to the field of gear oil additives. The general formula of the phosphorus-nitrogen multifunctional additive is as follows:

the method comprises the following steps: placing the alcohol substance inAdding phosphorus pentoxide into a reaction device, and reacting to obtain phosphate; and adding fatty amine containing benzotriazole group into phosphate ester, and reacting to obtain the phosphorus-nitrogen multifunctional additive. The phosphorus-nitrogen type multifunctional additive disclosed by the invention has good extreme pressure wear resistance, rust prevention and corrosion prevention performance, oil solubility and thermal oxidation stability.

Description

Phosphorus-nitrogen type multifunctional additive and preparation method thereof

Technical Field

The disclosure relates to the field of gear oil additives, in particular to a phosphorus-nitrogen type multifunctional additive and a preparation method thereof.

Background

With the rapid development of the machine manufacturing industry, the use of extreme pressure antiwear agents to improve the mechanical efficiency and prolong the service life becomes the key point of domestic and foreign research, and the extreme pressure antiwear agents are the most commonly used additives in gear oil. The phosphate extreme pressure antiwear agent is widely applied due to excellent wear resistance and friction reduction performance, but the phosphate extreme pressure antiwear agent can severely corrode the metal surface in the using process. Therefore, the selection of a nitrogen-containing compound with an appropriate molecular structure and the synthesis of phosphate amine salt with phosphate ester to make the phosphate amine salt have good anti-wear performance and not cause excessive corrosion becomes a key point of research on extreme pressure anti-wear agents.

The development direction of the phosphate amine salt extreme pressure antiwear agent is to reduce the consumption of phosphorus to prolong the service life of the extreme pressure antiwear agent on the premise of not reducing the extreme pressure antiwear performance; meanwhile, through molecular design, new functional groups and active elements are introduced to synthesize the multifunctional additive.

The related amine phosphate salts reported in the literature mainly focus on the research on the synthesis process and the extreme pressure antiwear property, and a multifunctional additive which has excellent extreme pressure antiwear property, good antirust and anticorrosive properties and the like is urgently needed.

Patent CN113512060 discloses a phosphorus ester amine salt extreme pressure antiwear agent and a preparation method thereof, monohydric alcohol and phosphorus-containing oxide are used for esterification reaction to obtain phosphate, and then the phosphate is reacted with alkyl primary amine to obtain phosphate amine salt, the product has good extreme pressure antiwear performance, but other performances are not evaluated, the function is single, and the phosphate amine salt synthesized by monohydric alcohol is very easy to dissolve in water, and the oil solubility is poor;

patent CN102260572 discloses a preparation method of a phosphorus-nitrogen type extreme pressure antiwear agent, which uses an amine compound containing a benzotriazole group to react with dialkyl phosphite to generate acid phosphate, wherein, the stability of thermal oxidation is relatively poor due to the structure of organic phosphite, meanwhile, the phosphorus retention capacity is poor, and hydrochloric acid is used as a catalyst in the synthesis process, which has certain requirements on equipment, and meanwhile, post-treatment is required, and the synthesis process is complex.

Disclosure of Invention

In order to solve the above problems in the prior art, the present disclosure is directed to provide a multifunctional additive having good extreme pressure antiwear properties, corrosion protection and rust protection properties, and a preparation method thereof.

In order to achieve the above purpose, the present disclosure adopts the following technical solutions:

the present disclosure provides a phosphorus-nitrogen type multifunctional additive, which is characterized in that the general formula of the phosphorus-nitrogen type multifunctional additive is as follows:

wherein R is ₁ 、R ₂ Is alkyl, R ₃ Is straight chain or branched chain C8-C18 alkyl.

In some embodiments, R ₁ 、R ₂ Is straight chain or branched chain C3-C12 alkyl.

The present disclosure also provides a method for preparing the phosphorus-nitrogen type multifunctional additive, comprising the steps of:

s1, putting the alcohol substance into a reaction device, adding phosphorus pentoxide, and reacting to obtain phosphate;

and S2, adding aliphatic amine containing benzotriazole groups into phosphate ester, and reacting to obtain the phosphorus-nitrogen multifunctional additive.

