CN111254000B

CN111254000B - Environment-friendly barium-free thin-layer anti-rust oil and preparation method and application thereof

Info

Publication number: CN111254000B
Application number: CN202010148919.0A
Authority: CN
Inventors: 武小满; 边苗苗; 张丽纳; 孙颖; 郭丽丽; 陈新华
Original assignee: Xuchang University
Current assignee: Xuchang University
Priority date: 2020-03-05
Filing date: 2020-03-05
Publication date: 2022-07-15
Anticipated expiration: 2040-03-05
Also published as: CN111254000A

Abstract

The invention provides environment-friendly barium-free thin-layer anti-rust oil as well as a preparation method and application thereof, wherein the environment-friendly barium-free thin-layer anti-rust oil comprises the following components in parts by weight of 100 parts by weight: 5.5-15 parts of antirust agent, 2-9 parts of solvent, 20-40 parts of cosolvent, 0.5-2 parts of antioxidant, 0.5-2 parts of film-forming agent and the balance of base oil; the antirust agent is a composite antirust agent of petroleum sodium sulfonate, dodecenyl succinic acid and sebacic acid, wherein the weight ratio of the petroleum sodium sulfonate, the dodecenyl succinic acid and the sebacic acid is (4-10): (1-2.5): (0.5-2.5). The environment-friendly barium-free thin-layer anti-rust oil disclosed by the invention does not contain heavy metal barium, is low in viscosity, stable in performance and excellent in damp-heat and salt mist resistance, and an oil film reaches a thin layer or even an ultrathin film.

Description

Environment-friendly barium-free thin-layer anti-rust oil and preparation method and application thereof

Technical Field

The invention belongs to the technical field of rust prevention, and particularly relates to environment-friendly barium-free thin-layer rust-preventative oil as well as a preparation method and application thereof.

Background

Metal is the most important structural material in modern mechanical industry, national defense industry, petroleum industry and other departments, but is easily deteriorated or damaged by the chemical and electrochemical actions of external environment or medium, wherein, corrosion is the most common metal corrosion form, and the performance and commercial value of metal products and mechanical equipment are greatly damaged by surface rust, even serious accidents are caused. The investigation result shows that: economic loss of all countries in the world caused by metal corrosion accounts for 2-4% of the total production value of the countries, which is far more than the average loss caused by disasters such as fire, flood, wind, earthquake and the like every year, and indirect loss caused by the disasters is more remarkable and difficult to estimate. Therefore, people have long searched for corrosion-resistant and rust-proof roads, and the selection of rust-proof oil for protecting metal products is one of the methods commonly used at present.

The barium sulfonate antirust agent has excellent antirust performance, but barium is heavy metal, has an enrichment effect and is difficult to degrade, and antirust oil containing barium salt can cause heavy metal pollution when being discharged in the environment for a long time. Along with the social progress and the enhancement of environmental awareness of people, the harmlessness and environmental protection call for the anti-rust oil is higher and higher, and the existence of barium element in the anti-rust oil is already clearly regulated in the United states and countries of European Union, so that the metal anti-rust oil with safety and no toxicity is the development trend of the anti-rust oil in the future.

The oil film of common oil products is usually more than 20 mu m, and the oil film not only is greasy and sticky to hands, but also influences the appearance of the oil film and limits the application range of the oil products when in use. The thin layer and even ultra-thin film (the thickness of the oil film is less than 5 mu m) of the antirust oil can reduce the defects to the minimum degree, so that the oil film is more beautiful and the oil consumption is more saved. Further, in the case where the use condition is satisfied, the viscosity of the rust preventive oil should be reduced as much as possible. The low viscosity is easy to coat, and the oil film thickness can be effectively reduced, so that the purposes of saving and reducing loss can be achieved.

Disclosure of Invention

In view of the above, the invention aims to provide an environment-friendly barium-free thin-layer anti-rust oil, which overcomes the defects of the prior art, does not contain heavy metal barium, has low viscosity, has an oil film reaching a thin layer or even an ultrathin film, has stable performance, and has excellent damp-heat and salt mist resistance.

In order to achieve the purpose, the technical scheme of the invention is realized as follows:

an environment-friendly barium-free thin-layer anti-rust oil comprises the following components in parts by weight of 100 parts by weight: 5.5-15 parts of antirust agent, 2-9 parts of solvent, 20-40 parts of cosolvent, 0.5-2 parts of antioxidant, 0.5-2 parts of film-forming agent and the balance of base oil;

the antirust agent is a composite antirust agent of petroleum sodium sulfonate, dodecenyl succinic acid and sebacic acid, wherein the weight ratio of the petroleum sodium sulfonate, the dodecenyl succinic acid and the sebacic acid is (4-10): (1-2.5): (0.5-2.5).

