阅读说明：本技术 一种合成型防锈剂浓缩液、其制备方法及应用 (Synthetic antirust agent concentrated solution, preparation method and application thereof ) 是由 孙晓勃 李霞 马楷 于 2021-08-12 设计创作，主要内容包括：本发明提供了一种可满足飞机发动机轴承等部件封存防锈的高效合成型防锈剂浓缩液,该浓缩液具有低酸值、无灰等特点,可根据飞机发动机所处环境的苛刻程度来调节浓缩液的加量比例,其中所含高效的防锈组分可为发动机内部金属部件提供长期的有效防护,防止部件锈蚀造成巨额经济损失。(The invention provides a high-efficiency synthetic antirust agent concentrated solution which can meet the sealing and rust prevention of parts such as airplane engine bearings and the like, the concentrated solution has the characteristics of low acid value, no ash and the like, the addition proportion of the concentrated solution can be adjusted according to the harsh degree of the environment where an airplane engine is located, and the contained high-efficiency antirust component can provide long-term effective protection for metal parts in the engine and prevent the parts from being rusted to cause huge economic loss.)

1. A synthetic antirust agent concentrated solution is characterized by comprising the following components:

2. the synthetic rust inhibitor concentrate as claimed in claim 1, wherein the polypropylene glycol has a molecular weight of 400 to 2000.

3. The synthetic rust inhibitor concentrate of claim 1, wherein the hydrotreated heavy naphthenic base oil consists of hydrocarbons in the range of C20 to C50.

4. The synthetic rust inhibitor concentrate of claim 1 wherein the antioxidant is selected from the group consisting of N-phenyl alpha naphthylamine; the neopentyl polyol ester is selected from pentaerythritol ester and/or trimethylolpropane ester.

5. The synthetic antirust agent concentrate as claimed in claim 1, wherein the carbon number of alkenyl groups in the long-chain alkenyl succinic anhydride is 12-17.

6. The synthetic antirust agent concentrate of claim 1, wherein the long-chain alkenyl imidazoline salt is selected from a reaction product of alkenyl succinic acid with 12-17 carbon atoms and 1-aminoethyl-2 (heptadecenyl) imidazoline.

7. The synthetic rust inhibitor concentrate of claim 1, comprising:

8. the method for preparing the synthetic antirust agent concentrated solution according to claim 1, which is characterized by comprising the following steps:

mixing polypropylene glycol, hydrotreated heavy naphthenic base oil, tricresyl phosphate, an antioxidant, a reaction product of propylene oxide and long-chain alkenyl succinic anhydride, long-chain alkenyl imidazoline salt, oleoyl sarcosine and/or amine salt thereof and neopentyl polyol ester, and heating to dissolve to obtain the synthetic antirust agent concentrated solution.

9. The method according to claim 8, wherein the temperature for heating and dissolving is 60 to 80 ℃.

10. The use of the synthetic rust inhibitor concentrate of any one of claims 1 to 7 or the synthetic rust inhibitor concentrate prepared by the preparation method of claim 8 or 9 in the sealing and rust prevention of turbine engines and/or helicopter transmission systems.

Technical Field

The invention belongs to the technical field of rust prevention, and particularly relates to a synthetic rust inhibitor concentrated solution, and a preparation method and application thereof.

Background

When the aeroengine needs to be sealed for a long time due to maintenance, detection and the like, in order to prevent metal parts in the engine from being directly contacted with air, moisture and other corrosive substances to generate corrosion, the aeroengine needs to be sealed by using aeroengine sealing antirust oil.

The antirust agent is directly added into the lubricating oil, which is the most common method for improving the antirust capacity of the lubricating oil, but at present, the traditional aviation seal antirust oil generally adopts the antirust agent with large ash content and high acid value, and although the antirust effect of the antirust agent is better, the traditional aviation seal antirust oil cannot meet the use requirement of an aircraft engine system along with the continuous maturity of the aviation lubricating oil technology and the harsh requirement on environmental protection.