In some embodiments, the alcohol is a linear or branched C3-C12 fatty alcohol.

In some embodiments, the reaction apparatus is maintained at a temperature of less than 70 ℃ and the phosphorus pentoxide is added.

In some embodiments, the reaction conditions of the alcohol and the phosphorus pentoxide are 70-100 ℃ for 6-8 hours.

In some embodiments, the molar ratio of phosphorus pentoxide to the alcohol is 1: 3.0 to 4.0.

In some embodiments, the reaction conditions of the phosphate and the aliphatic amine containing a benzotriazole group are 80-100 ℃ for 2-4 hours.

In some embodiments, the molar ratio of phosphorus pentoxide to the aliphatic amine containing a benzotriazole group is 1: 1.0 to 2.0.

In some embodiments, the aliphatic amine containing a benzotriazole group has the formula:

wherein R is ₃ Is straight chain or branched chain C8-C18 alkyl.

The beneficial effects of the above technical scheme that this disclosure provided include at least:

the gear oil prepared by using the phosphorus-nitrogen multifunctional additive disclosed by the invention has excellent extreme wear resistance, good rust and corrosion resistance, and good oil solubility, durability and thermal oxidation stability. The preparation method of the phosphorus-nitrogen multifunctional additive has the advantages of simple process flow, no need of complex devices, reduction of production cost, 99% of yield of the prepared product, no generation of toxic and harmful gases in the preparation process, no unpleasant odor of the synthesized product and less environmental pollution.

Drawings

In order to more clearly explain the technical solutions in the embodiments of the present disclosure, the drawings that are needed to be used in the description of the embodiments will be briefly introduced below. Other features, objects, and advantages of the present disclosure will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, with reference to the accompanying drawings.

Fig. 1 is a flow chart of a method for preparing a multifunctional additive of phosphorus-nitrogen type according to an embodiment of the present disclosure.

Detailed Description

For a better understanding of the present disclosure, the present disclosure is further illustrated by the following examples, and it is to be understood that these detailed descriptions are merely descriptive of exemplary embodiments of the present disclosure and are not intended to limit the scope of the present disclosure in any way. The expression "and/or" includes any and all combinations of one or more of the associated listed items.

The present disclosure is described in further detail below:

Fig. 1 is a flow chart of a method for preparing a multifunctional phosphorus-nitrogen additive according to an embodiment of the present disclosure, and referring to fig. 1, the present disclosure further provides a method for preparing a multifunctional phosphorus-nitrogen additive, including the following steps:

further, placing straight-chain or branched-chain C3-C12 fatty alcohol into a reaction device with a condensation reflux device, keeping the temperature of the reaction device less than or equal to 70 ℃, adding phosphorus pentoxide in batches, heating to 70-100 ℃ after all the phosphorus pentoxide is added, and reacting for 6-8 hours to obtain an intermediate phosphate; optionally, in order to avoid the volatilization of the alcohol in the reaction process, the reaction device can be provided with a condensation reflux device;

further, the molar ratio of phosphorus pentoxide to alcohol is 1: 3.0 to 4.0;

s2, adding aliphatic amine containing benzotriazole groups into phosphate ester, and reacting to obtain a phosphorus-nitrogen multifunctional additive;

further, adding aliphatic amine containing benzotriazole groups into the phosphate, keeping the temperature at 80-100 ℃ after the addition is finished, and reacting for 2-4 hours to obtain phosphate amine salt;

further, the molar ratio of phosphorus pentoxide to the aliphatic amine containing a benzotriazole group is 1: 1.0 to 2.0;

specifically, the general formula of the aliphatic amine containing a benzotriazole group is as follows:

wherein R is ₃ Is straight chain or branched chain C8-C18 alkyl.