Preferably, the solvent is dimethyl sulfoxide.

Preferably, the cosolvent is n-butanol.

Preferably, the antioxidant is benzotriazole or/and span-80.

Preferably, the film forming agent is natural rosin or/and vaseline.

Preferably, the base oil is a mineral oil having 9 to 16 carbon atoms.

The invention also aims to provide a preparation method of the environment-friendly barium-free thin-layer anti-rust oil, so as to prepare the environment-friendly barium-free thin-layer anti-rust oil.

a preparation method of environment-friendly barium-free thin-layer anti-rust oil comprises the following steps:

(a) mixing the petroleum sodium sulfonate and the dodecenylsuccinic acid according to the formula ratio, heating to 35-40 ℃, stirring to a completely mutual soluble transparent state to obtain a reddish brown compound A, and naturally cooling to room temperature;

(b) adding the compound A into the base oil according to the formula amount, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B;

(c) adding the sebacic acid, the antioxidant and the film forming agent into the solvent according to the formula amount, and stirring at room temperature until the sebacic acid, the antioxidant and the film forming agent are completely dissolved to obtain a yellow solution C;

(d) and (3) after the solution C is added into the mixture B, the cosolvent with the formula amount is rapidly and gradually added under stirring to obtain the clear and transparent environment-friendly barium-free thin-layer antirust oil.

It should be noted that, because both sodium petroleum sulfonate and dodecenylsuccinic acid are viscous, the faster the stirring speed during the mixing process, the faster the stirring, the faster the mixing.

The invention also relates to application of the environment-friendly barium-free thin-layer anti-rust oil in thin-layer anti-rust treatment of bearings and mechanical parts, and when the environment-friendly barium-free thin-layer anti-rust oil is used for the anti-rust treatment of the bearings and the mechanical parts in the marine transportation process, the environment-friendly barium-free thin-layer anti-rust oil can meet the requirement of non-rusting and can also meet the requirement of outsourcing traders on the thickness of an oil film.

Compared with the prior art, the environment-friendly barium-free thin-layer anti-rust oil disclosed by the invention has the following advantages:

(1) the oil-soluble antirust agent without heavy metals such as barium and lead is adopted, so that the antirust agent is environment-friendly; the base oil does not contain harmful substances such as aromatic hydrocarbon and the like.

(2) The antirust oil has low viscosity, the thickness of the oil film reaches a thin layer or even an ultra-thin layer, the drying time is short, the salt spray resistance effect is excellent, the cleaning is easy, and the antirust oil is environment-friendly and economical.

The preparation method of the environment-friendly barium-free thin-layer anti-rust oil has the following advantages:

(1) the sebacic acid solid, the antioxidant (benzotriazole or/and span-80) solid and the film forming agent (natural rosin or/and vaseline) solid which are difficult to dissolve in the base oil are firstly dissolved in a dimethyl sulfoxide solvent, so that the dissolving process of the sebacic acid, the antioxidant (benzotriazole or/and span-80) and the film forming agent (natural rosin or/and vaseline) is simplified and accelerated, and the weight parts of the sebacic acid, the antioxidant (benzotriazole or/and span-80) and the film forming agent (natural rosin or/and vaseline) in the dimethyl sulfoxide solvent are very high in solubility, so that the weight parts of the sebacic acid, the antioxidant (benzotriazole or/and span-80) and the film forming agent (natural rosin or/and vaseline) in the antirust oil can be conveniently adjusted.

(2) When the solution obtained in the step (1) is further compounded with oil-soluble petroleum sodium sulfonate and dodecenylsuccinic acid in base oil, the polarity of the solvent dimethyl sulfoxide is high, the polarity of the base oil is low, and the two are easy to separate. By adding cosolvent n-butyl alcohol with synergistic effect, the rust preventive oil with characteristics of clarity, transparency, stability and no layering can be obtained.

Drawings

FIG. 1 is a diagram illustrating the clear and transparent state exhibited by the stabilized products obtained in examples 1-4 and comparative example 2;

FIG. 2 is a schematic illustration of the hazy and opaque state of the unstable product obtained in comparative example 1;

FIG. 3 is an exemplary graph of the delamination state of the unstable products obtained in comparative example 1 and comparative example 3.

Detailed Description

Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are all conventional methods unless otherwise specified.

The present invention will be described in detail with reference to examples.

The unit "part" of each component referred to in the following examples and comparative examples means "part by weight". Wherein "room temperature" means a temperature between "20-27 ℃. In all examples and comparative examples, liquid paraffin, which is a mixture of refined liquid hydrocarbons obtained from petroleum, mainly composed of normal paraffins of C9 to C16, was used as the base oil.