For example, chinese patent publication No. CN106675710A provides a special rust preventive oil composition for engine parts, which uses dinonylbenzenesulfonic acid, barium petroleum sulfate, benzotriazole and other rust preventive agents to enhance rust preventive performance, but contains a large amount of ash, barium and other heavy metals which are harmful to the environment.

Disclosure of Invention

In view of the above, the technical problem to be solved by the present invention is to provide a low acid value, ashless synthetic rust inhibitor concentrate, a preparation method thereof and an application thereof.

The invention provides a synthetic antirust agent concentrated solution, which comprises the following components:

preferably, the molecular weight of the polypropylene glycol is 400 to 2000.

Preferably, the hydrotreated heavy naphthenic base oil consists of hydrocarbons ranging from C20 to C50.

Preferably, the antioxidant is selected from N-phenyl alpha naphthylamine; the neopentyl polyol ester is selected from pentaerythritol ester and/or trimethylolpropane ester.

Preferably, the carbon number of the alkenyl in the long-chain alkenyl succinic anhydride is 12-17.

Preferably, the long-chain alkenyl imidazoline salt is selected from a reaction product of alkenyl succinic acid with 12-17 carbon atoms and 1-aminoethyl-2 (heptadecenyl) imidazoline.

Preferably, the method comprises the following steps:

the invention also provides a preparation method of the synthetic antirust agent concentrated solution, which comprises the following steps:

mixing polypropylene glycol, hydrotreated heavy naphthenic base oil, tricresyl phosphate, an antioxidant, a reaction product of propylene oxide and long-chain alkenyl succinic anhydride, long-chain alkenyl imidazoline salt, oleoyl sarcosine and/or amine salt thereof and neopentyl polyol ester, and heating to dissolve to obtain the synthetic antirust agent concentrated solution.

Preferably, the temperature for heating and dissolving is 60-80 ℃.

The invention also provides application of the synthetic antirust agent concentrated solution in sealing and rust prevention of turbine engines and/or helicopter transmission systems.

The invention provides a synthetic antirust agent concentrated solution, which comprises the following components: 0.001 to 10 parts by weight of polypropylene glycol; 0.01-10 parts by weight of a hydrotreated heavy naphthenic oil; 0.02-3 parts by weight of tricresyl phosphate; 0.01-4 parts by weight of an antioxidant; 1-30 parts by weight of a reaction product of propylene oxide and long-chain alkenyl succinic anhydride; 0.01-1 part by weight of long-chain alkenyl imidazoline salt; 0.001-5 parts by weight of oleoyl sarcosine and/or amine salt thereof; and supplementing the synthetic antirust agent concentrated solution to 100 parts by weight with neopentyl polyol ester. Compared with the prior art, the low-acid-value high-efficiency ashless antirust agent composition is selected and matched with other auxiliary agents to form the antirust agent concentrated solution, and the addition amount of the concentrated solution can be adjusted according to the rigor degree of the engine sealing condition; and the antirust agent compositions have good synergistic effect, can exert antirust effect to a greater extent, can provide effective protection for bearings, gear boxes and other parts of aircraft engines under severe conditions such as humidity, high temperature and the like, wherein nitrogen in oleoyl sarcosine and amine salts thereof can interact with free d-rail metal, so that adsorption of antirust agent molecules on the metal surface is facilitated, long-chain alkenyl imidazoline salt can generate synergistic effect with oleoyl sarcosine, a reaction product of epoxypropane and long-chain alkenyl succinic anhydride can provide damp-heat resistance in a high-temperature environment, polypropylene glycol can play a role in regulating the kinematic viscosity of an antirust agent concentrated solution, and heavy naphthenic base oil can dissolve the antirust agent and other auxiliary agents to a greater extent, so that the stability of an antirust agent concentrated liquid system is ensured.

