CN113817527A - Barium-free type cold-rolled steel plate anti-rust oil and preparation method thereof - Google Patents

Abstract

The invention belongs to the technical field of anti-rust oil, and particularly relates to barium-free type anti-rust oil for cold-rolled steel plates and a preparation method thereof, wherein the barium-free type anti-rust oil comprises the following components in percentage by mass: 10-25% of calcium sulfonate, 1-4% of oxidized ester, 0.1-0.6% of lauric acid, 0.1-0.6% of diethanolamine, 2-6% of antirust agent, 1-3% of surfactant, 1-3% of soap, 0.1-1% of antioxidant and the balance of base oil; the oxidation ester and the lauryl diethanol amine are mixed and added into a base oil system, so that the integral salt spray time of the antirust oil is effectively prolonged, an amide bond in the lauryl diethanol amine can form a compact adsorption layer on the metal surface, and the adhesion performance of the oxidation ester is utilized to firmly fix the base system on the metal surface, so that corrosion media are effectively prevented from invading the metal surface, and the antirust effect is superior to that of barium antirust oil.

Description

Barium-free type cold-rolled steel plate anti-rust oil and preparation method thereof

Technical Field

The invention relates to the technical field of anti-rust oil, in particular to barium-free type cold-rolled steel plate anti-rust oil and a preparation method thereof.

Background

The rust preventive oil is an oil solvent with a rust preventive function. Consists of oil soluble corrosion inhibitor, base oil, auxiliary additive, etc. The rust removing oil can be classified into fingerprint removing type rust preventing oil, water diluting type rust preventing oil, solvent diluting type rust preventing oil, dual-purpose oil for rust preventing and lubricating, sealing type rust preventing oil, replacing type rust preventing oil, thin-layer oil, rust preventing grease, gas phase rust preventing oil and the like according to performance and application, in the aspect of rust prevention of steel plates, most of the currently used rust-preventing oil is a barium sulfonate series rust-preventing oil product, the rust-preventing performance of oil-soluble sulfonate is enhanced along with the increase of the cationic ionic radius of the oil-soluble sulfonate, the ionic radius is in the order of barium, calcium, magnesium and sodium, so the oil soluble barium sulfonate has the best antirust performance, excellent salt mist resistance and heat and humidity resistance, can be used for preparing various types of rust-proof oil products such as medium and short-term rust-proof oil, sealed rust-proof oil, solvent type hard film rust-proof oil, soft film rust-proof oil and the like with different dosages, and almost more than 90 percent of the rust-proof oil products use oil-soluble barium sulfonate as a main rust-proof agent. Although the oil-soluble barium salt is non-toxic, the oil-soluble barium salt is scattered in the natural environment and can be decomposed into the toxic soluble barium salt, which has serious harm to the environment and human bodies. Because the toxicity of barium salt is determined by its solubility, the insoluble barium sulfate is nontoxic and can be used for medical barium meal radiography, but soluble barium salts which are easily dissolved in water, such as barium chloride, barium nitrate, barium chlorate, etc., are toxic, for example, barium chloride belongs to B-grade inorganic highly toxic articles. Therefore, the antirust oil containing barium has potential serious harm to the environment and human body. Along with the enhancement of environmental awareness, the use of barium sulfonate is increasingly limited, and the existing barium-free antirust oil has poor antirust effect on cold-rolled plates and has a certain difference with barium type antirust oil.

Disclosure of Invention

The invention aims to provide barium-free type cold-rolled steel sheet anti-rust oil and a preparation method thereof so as to solve the technical problems mentioned in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: the barium-free type cold-rolled steel plate antirust oil comprises the following components in percentage by mass: 10 to 25 percent of calcium sulfonate, 1 to 4 percent of oxidized ester, 0.1 to 0.6 percent of lauric acid, 0.1 to 0.6 percent of diethanolamine, 2 to 6 percent of antirust agent, 1 to 3 percent of surfactant, 1 to 3 percent of soap, 0.1 to 1 percent of antioxidant and the balance of base oil.