The phosphate forms a layer of iron phosphite protective film with the metal surface through phosphorus in the using process, so the phosphate has excellent extreme pressure abrasion resistance, but can generate serious corrosion to the metal surface, so the nitrogen-containing compound with a proper molecular structure is selected to be combined with the phosphate, and the prepared phosphate amine salt has good abrasion resistance and can not cause excessive corrosion. The nitrogen-containing heterocycle and the derivatives thereof have excellent antirust performance, oxidation resistance, corrosion resistance and certain abrasion resistance, but the application range is greatly influenced due to poor oil solubility. Therefore, the fatty amine containing the benzotriazole group is selected to be combined with the phosphate, so that the excessive corrosion of the phosphate alone to metals can be prevented, the antirust and anticorrosive properties of the phosphate amine salt can be improved, and the oil solubility problem of the benzotriazole can be improved.

Example 1

Putting 82.6g (0.634mol) of isooctanol in a four-mouth bottle, adding 30g (0.211mol) of phosphorus pentoxide in batches under the condition of ensuring that the temperature in the four-mouth bottle is less than or equal to 70 ℃, heating to 80 ℃ after the addition is finished, and preserving the temperature for 6 hours to obtain an intermediate isooctyl phosphate, wherein the molar ratio of the phosphorus pentoxide to the isooctanol is 1: 3.0 of the total weight of the mixture; 169.35g (0.423mol) of benzotriazole methylene octadecylamine is added, the temperature is raised to 90 ℃, and the temperature is kept for 2h, so that the product 1, namely the isooctyl phosphate benzotriazole methylene octadecylamine salt is obtained, wherein the molar ratio of the phosphorus pentoxide to the benzotriazole methylene octadecylamine is 1: 2.0. The yield of product 1 was 279.3g, 99.06% yield. The phosphorus content in the product 1 was 4.5 mass%, and the nitrogen content was 8.40 mass%.

Example 2

By replacing isooctanol with an equivalent amount of isopropanol and keeping the same conditions and preparation method as in example 1, product 2, i.e., isopropyl phosphate benzotriazole methylene octadecylamine salt was obtained at a yield of 235.75g and a yield of 99.27%. The phosphorus content in the product 2 was 5.43 mass%, and the nitrogen content was 9.98 mass%.

Example 3

The isooctanol was replaced with an equivalent amount of n-propanol, and the remaining conditions and preparation method were kept the same as in example 1 to obtain product 3 in light yellow color. The yield of product 3 was 236.43g, 99.56%. The phosphorus content in the product 3 was 5.42 mass%, and the nitrogen content was 9.96 mass%.

Example 4

The amount of isooctanol used was changed to 110g (0.845mol), where the molar ratio of phosphorus pentoxide to isooctanol was 1:4.0, and the other conditions and preparation were kept the same as in example 1, yielding product 4 as pale yellow. The yield of product 4 was 306.59g, 99.11%. The phosphorus content in the product 4 was 4.15 mass%, and the nitrogen content was 7.72 mass%.

Example 5

The isooctanol was replaced with n-butanol in an equivalent amount, and the remaining conditions and preparation method were the same as in example 1, to obtain a pale yellow product 5. The yield of product 5 was 244.53g, 99.3%. The phosphorus content in the product 5 was 5.21 mass%, and the nitrogen content was 9.6 mass%.

Example 6

The iso-octanol was replaced with an equal amount of sec-butanol, and the remaining conditions and preparation method remained the same as in example 1, yielding product 6 as a pale yellow color. The yield of product 6 was 245.23g, 99.5%. The phosphorus content in the product 6 was 5.22 mass%, and the nitrogen content was 9.58 mass%.

Example 7

The iso-octanol was changed to n-octanol in an equivalent amount, and the remaining conditions and preparation method were maintained the same as in example 1, to obtain product 7 in pale yellow color. The yield of product 7 was 280.36g, 99.4% yield. The phosphorus content in the product 7 was 4.4 mass%, and the nitrogen content was 8.39 mass%.

Example 8

The isooctanol was replaced with an equivalent amount of dodecanol, and the remaining conditions and preparation method remained the same as in example 1, to obtain product 8 in pale yellow color. The yield of product 8 was 315.76g, 99.3%. The phosphorus content in the product 8 was 4.8 mass%, and the nitrogen content was 8.9 mass%.