The synthetic antirust agent concentrated solution provided by the invention can meet the requirements of sealing and storing antirust components such as airplane engine bearings and the like, has the characteristics of low acid value, no ash and the like, can adjust the addition proportion of the concentrated solution according to the harsh degree of the environment where the airplane engine is located, and can provide long-term effective protection for metal components in the engine and prevent the components from being corroded to cause huge economic loss.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The invention provides a synthetic antirust agent concentrated solution, which comprises the following components:

wherein the content of the polypropylene glycol is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, still more preferably 0.3 to 6 parts by weight, still more preferably 0.5 to 4 parts by weight, still more preferably 0.5 to 2 parts by weight, and most preferably 0.5 to 1 part by weight; the molecular weight of the polypropylene glycol is preferably 400-2000, more preferably 600-2000, and still more preferably 1000-2000.

In the present invention, the content of the hydrotreated heavy naphthenic oil is preferably 0.1 to 10 parts by weight, more preferably 1 to 10 parts by weight, still more preferably 2 to 8 parts by weight, still more preferably 4 to 6 parts by weight, and most preferably 5 parts by weight; the hydrotreated heavy naphthenic oil is a complex hydrocarbon composition obtained by treating a petroleum fraction with hydrogen in the presence of a catalyst; the catalyst is preferably alumina or molecular sieve which takes nickel, molybdenum and palladium as active components; the hydrotreated heavy naphthenic oil preferably consists of hydrocarbons in the range of C20 to C50; more preferably a product oil consisting of hydrocarbons in the range of C20 to C50 and having a product of at least 19cSt (40 ℃); most preferably, the hydrotreated heavy naphthenic oil is a heavy hydrogenated naphthenic oil of Alfa Chemistry.

In the present invention, the content of the tricresyl phosphate is preferably 0.1 to 3 parts by weight, more preferably 0.5 to 3 parts by weight, still more preferably 1 to 3 parts by weight, still more preferably 1.5 to 2.5 parts by weight, and most preferably 2 parts by weight.

In the invention, the content of the antioxidant is preferably 0.05 to 3 parts by weight, more preferably 0.05 to 2 parts by weight, still more preferably 0.05 to 1 part by weight, and most preferably 0.1 to 0.5 part by weight; the antioxidant is preferably an amine antioxidant, more preferably N-phenyl alpha naphthylamine.

In the invention, the content of the reaction product of the propylene oxide and the long-chain alkenyl succinic anhydride is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight, still more preferably 5 to 15 parts by weight, and most preferably 8 to 10 parts by weight; the carbon atom number of alkenyl in the long-chain alkenyl succinic anhydride is preferably 12-17, more preferably 14-17, further preferably 15-17, and most preferably 16-17; in the present invention, most preferably, the reaction product of propylene oxide and long chain alkenyl succinic anhydride is a hydroxyalkyl carboxylate from Amadis Chemical company.

In the invention, the content of the long-chain alkenyl imidazoline salt is preferably 0.1-0.8 weight part, more preferably 0.1-0.6 weight part, and still more preferably 0.2-0.4 weight part; the carbon atom number of alkenyl in the long-chain alkenyl imidazoline salt is preferably 12-17; more preferably, the long-chain alkenyl imidazoline salt is a reaction product of alkenyl succinic acid with 12-17 carbon atoms and 1-aminoethyl-2 (heptadecenyl) imidazoline, and still more preferably, the long-chain alkenyl imidazoline salt is heptadecenyl imidazoline dodecenyl succinate; most preferably, the long chain alkenyl imidazolium salt is 1-aminoethyl-2 (heptadecenyl) imidazoline.

In the present invention, the content of oleoyl sarcosine and/or amine salt thereof is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, still more preferably 1 to 5 parts by weight, still more preferably 2 to 4 parts by weight, and most preferably 3 to 4 parts by weight; the oleoyl sarcosine amine salt is preferably oleoyl sarcosine octadecylamine.

