阅读说明：本技术 一种防锈剂组合物 (Antirust agent composition ) 是由 李团乐 王俊明 周旭光 于 2019-02-19 设计创作，主要内容包括：本发明涉及一种防锈剂组合物,其特征在于,以总重量百分比计,由下列原料制成：基础油5％～30％、有机羧酸类防锈剂30％～90％、如式(I)所示的双子咪唑啉衍生物5％～40％,式(I)中R1、R2均为C10～C21的直连或支链烃基。本发明的防锈剂组合物油溶性好,加剂量小,防锈性能优异,酸值低,抗乳化性好,可用于调配各种类型的工业润滑油品和防锈油脂。<Image he="425" wi="700" file="DDA0001972386720000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>。(The invention relates to an antirust agent composition which is characterized by being prepared from the following raw materials in percentage by weight: 5-30% of base oil, 30-90% of organic carboxylic acid antirust agent and 5-40% of gemini imidazoline derivative shown as formula (I), wherein R1 and R2 in the formula (I) are both C10-C21 straight-chain or branched-chain alkyl. The antirust agent composition has the advantages of good oil solubility, small dosage, excellent antirust performance, low acid value and good anti-emulsifying property, and can be used for preparing various industrial lubricating oil products and antirust grease.)

1. The antirust agent composition comprises the following components in percentage by weight:

5 to 30 percent of base oil,

30 to 90 percent of organic carboxylic acid antirust agent,

5 to 40 percent of gemini imidazoline compound;

the gemini imidazoline compound is characterized in that the gemini imidazoline compound has the following structure:

wherein R is₁、R₂Independently selected from C10-C21 hydrocarbon groups.

2. The rust inhibitor composition according to claim 1, wherein said hydrocarbon group is a straight-chain alkyl group or a straight-chain alkylene group.

3. The rust inhibitor composition according to claim 2, wherein said straight chain alkyl group is selected from the group consisting of lauryl, tridecyl, pentadecyl, heptadecyl, and nonadecyl.

4. The rust inhibitor composition according to claim 2, wherein said linear alkenyl group is a decenyl group, an undecenyl group, a tridecenyl group, a tridecadienyl group, a heptadecenyl group, a heptadecadienyl group, or a cis-13-heneicosenyl group.

5. The rust inhibitor composition according to any one of claims 1 to 4, wherein the base oil is contained in an amount of 10 to 20% by mass based on the total mass of the composition.

6. The rust inhibitor composition according to any one of claims 1 to 4, wherein the content of the organic carboxylic acid-based rust inhibitor is 35 to 75% by mass of the total composition.

7. The rust inhibitor composition according to any one of claims 1 to 4, wherein the content of the gemini imidazoline corrosion inhibitor is 10% to 30% of the total mass of the composition.

8. The rust inhibitor composition according to any one of claims 1 to 4, wherein the base oil is selected from one or more of group APII, II, III, IV, V lubricant base oils.

9. The rust inhibitor composition according to any one of claims 1 to 4, wherein the base oil is one or more of APII, II, III lubricant base oils.

10. The rust inhibitor composition according to any one of claims 1 to 4, wherein the organic carboxylic acid-based rust inhibitor is selected from one or more of n-heptanoic acid, n-octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, sebacic acid, 10-undecylenic acid, undecenoic acid, lauric acid, dodecanedioic acid, dodecenoic acid, dodecenylsuccinic acid half ester, myristic acid, tetradecenoic acid, tetradecadienoic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, eicosanoic acid, erucic acid, ricinoleic acid, naphthenic acid, lanolin fatty acid.

11. Use of the rust inhibitor composition according to any one of claims 1 to 4 in industrial lubricating oils such as turbine oils, ashless hydraulic oils, and rust-inhibiting oils and fats.

Technical Field

The invention relates to an antirust agent composition, and belongs to the technical field of antirust agents.