Example 9

After the phosphorus pentoxide addition was complete, the temperature was raised to 70 ℃ and the remaining conditions and preparation were the same as in example 1, giving product 9 in a pale yellow color. The yield of product 9 was 278.6g, 98.8%. The phosphorus content in the product 9 was 4.3 mass%, and the nitrogen content was 8.4 mass%.

Example 10

After the addition of phosphorus pentoxide was completed, the temperature was raised to 100 ℃ and the remaining conditions and preparation method were the same as in example 1, to obtain a dark yellow product 10. The yield of product 10 was 278.4g, 98.7%. The phosphorus content in the product 10 was 4.4 mass%, and the nitrogen content was 8.4 mass%.

Example 11

After the addition of phosphorus pentoxide is finished, the temperature is raised to 80 ℃, the temperature is kept for 8h, and the rest conditions and the preparation method are kept the same as those in example 1, so that a light yellow product 11 is prepared. The yield of product 11 was 278.9g, 99%. The phosphorus content in the product 11 was 4.5 mass%, and the nitrogen content was 8.4 mass%.

Example 12

After the addition of the benzotriazole methylene octadecylamine was completed, the temperature was raised to 80 ℃, and the remaining conditions and preparation method were the same as in example 1, to obtain a pale yellow product 12. The yield of product 12 was 279.1g, 99%. The phosphorus content in the product 12 was 4.5 mass%, and the nitrogen content was 8.4 mass%.

Example 13

After the end of the addition of the benzotriazolylmethyleneoctadecylamine, the temperature was raised to 100 ℃ and the remaining conditions and preparation were the same as in example 1, giving product 13 in yellow color. The yield of product 13 was 279.6g, 99.2%. The phosphorus content in the product 13 was 4.5 mass%, and the nitrogen content was 8.4 mass%.

Example 14

And after the addition of the benzotriazole methylene octadecylamine is finished, the temperature is raised to 90 ℃, the temperature is kept for 4 hours, and the rest conditions and the preparation method are kept the same as those in example 1, so that a light yellow product 14 is prepared. The yield of product 14 was 279.5g, 99.1% yield. The phosphorus content in the product 14 was 4.5 mass%, and the nitrogen content was 8.4 mass%.

Example 15

The benzotriazole methylene octadecyl amine was replaced with the equivalent amount of benzotriazole methylene octyl amine, and the remaining conditions and the preparation method were the same as in example 1 to give a pale yellow product 15. The yield of product 15 was 220.3g, 99%. The phosphorus content in the product 15 was 5.6 mass%, and the nitrogen content was 2.6 mass%.

Example 16

The amount of benzotriazole methylene octadecylamine used was changed to 84.68g (0.212mol), where the molar ratio of phosphorus pentoxide to benzotriazole methylene octadecylamine was 1: 1.0, the remaining conditions and preparation remain the same as in example 1, giving a pale yellow product 16. The yield of product 16 was 195.9g, 99.3%. The phosphorus content in the product 16 was 6.5 mass%, and the nitrogen content was 1.5 mass%.

Comparative example 1

The product 17, i.e., isooctyl ester octadecylamine phosphate, was prepared by replacing the benzenetriazolylmethyleneoctadecylamine with an equivalent amount of octadecylamine, and the remaining conditions and preparation method were the same as in example 1.

Comparative example 2

The product 18 is prepared by replacing benzene triazole methylene octadecylamine with benzene triazole with equal amount of substances, and reacting phosphate with benzene triazole under the condition of heating to 140 ℃ for 4 hours, wherein the rest conditions and the preparation method are the same as those of the example 4.

Comparative example 3

The benzotriazole methylene octadecylamine was replaced by equal amount of T406, and the reaction conditions of the phosphate ester and T406 were heating to 140 ℃ for 4h, while the rest conditions and preparation method were the same as those in example 1, to obtain product 19.

Specifically, T406 is octadecyl benzotriazole amine salt, having the formula:

comparative example 4

80g (0.412mol) of di-n-butyl phosphite is placed in a reaction bottle, 165g (0.413mol) of benzotriazole methylene octadecylamine is added, and the mixture is heated to 140 ℃ for reaction for 4h to obtain a product 20.