Example 1

Mixing 5 parts of petroleum sodium sulfonate and 1 part of dodecenylsuccinic acid, heating to 35 ℃, stirring to a transparent state of complete mutual solubility to obtain a reddish brown compound A, and naturally cooling to room temperature. And adding the compound A into 50 parts of base oil, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B. Adding 1 part of sebacic acid, 1 part of benzotriazole and 1 part of natural rosin into 4 parts of dimethyl sulfoxide, and stirring at room temperature until the materials are completely dissolved to obtain a yellow solution C. After addition of solution C to mixture B, 37 parts of solution C are added rapidly with stirring

N-butyl alcohol to obtain bright yellow transparent liquid.

Example 2

Mixing 7 parts of petroleum sodium sulfonate and 1 part of dodecenylsuccinic acid, heating to 37 ℃, stirring to a transparent state of complete mutual solubility to obtain a reddish brown compound A, and naturally cooling to room temperature. And adding the compound A into 55 parts of base oil, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B. Adding 1 part of sebacic acid, 1 part of benzotriazole and 1 part of natural rosin into 4 parts of dimethyl sulfoxide, and stirring at room temperature until the materials are completely dissolved to obtain a yellow solution C. After addition of solution C to mixture B, 30 parts of solution C are added rapidly with stirring

N-butanol to obtain bright yellow transparent liquid.

Example 3

Mixing 6 parts of petroleum sodium sulfonate and 1 part of dodecenylsuccinic acid, heating to 40 ℃, stirring to a transparent state of complete mutual solubility to obtain a reddish brown compound A, and naturally cooling to room temperature. And adding the compound A into 57 parts of base oil, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B. Adding 0.5 part of sebacic acid, 0.5 part of benzotriazole and 1.5 parts of natural rosin into 2.5 parts of dimethyl sulfoxide, and stirring at room temperature until the materials are completely dissolved to obtain a yellow solution C. After addition of solution C to mixture B, 31 parts of n-butanol were added rapidly with stirring to give a bright yellow transparent liquid.

Example 4

Mixing 6 parts of petroleum sodium sulfonate and 1.5 parts of dodecenylsuccinic acid, heating to 35 ℃, stirring to a transparent state of complete mutual solubility to obtain a reddish brown compound A, and naturally cooling to room temperature. And adding the compound A into 61 parts of base oil, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B. Adding 2 parts of sebacic acid, 0.5 part of benzotriazole and 1 part of natural rosin into 5 parts of dimethyl sulfoxide, and stirring at room temperature until the materials are completely dissolved to obtain a yellow solution C. After addition of solution C to mixture B, 23 parts of n-butanol were added rapidly with stirring to give a bright yellow transparent liquid.

Comparative example 1

Mixing 8 parts of petroleum sodium sulfonate and 1.5 parts of dodecenylsuccinic acid, heating to 35-40 ℃, stirring to a transparent state of complete mutual solubility to obtain a reddish brown compound A, and naturally cooling to room temperature. And adding the compound A into 80 parts of base oil, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B. Adding 0.5 part of sebacic acid, 0.5 part of benzotriazole and 0.5 part of natural rosin into 9 parts of dimethyl sulfoxide, and stirring at room temperature until the materials are completely dissolved to obtain a yellow solution C. And adding the solution C into the mixture B, and quickly and uniformly stirring to obtain a turbid and opaque product.

The product obtained in comparative example 1 was subjected to a damp heat test (40 ℃, 10# steel), and rust was observed after 4 hours. The product is layered after standing for 12 h. The polarity of the solvent dimethyl sulfoxide is larger, the polarity of the base oil is smaller, and the cosolvent n-butyl alcohol with a synergistic effect is not added in the comparative example 1, so that the product is unstable, is easy to delaminate and has a poor antirust effect.

Comparative example 1 also indirectly assists in demonstrating that, when the contents of each component are within the claimed range, the contents of other components are not a major factor affecting the stability of the product, i.e., n-butanol is absent, and a stable and non-stratified product cannot be obtained by varying the contents of other components.

Comparative example 2

Mixing 5 parts of petroleum sodium sulfonate and 1.5 parts of dodecenylsuccinic acid, heating to 35 ℃, stirring to a transparent state of complete mutual solubility to obtain a reddish brown compound A, and naturally cooling to room temperature. And adding the compound A into 51 parts of base oil, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B. And adding 1 part of benzotriazole and 1 part of natural rosin into 4 parts of dimethyl sulfoxide, and stirring at room temperature until the materials are completely dissolved to obtain a solution C. After addition of solution C to mixture B, 37 parts of n-butanol are added rapidly with stirring to give a bright yellow transparent liquid.