Background

Metal corrosion not only causes loss of metal materials, but also causes greater indirect loss due to damage of metal members, which is one of the main causes of production stoppage and environmental pollution. Among various protection methods, corrosion inhibitor technology has good effect and high economic benefit, and has become one of the most important methods in corrosion prevention technology. The oil-soluble antirust agent which is most widely applied at present is an organic carboxylic acid antirust agent, but the antirust agent has high acid value and is not suitable for the working condition requiring low acid value. Meanwhile, due to the strong molecular polarity, when the lubricating oil is used in a working condition with water, the content of the organic carboxylic acid antirust agent in the oil is reduced due to the extraction effect of the water, so that the antirust capability of the lubricating oil is reduced or even disappears, equipment is corroded, and the oil change period of the oil is shortened.

In recent years, rust preventive compositions containing a gemini imidazoline derivative as a component have been frequently reported. Patent CN103289671A reports a high temperature resistant corrosion inhibitor for acidizing treatment in the process of oil and gas well development, which comprises gemini imidazoline based quaternary ammonium salt surfactant, gemini pyridine quaternary ammonium salt surfactant, mutual solvent, synergist and solvent, the antirust composition has significant performance at high temperature, and is mainly used for oil well acidizing operation.

Patent CN102020978A discloses an oil-gas well corrosion inhibitor and a preparation method thereof, wherein the corrosion inhibitor comprises a gemini imidazoline surfactant, fatty alcohol polyoxyethylene ether phosphate, a polyether demulsifier, fatty acid amide boric acid ester and a solvent. The oil and gas well corrosion inhibitor can form a firm adsorption film and a hydrophobic protective film on the surface of metal to block the transfer of charges or substances related to electrochemical reaction, has good capabilities of overcoming local corrosion and inhibiting pitting corrosion, and is mainly used for rust prevention of materials in oil and gas exploitation.

As can be seen from the above patents, all the gemini imidazolines involved in the currently reported antirust agent compositions are gemini imidazoline quaternary ammonium salts, and the gemini imidazoline quaternary ammonium salts have high surface activity and poor anti-emulsification capability, so that the formed antirust agent compositions are mainly used for aqueous emulsions. The gemini imidazoline in the antirust agent composition has a molecular structure which is not in a quaternary ammonium salt form and has no anions and cations, so that the emulsification resistance and the oil solubility of the gemini imidazoline quaternary ammonium salt are superior to those of the gemini imidazoline quaternary ammonium salt, and the formed antirust agent composition can be used for industrial lubricating oil products such as turbine oil, ashless hydraulic oil and the like and antirust oil. Further, the composition of the rust inhibitor composition of the present invention is significantly different from the above patent. In summary, this patent is significantly different from the above patents.

Disclosure of Invention

The invention aims to provide a rust inhibitor composition which has excellent rust resistance and emulsification resistance and low acid value.

The technical problem to be solved by the invention is realized by the following technical scheme:

the invention provides an antirust agent composition which comprises the following components in percentage by weight:

5 to 30 percent of base oil,

30 to 90 percent of organic carboxylic acid antirust agent,

5 to 40 percent of gemini imidazoline compound;

wherein the gemini imidazoline compound has the following structure:

wherein R is₁、R₂Independently selected from C10-C21 straight chain or branched chain alkyl.

Preferably, the present invention provides a rust inhibitor composition, wherein the hydrocarbon group is a straight-chain alkyl group or a straight-chain alkylene group.

Preferably, the invention provides the antirust agent composition, wherein the linear alkyl of the structural formula (I) is lauryl, tridecyl, pentadecyl, heptadecyl and nonadecyl.

Preferably, the antirust agent composition provided by the invention is characterized in that the linear alkenyl of the structural formula (I) is decenyl, undecenyl, tridecenyl, tridecadienyl, heptadecenyl, heptadecadienyl, cis-13-heneicosenyl.

Preferably, the content of the base oil in the antirust agent composition is 10-20% of the total mass of the composition.

Preferably, the content of the organic carboxylic acid type antirust agent is 35-75% of the total mass of the composition.

Preferably, the content of the gemini imidazoline corrosion inhibitor in the antirust agent composition provided by the invention is 10-30% of the total mass of the composition.