Extreme pressure antiwear, anticorrosive and antirust performance

The products 1 to 20 prepared in the above examples 1 to 4 were blended with 80W-90 thickened base oil in an amount of 1% to perform extreme pressure antiwear performance, anticorrosive performance and rust preventive performance tests, and the results are shown in the following table:

note: the evaluation conditions of the long grinding are 1200r/min, 75 ℃, 40kg and 1 h.

In the above table, P is _B 、P _D And D is used to express the extreme pressure antiwear performance of the material, and a four-ball method is adopted as an evaluation method. Wherein, P _B Denotes the maximum seizure-free load, i.e. the maximum load at which seizure does not occur under the test conditions, in N, and represents the pressure resistance of the lubricating oil, P _B The larger the value, the better the performance of the material; p _D Denotes the sintering load, i.e. the lowest load at which sintering of the steel balls takes place under the test conditions, in N, and represents the ultimate working capacity of the lubricating oil, P _D The larger the value, the better the performance of the material; d represents the diameter of the abrasion marks, and the smaller the value of D, the better the abrasion resistance of the material is. In summary, when P is _B Value, P _D The larger the value, the smaller the D value, indicating the better extreme pressure antiwear performance of the material.

According to the test results in the table above, the test results of the products of example 1, example 2, example 3, example 5, example 6, example 7 and example 8 are compared to find that the amine salt of phosphoric acid ester synthesized by lower alcohol has better extreme pressure antiwear performance under the same conditions; the test results of the products of the above groups of examples 1 and 7, 2 and 3, 5 and 6 are compared to find that the products prepared by using the branched alkyl alcohol as the reactant have more excellent extreme pressure anti-wear performance under the same conditions; the comparison of the products obtained in example 1 with that in example 9, example 10 and example 11 shows that by changing the reaction temperature and time of the alcohol and the phosphorus pentoxide, the products have only slight differences in appearance, phosphorus content and yield, in example 9, the reaction temperature is slightly low, the yield of the synthesized product is low, the incomplete reaction is mainly caused by the low reaction temperature, so that the phosphorus content is low, in example 10, the color of the reaction product is dark, and the comparison of the test results of the products in the above groups shows that the reaction temperature and time of the alcohol and the phosphorus pentoxide have no obvious influence on the extreme pressure wear resistance, the rust prevention and corrosion prevention, the durability and the like; the reaction temperature and the reaction time of the phosphate ester and the aliphatic amine containing the benzotriazole group are changed in the examples 1, 12, 13 and 14, and the comparison of the test results of the above groups of products shows that the reaction temperature and the reaction time of the phosphate ester and the aliphatic amine containing the benzotriazole group have no obvious influence on the yield, the element content, the performance and the like of the products. Examples 1 and 15, the length of the carbon chain in the aliphatic amine containing a benzotriazole group was changed, and P was found to be increased due to the increased phosphorus content _B The value is slightly improved, and other properties are not obviously influenced. Examples 1 and 16 the phosphorus content was increased by varying the amount of benzotriazole methylene octadecylamine _B The value is relatively increased and other properties have no obvious influence. As a result of comparing the test results of the product of example 1 with the product of comparative example 1, it can be found that the product prepared by using the aliphatic amine compound containing a benzotriazole group of the present disclosure as a reactant has more excellent anti-wear properties and rust and corrosion prevention properties under the same conditions; the test results for the product of comparative example 2 show that,the product 18 has excellent extreme pressure performance, but has poor wear resistance, and 1 percent of oil sample becomes turbid after being placed at room temperature, and has poor oil solubility; the test results of the product of comparative example 3 show that the product 19 has excellent extreme pressure antiwear properties, but has poor rust prevention properties during use; the test result of the product of comparative example 4 shows that the product 20 has excellent extreme pressure anti-wear performance, but poor copper corrosion and rust prevention performance; the results of the tests on the products of example 5 and comparative example 4 were compared, and it was found that the product prepared using phosphite ester had relatively excellent extreme pressure properties, but had poor anti-wear, anti-corrosion and anti-rust properties.