The synthetic antirust agent concentrated solution provided by the invention is supplemented to 100 parts by weight by neopentyl polyol ester; the neopentyl polyol ester is preferably pentaerythritol ester and/or trimethylolpropane ester; the pentaerythritol ester is preferably the pentaerythritol ester of a mixed acid of C4-C10.

According to the present invention, specifically, the synthetic rust inhibitor concentrate includes:

more specifically, the synthetic rust inhibitor concentrate includes:

or comprises the following steps:

or comprises the following steps:

the low-acid-value high-efficiency ashless antirust agent composition is selected and matched with other auxiliary agents to form the antirust agent concentrated solution, and the addition amount of the concentrated solution can be adjusted according to the rigor degree of the engine sealing condition; and the antirust agent compositions have good synergistic effect, can exert antirust effect to a greater extent, can provide effective protection for bearings, gear boxes and other parts of aircraft engines under severe conditions such as humidity, high temperature and the like, wherein nitrogen in oleoyl sarcosine and amine salts thereof can interact with free d-rail metal, so that adsorption of antirust agent molecules on the metal surface is facilitated, long-chain alkenyl imidazoline salt can generate synergistic effect with oleoyl sarcosine, a reaction product of epoxypropane and long-chain alkenyl succinic anhydride can provide damp-heat resistance in a high-temperature environment, polypropylene glycol can play a role in regulating the kinematic viscosity of an antirust agent concentrated solution, and heavy naphthenic base oil can dissolve the antirust agent and other auxiliary agents to a greater extent, so that the stability of an antirust agent concentrated liquid system is ensured.

The invention also provides a preparation method of the synthetic antirust agent concentrated solution, which comprises the following steps: mixing polypropylene glycol, hydrotreated heavy naphthenic base oil, tricresyl phosphate, an antioxidant, a reaction product of propylene oxide and long-chain alkenyl succinic anhydride, long-chain alkenyl imidazoline salt, oleoyl sarcosine and/or amine salt thereof and neopentyl polyol ester, and heating to dissolve to obtain the synthetic antirust agent concentrated solution.

Wherein, the contents and types of the polypropylene glycol, the hydrotreated heavy naphthenic base oil, the tricresyl phosphate, the antioxidant, the reaction product of the propylene oxide and the long-chain alkenyl succinic anhydride, the long-chain alkenyl imidazoline salt, the oleoyl sarcosine and/or the amine salt thereof and the neopentyl polyol ester are the same as the above, and are not described again.

In the present invention, the hydrotreated heavy naphthenic oil is preferably prepared according to the following process: two-stage series full hydrogenation process of hydrotreating/dewaxing-hydrogenating post-refining is used as material. In the first section, non-noble metal sulfurizing catalyst is used to perform demetallization, desulfurization, denitrogenation, dearomatization and dewaxing reactions in hydrogen environment. And in the second stage, noble metal catalyst is used, and the reaction product in the first stage is further hydrofined in hydrogen environment, preferably hydrocarbon in the range of C20-C50, and the product is finished oil of at least 19cSt (40 ℃).

The reaction product of propylene oxide and long chain alkenyl succinic anhydride is preferably prepared according to the following method: adding zinc glutarate and long-chain alkenyl succinic anhydride into a reactor, vacuumizing, then adding a mixture of epoxypropane and toluene, magnetically stirring at 60-100 ℃ for reacting for 5-40 hours, cooling to room temperature, taking out a viscous compound in the reactor, dissolving the polymer with chloroform, washing with water for several times, settling with n-hexane, and repeating for 2-3 times to obtain a product; wherein the mass ratio of the long-chain alkenyl succinic anhydride to the propylene oxide is preferably 1: (1-5), more preferably 1: (2-4), and more preferably 1: 3; the mass of the zinc glutarate is preferably 1% to 5%, more preferably 2% to 4%, still more preferably 2% to 3%, and most preferably 2.5% of the mass of the long-chain alkenyl succinic anhydride.

Mixing and heating the raw materials to obtain a synthetic antirust agent concentrated solution; the heating temperature is preferably 60 ℃ to 80 ℃.