Preferably, the invention provides the antirust agent composition, wherein the base oil is selected from one or more of API I, II, III, IV and V lubricating oil base oils.

Preferably, the antirust agent composition provided by the invention is characterized in that the base oil is one or more of API I, II and III lubricating oil base oils.

Preferably, the rust inhibitor composition provided by the invention is characterized in that the organic carboxylic acid type rust inhibitor is selected from one or more of n-heptanoic acid, n-octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, sebacic acid, 10-undecylenic acid, undecanedioic acid, lauric acid, dodecanedioic acid, dodecenoic acid, dodecenylsuccinic acid half ester, myristic acid, tetradecenoic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, eicosanoic acid, erucic acid, ricinoleic acid, naphthenic acid and lanolin fatty acid.

The preparation method of the antirust agent composition comprises the following steps: adding various components in advance into a reactor at a certain temperature, and stirring for 1-6h until the system is uniform.

The antirust agent composition provided by the invention can be applied to industrial lubricating oil products such as turbine oil, ashless hydraulic oil and the like and antirust grease.

The present invention can be described in detail as follows:

the invention provides an antirust agent composition, which comprises the following components in percentage by weight:

5 to 30 percent of base oil;

30-90% of organic carboxylic acid antirust agent;

5 to 40 percent of gemini imidazoline compound.

The preparation method of the antirust agent composition comprises the following steps: adding various components in advance into a reactor at a certain temperature, and stirring for 1-6h until the system is uniform.

Wherein, the base oil is a viscosity regulator and a carrier, so that all functional additives are uniformly dissolved or dispersed. The invention takes one or more of APII, II, III, IV and V lubricating oil base oils as base oil, preferably one or more of APII, II and III lubricating oil base oils as base oil. The base oil accounts for 5-30% of the total weight of the antirust agent composition, and preferably accounts for 10-20%.

The organic carboxylic acid antirust agent is one or more of n-heptanoic acid, n-octanoic acid, isooctanoic acid, nonanoic acid, isononanoic acid, decanoic acid, neodecanoic acid, sebacic acid, 10-undecylenic acid, undecanedioic acid, lauric acid, dodecanedioic acid, dodecenoic acid, dodecenylsuccinic acid half ester, myristic acid, tetradecenoic acid, tetradecadienoic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, eicosanoic acid, erucic acid, ricinoleic acid, naphthenic acid and lanolin fatty acid. The organic carboxylic acid antirust agent accounts for 30-90%, preferably 35-75% of the total weight of the antirust agent composition. The molecule of the organic carboxylic acid type antirust agent has a long hydrophobic hydrocarbon chain tail part and a head part with strong affinity with the metal surface. These elongated molecules are aligned parallel to each other and perpendicular to the metal surface to form a film that is resistant to water and oxygen, thereby acting as a barrier to corrosion factors.

The molecular structure of the gemini imidazoline derivative is shown as the formula (I):

r in the formula (I)₁、R₂Independently selected from C10-C21 straight-chain or branched chain, saturated or unsaturated alkyl.

The gemini imidazoline compound accounts for 5-40%, preferably 10-30% of the total weight of the antirust agent composition.

The gemini imidazoline compound is formed by connecting two hydrophilic groups, two hydrophobic groups and a spacer group, and the C ═ N double bond on the ring and the lone pair electrons on the N atom can generate covalent adsorption on the metal surface, so that the corrosion inhibitor molecules are firmly adsorbed on the metal surface to form a layer of protective film. Meanwhile, compared with an oil-based imidazoline corrosion inhibitor, the emulsifying tendency of the gemini imidazoline is weaker, and the larger rigid structure of the gemini imidazoline reduces the close arrangement of molecules at an oil-water interface, so that the emulsifying property is reduced.

Preferably, the hydrocarbyl group of formula (I) is a straight chain alkyl or alkenyl group

More preferably, the straight-chain alkyl group of the structural formula (I) is lauryl, tridecyl, pentadecyl, heptadecyl, nonadecyl.