Durability performance

The products 1-20 from example 1 to comparative example 4 were blended at 1% loading with 80W-90 thickened base oil and subjected to 135 ℃ 72h oven oxidation tests, the results of which are shown in the following table:

note: steel sheet rating regulation: 0-steel sheet does not change color; 1-slight discoloration, almost identical to the new tablet; 2-local pale white; 3-mostly pale white; 4-gray, blue, yellow or gray-white; 5-local grayish black, flaking. The cup bottom sediment is distinguished by no sediment, little sediment, medium sediment and more sediment.

From the test results in the table above, it can be seen that the product prepared using phosphite has poor thermal oxidation stability as compared with the product of comparative example 4. From the test results in the above table, it can be found that the products 1 to 16 prepared using the preparation method of the present disclosure have good thermal oxidation stability and durability, and at the same time, have good phosphorus retention ability.

Comprehensive performance of gear oil

Adding 92% of extreme pressure antiwear agent, 5% of antirust preservative and 3% of metal deactivator into 80W-90 thickened base oil, and blending to obtain finished oil A; adding the product 1 prepared in the embodiment 1 of the disclosure into a gear oil complexing agent, adding the gear oil complexing agent added with the product 1 into 80W-90 thickened base oil, and blending to obtain a finished oil B; the product 20 prepared in comparative example 4 was added to the gear oil complex in the same amount as the product 1, and the gear oil complex with the product 20 added was added to 80W-90W thickened base oil to prepare a finished oil C. The performance of the finished oil A, the finished oil B and the finished oil C is tested, the extreme pressure antiwear performance is evaluated, and the test results are shown in the following table:

according to the test results in the table above, it can be found that the complexing agent added with the product prepared by the embodiment of the present disclosure has more excellent extreme pressure anti-wear performance and rust-proof and anti-corrosion performance during the use process.

While particular embodiments of the present invention have been described in the foregoing specification, various modifications, alterations and adaptations to those previously described embodiments may occur to persons skilled in the art upon reading the foregoing description without departing from the spirit and scope of the present invention.

Claims

1. A phosphorus-nitrogen type multifunctional additive, which is characterized in that the general formula of the phosphorus-nitrogen type multifunctional additive is as follows:

2. The multifunctional additive of phosphorus-nitrogen type according to claim 1, wherein R is ₁ 、R ₂ Is straight chain or branched chain C3-C12 alkyl.

3. A method for preparing the multifunctional additive of phosphorus-nitrogen type according to any one of claims 1 to 2, comprising the steps of:

4. The method for preparing multifunctional additive of phosphorus-nitrogen type as claimed in claim 3, wherein the alcohol is a linear or branched aliphatic alcohol of C3-C12.

5. The method for preparing a multifunctional additive of phosphorus-nitrogen type according to claim 3, wherein the reaction apparatus is maintained at a temperature of less than 70 ℃ and the phosphorus pentoxide is added.

6. The method for preparing the phosphorus-nitrogen multifunctional additive according to claim 3, wherein the reaction condition of the alcohol substance and the phosphorus pentoxide is 70-100 ℃ for 6-8 hours.

7. The method for preparing the multifunctional additive of phosphorus-nitrogen type according to claim 3, wherein the molar ratio of the phosphorus pentoxide to the alcohol is 1: 3.0 to 4.0.

8. The method for preparing the multifunctional additive of phosphorus-nitrogen type according to claim 3, wherein the reaction condition of the phosphoric acid ester and the aliphatic amine containing the benzotriazole group is 80 to 100 ℃ for 2 to 4 hours.

9. The method for preparing the multifunctional additive of phosphorus-nitrogen type according to claim 3, wherein the molar ratio of the phosphorus pentoxide to the aliphatic amine containing a benzotriazole group is 1: 1.0 to 2.0.

10. The method for preparing multifunctional additive of phosphorus-nitrogen type according to claim 3, wherein the aliphatic amine containing benzotriazole group has the following general formula:

wherein R is ₃ Is straight chain or branched chain C8-C18 alkyl.