The invention also provides application of the synthetic antirust agent concentrated solution in sealing and rust prevention of turbine engines and/or helicopter transmission systems.

The synthetic antirust agent concentrated solution provided by the invention has good compatibility with the existing aircraft engine lubricating oil.

In order to further illustrate the present invention, the following will describe in detail a synthetic rust inhibitor concentrate, its preparation method and application in combination with the examples.

The reagents used in the following examples are all commercially available.

Example 1

1 part by weight of polypropylene glycol (molecular weight 2000), 5 parts by weight of hydrotreated heavy naphthenic oil (heavy hydrogenated naphthenic oil of Alfa Chemistry), 2 parts by weight of tricresyl phosphate, 0.1 part by weight of N-phenyl alpha naphthylamine, 8 parts by weight of a reaction product of propylene oxide and heptadecenyl succinic anhydride (hydroxyalkylcarboxylate provided by Amadis Chemical), 0.2 part by weight of 1-aminoethyl-2 (heptadecenyl) imidazoline, 4 parts by weight of oleoyl sarcosine, and the balance of neopentyl polyol ester (pentaerythritol ester of mixed acid C4-C10) were mixed, and the mixture was heated to 60 ℃ until completely dissolved to form an amber concentrate, i.e., a synthetic rust inhibitor concentrate. The acid value of the resulting concentrate was determined to be 30 mgKOH/g.

The synthetic antirust agent concentrated solution obtained in the example 1 is subjected to a corrosion performance test by using GB/T2361, and is added into pentaerythritol ester of a C4-C10 mixed acid in a proportion of 3% for testing, and a steel sheet is bright and rustless after 168 hours.

The synthetic antirust agent concentrated solution obtained in the example 1 is added into pentaerythritol mixed acid C4-C10 in a proportion of 3% by adopting MIL-PRF-23699G appendix A for testing, and a bearing raceway is bright and rustless for 48 hours.

Example 2

1 part by weight of polypropylene glycol (molecular weight 2000), 5 parts by weight of hydrotreated heavy naphthenic oil (heavy hydrogenated naphthenic oil of Alfa Chemistry), 2 parts by weight of tricresyl phosphate, 0.1 part by weight of N-phenyl alpha naphthylamine, 8 parts by weight of a reaction product of propylene oxide and heptadecenyl succinic anhydride (hydroxyalkylcarboxylate provided by Amadis Chemical), 0.2 part by weight of 1-aminoethyl-2 (heptadecenyl) imidazoline, 2 parts by weight of oleoyl sarcosine, and the balance of neopentyl polyol ester (pentaerythritol ester of a mixed acid of C4-C10) were mixed, and the mixture was heated to 60 ℃ until completely dissolved to form an amber concentrate, i.e., a synthetic rust inhibitor concentrate. The acid value of the resulting concentrate was found to be 24 mgKOH/g.

The synthetic antirust agent concentrated solution obtained in the example 1 is subjected to a corrosion performance test by using GB/T2361, the synthetic antirust agent concentrated solution is added into pentaerythritol mixed acid of C4-C10 in a proportion of 3% for a test, and 2-3 needle-shaped rust points appear on the steel sheet after 168 hours.

The synthetic antirust agent concentrated solution obtained in the example 1 is added into pentaerythritol mixed acid C4-C10 in a proportion of 3% by adopting MIL-PRF-23699G appendix A for testing, and 1-2 needle-shaped rust points appear on a bearing raceway within 48 hours.