More preferably, the linear alkenyl group of formula (I) is decenyl, undecenyl, tridecenyl, tridecadienyl, heptadecenyl, heptadecadienyl, cis-13-heneicosenyl.

The gemini imidazoline compound provided by the invention is prepared by reacting triethylene tetramine with organic acid, and the preparation method comprises the following steps:

(1) adding a catalyst into a certain amount of triethylene tetramine, and heating to 100-120 ℃;

(2) dropwise adding a certain amount of fatty acid into the system within 20-60 min, heating to 150-190 ℃, and continuously reacting for 2-6 h;

(3) and after no byproduct is generated in the reaction system, heating to 220-300 ℃, continuing to react for 2-6 h, and after the reaction is finished, carrying out reduced pressure distillation to remove the byproduct, thus obtaining the gemini imidazoline corrosion inhibitor.

The organic acid for preparing the gemini imidazoline compound is a direct-chain or branched-chain organic acid of C11-C22, and preferably one or more of 10-undecylenic acid, lauric acid, dodecenoic acid, myristic acid, tetradecenoic acid, tetradecadienoic acid, palmitic acid, oleic acid, linoleic acid, stearic acid, eicosanoic acid and erucic acid.

The catalyst for preparing the gemini imidazoline compound is one or more of active alumina, solid acid, urea and zinc particles.

The dosage of the catalyst for preparing the gemini imidazoline compound is calculated by the total reactants of unit mass, and the mass of the catalyst accounts for 0.05-0.5% of the total amount of the reactants; the organic acid used for preparing the gemini imidazoline compound is used in an amount that the mol ratio of the triethylene tetramine to the organic acid is 1: 1.5-3, preferably 1: 1.8 to 2.5.

The invention has the following beneficial effects:

the invention provides an antirust agent composition with good oil solubility, excellent antirust performance, low acid value and good emulsification resistance, which is suitable for preparing industrial lubricating oil products such as various turbine oils and ashless hydraulic oils. Meanwhile, the antirust agent composition can also be used for preparing various types of antirust grease.

Detailed description of the invention

The present invention is further explained by the following examples, which are not intended to limit the invention in any way and all changes which do not depart from the spirit and scope of the present invention are intended to be within the scope of the present invention.

Amount of base oil

In the present invention, the amount of the base oil is not particularly limited, and is usually 5 to 30% by mass, preferably 10 to 20% by mass based on the total mass of the rust inhibitor composition. If the value is less than 5%, the dosage is too small, which causes the viscosity of the product to be too high; if the value is more than 30%, the use amount is too large, resulting in a decrease in the effective rust inhibitor content in the product, thereby lowering the rust inhibitive performance of the rust inhibitive agent composition.

Amount of organic carboxylic acid rust inhibitor

In the present invention, the amount of the organic carboxylic acid based rust inhibitor used is not particularly limited, and is usually 30 to 90% by weight, preferably 35 to 75% by weight, based on the total weight of the rust inhibitor composition. If the value is less than 30 percent, the use amount is too small, the content of the gemini imidazoline compound in the product is increased, and the production cost of the gemini imidazoline compound is higher than that of the organic carboxylic acid antirust agent, so the comprehensive cost of the product is increased; if the value is more than 90%, the use amount is too large, which may result in too high acid value of the product and may adversely affect the application effect.

Use amount of gemini imidazoline compound

In the present invention, the amount of the gemini imidazoline compound used is not particularly limited, and is usually 5% to 40%, preferably 10% to 30%, of the total weight of the composition, based on the total weight of the rust inhibitor composition. If the value is less than 5 percent, the use amount is too small, so that the acid value of the product is too high, and the application effect of the product is influenced; if the amount is more than 40%, the amount is too large, and the production cost of the gemini imidazoline compound is higher than that of the organic carboxylic acid type rust inhibitor, so that the comprehensive cost of the product is increased.

The measurements relating to the acid number in the following examples were measured using GB/T4945; the liquid phase corrosion test adopts GB/T11143 to measure; the demulsification performance test is measured by GB/T7305-2003.