The product obtained in the comparative example 2 is subjected to a damp heat test (40 ℃, 10# steel), and a large-area rust sign appears after 8 hours. Compared with the example 1, the components and the parts by mass are the same except that the sebacic acid is not added, but the antirust effect of the product obtained in the comparative example 2 is obviously poor, which shows that the sebacic acid has an obvious synergistic effect in the composite antirust agent.

Comparative example 3

Mixing 7 parts of petroleum sodium sulfonate and 1 part of dodecenylsuccinic acid, heating to 35-40 ℃, stirring to a transparent state of complete mutual solubility to obtain a reddish brown compound A, and naturally cooling to room temperature. And adding the compound A into 66 parts of base oil, and stirring at room temperature until the mixture is uniformly mixed to obtain an orange-red transparent mixture B. Adding 2 parts of sebacic acid, 2 parts of benzotriazole and 2 parts of natural rosin into 8 parts of dimethyl sulfoxide, and stirring at room temperature until the materials are completely dissolved to obtain a solution C. After the solution C was added to the mixture B, 12 parts of n-butanol were rapidly added under stirring to obtain a yellow transparent liquid.

The product obtained in comparative example 3 was subjected to a damp heat test (40 ℃, 10# steel), and no obvious rust was observed after 72 hours, but was delaminated after standing for 8 hours. Compared with the examples 1-4, the obvious difference is that the dosage of the cosolvent n-butyl alcohol is less than 20 parts by weight, which shows that the content of the cosolvent n-butyl alcohol is a main factor influencing the stability of the product, and the cosolvent n-butyl alcohol has a synergistic effect when a sufficient amount is needed, so that the antirust oil has good stability.

The formulation compositions of the rust preventive oils in examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1.

TABLE 1 formulation composition of rust preventive oil for each comparative example and example

The environmentally friendly barium-free type thin layer rust preventive oils prepared in examples 1 to 4 were each examined according to the relevant standards, and the results are shown in Table 2. The products obtained in comparative examples 1 to 3 have poor stability, are layered after standing, and have no practical significance, so other performance tests are not carried out.

TABLE 2 results of performance test of rust preventive oil obtained in examples

The environment-friendly thin-layer antirust oil does not contain heavy metal sulfonate, does not pollute the environment in the processes of production, manufacture and use, has stable performance, thin and firm oil film, is easy to clean, and has excellent damp-heat resistance and salt mist resistance and antirust performance.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. An environment-friendly barium-free thin-layer anti-rust oil, which is characterized in that: comprises the following components with the total weight of 100 parts by weight: 5.5-15 parts of antirust agent, 2-9 parts of solvent, 20-40 parts of cosolvent, 0.5-2 parts of antioxidant, 0.5-2 parts of film-forming agent and the balance of base oil;

the antirust agent is a composite antirust agent of petroleum sodium sulfonate, dodecenyl succinic acid and sebacic acid, wherein the weight ratio of the petroleum sodium sulfonate, the dodecenyl succinic acid and the sebacic acid is (4-10): (1-2.5): (0.5-2.5);

the solvent is dimethyl sulfoxide;

the cosolvent is n-butyl alcohol;

the antioxidant is benzotriazole or/and span-80.

2. The environment-friendly barium-free thin-layer rust preventative oil as claimed in claim 1, wherein: the film forming agent is natural rosin or/and vaseline.

3. The environment-friendly barium-free thin layer rust preventive oil according to claim 1, characterized in that: the base oil is mineral oil with 9-16 carbon atoms.

4. A method for preparing the environment-friendly barium-free type thin layer rust preventive oil according to any one of claims 1 to 3, characterized by: the method comprises the following steps:

(a) mixing the petroleum sodium sulfonate and the dodecenylsuccinic acid according to the formula ratio, heating to 35-40 ℃, stirring to a completely mutual-soluble transparent state to obtain a reddish brown compound A, and naturally cooling to room temperature;

(c) adding the sebacic acid, the antioxidant and the film forming agent in the formula amount into the solvent in the formula amount, and stirring at room temperature until the sebacic acid, the antioxidant and the film forming agent are completely dissolved to obtain a yellow solution C;

(d) and after the solution C is added into the mixture B, the cosolvent with the formula amount is rapidly and gradually added into the mixture B under stirring to obtain the clear and transparent environment-friendly barium-free thin-layer antirust oil.

5. Use of the environmentally friendly barium-free type thin layer rust inhibitor according to any one of claims 1 to 3 or the method for environmentally friendly barium-free type thin layer rust preventive oil according to claim 4 for thin layer rust preventive treatment of bearings, machine parts.