Example 3

0.5 parts by weight of polypropylene glycol (molecular weight 2000), 5 parts by weight of hydrotreated heavy naphthenic oil (heavy hydrogenated naphthenic oil of Alfa Chemistry), 2 parts by weight of tricresyl phosphate, 0.1 part by weight of N-phenyl alpha naphthylamine, 10 parts by weight of a reaction product of propylene oxide and heptadecenyl succinic anhydride (hydroxyalkylcarboxylate supplied by Amadis Chemical), 0.2 part by weight of 1-aminoethyl-2 (heptadecenyl) imidazoline dodecenyl succinate, 4 parts by weight of oleoylsarcosine, and the balance neopentyl polyol ester (pentaerythritol ester of mixed acid C4-C10) were mixed, and the mixture was heated to 60 to 80 ℃ until completely dissolved to form an amber concentrate, i.e., a synthetic rust inhibitor concentrate. The acid value of the obtained concentrated solution was determined to be 30mgKOH/g

The synthetic antirust agent concentrated solution obtained in the example 1 is subjected to a corrosion performance test by using GB/T2361, is added into pentaerythritol ester of a C4-C10 mixed acid in a proportion of 3% for testing, and a steel sheet is bright and rustless after 168 hours.

The synthetic antirust agent concentrated solution obtained in the example 1 is added into pentaerythritol mixed acid C4-C10 in a proportion of 3% by adopting MIL-PRF-23699G appendix A for testing, and a bearing raceway is bright and rustless for 48 hours.

Example 4

0.5 part by weight of polypropylene glycol (molecular weight 2000), 5 parts by weight of hydrotreated heavy naphthenic oil (heavy hydrogenated naphthenic oil of Alfa Chemistry), 2 parts by weight of tricresyl phosphate; 0.1 part by weight of N-phenyl alpha naphthylamine; 10 parts by weight of a reaction product of propylene oxide and heptadecenyl succinic anhydride (hydroxyalkylcarboxylate supplied by Amadis Chemical company), 0.2 part by weight of 1-aminoethyl-2 (heptadecenyl) imidazoline dodecenyl succinate, 4 parts by weight of oleoyl sarcosine octadecylamine, and the balance neopentyl polyol ester (pentaerythritol ester mixed with C4-C10) were mixed, and the mixture was heated to 60 ℃ to 80 ℃ until completely dissolved to form an amber concentrated solution, which was a synthetic antirust concentrated solution. The acid value of the obtained concentrated solution was found to be 12mgKOH/g

The synthetic antirust agent concentrated solution obtained in the example 1 is subjected to a corrosion performance test by using GB/T2361, is added into pentaerythritol ester of a C4-C10 mixed acid in a proportion of 3% for testing, and a steel sheet is bright and rustless after 168 hours.

The synthetic antirust agent concentrated solution obtained in the example 1 is added into pentaerythritol mixed acid C4-C10 in a proportion of 3% by adopting MIL-PRF-23699G appendix A for testing, and a bearing raceway is bright and rustless for 48 hours.

Comparative example 1

1 part by weight of polypropylene glycol (molecular weight 2000), 5 parts by weight of hydrotreated heavy naphthenic oil (heavy hydrogenated naphthenic oil of Alfa Chemistry), 2 parts by weight of tricresyl phosphate, 0.1 part by weight of N-phenyl alpha naphthylamine, 8 parts by weight of a reaction product of propylene oxide and heptadecenyl succinic anhydride (hydroxyalkylcarboxylate provided by Amadis Chemical), 0.2 part by weight of 1-aminoethyl-2 (heptadecenyl) imidazoline, and the balance of neopentyl polyol ester (pentaerythritol mixed acid ester of C4 to C10) were mixed, and the mixture was heated to 60 ℃ until completely dissolved to form an amber concentrate, i.e., a synthetic rust inhibitor concentrate. The acid value of the obtained concentrated solution was found to be 15 mgKOH/g.

The synthetic antirust agent concentrated solution obtained in the example 1 is subjected to a corrosion performance test by using GB/T2361, is added into pentaerythritol mixed acid C4-C10 in a proportion of 3% for a test, and a steel sheet has partial rusty spots after 168 hours.

The synthetic antirust agent concentrated solution obtained in the example 1 is added into pentaerythritol mixed acid C4-C10 in a proportion of 3% by adopting MIL-PRF-23699G appendix A for testing, and a small amount of rust points appear on a bearing raceway within 48 hours.