Preferably, the barium-free type cold-rolled steel sheet anti-rust oil comprises the following components in percentage by mass: 12 to 22 percent of calcium sulfonate, 1.5 to 3 percent of oxidized ester, 0.2 to 0.5 percent of lauric acid, 0.2 to 0.5 percent of diethanolamine, 3 to 5 percent of antirust agent, 2 percent of surfactant, 2 percent of soap, 0.6 percent of antioxidant and the balance of base oil.

Preferably, the barium-free type cold-rolled steel sheet anti-rust oil comprises the following components in percentage by mass: 15% of calcium sulfonate, 2% of oxidized ester, 0.4% of lauric acid, 0.4% of diethanolamine, 4% of antirust agent, 2% of surfactant, 2% of soap, 0.6% of antioxidant and the balance of base oil.

Preferably, the calcium sulfonate is high-base-number calcium sulfonate.

Preferably, the surfactant is a polyoxyethylene fatty alcohol ether.

Preferably, the soap is one or a mixture of more than two of calcium soap of petroleum sulfonic acid, sodium soap of petroleum sulfonic acid or potassium soap of petroleum sulfonic acid.

A preparation method of barium-free cold-rolled steel sheet anti-rust oil comprises the following steps:

step 1: carrying out condensation reaction on lauric acid and diethanol amine under the protection of nitrogen at the reaction temperature of 70-80 ℃ to generate lauroyl diethanol amine for later use;

step 2: putting the lauroyl diethanol amine prepared in the step 1 and the oxidation ester into a reaction kettle, mixing, and stirring the mixture at the stirring speed of 300r/min for 15-20 min;

and step 3: adding base oil, calcium sulfonate, a surfactant and an antirust agent into a reaction kettle, heating to 100-.

The invention has the beneficial effects that: according to the barium-free type anti-rust oil for the cold-rolled steel plate, the oxidized ester and the lauroyl diethanol amine are mixed and added into the base oil system, so that the overall salt spray time of the anti-rust oil is effectively prolonged, a compact adsorption layer can be formed on the metal surface by amido bonds in the lauroyl diethanol amine, the base system is firmly fixed on the metal surface by utilizing the adhesion performance of the oxidized ester, the corrosion medium is effectively prevented from invading the metal surface, and the anti-rust effect is better than that of barium type anti-rust oil.

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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.

Example 1:

step 1: carrying out condensation reaction on 0.1% of lauric acid and 0.1% of diethanol amine under the protection of nitrogen, wherein the reaction temperature is 70 ℃, and lauroyl diethanol amine is generated for later use;

step 2: putting the lauroyl diethanol amine prepared in the step 1 and 1% of the oxidation ester into a reaction kettle, and stirring the mixture at the stirring speed of 300r/min for 15 min;

and step 3: adding 84.7% of base oil, 10% of calcium sulfonate, 1% of surfactant and 2% of antirust agent into a reaction kettle, heating to 100 ℃, stirring for 20min, continuously adding 1% of soap into the reaction kettle, keeping the temperature at 100 ℃, continuously stirring for 30min, cooling to 40 ℃, adding 0.1% of antioxidant, continuously stirring for 30min, and filtering to obtain the barium-free cold-rolled steel sheet antirust oil.

Wherein: base oil: 150SN base oil;

calcium sulfonate: high base number calcium sulfonate;

surfactant (b): polyoxyethylene fatty alcohol ethers

Antirust agent: polyethylene wax

Soaps: calcium soap of petroleum sulfonic acid

Antioxidant: phenolic antioxidants

Oxidized ester R23 is from Rickett Luck, Guangzhou, a highly carbon oxidized fatty acid ester

Example 2:

step 1: carrying out condensation reaction on 0.2% of lauric acid and 0.2% of diethanol amine under the protection of nitrogen, wherein the reaction temperature is 75 ℃, and lauroyl diethanol amine is generated for later use;

step 2: putting the lauroyl diethanol amine prepared in the step 1 and 1.5 percent of oxidation ester into a reaction kettle, mixing, and stirring the mixture at the stirring speed of 300r/min for 15 min;

and step 3: adding 78.5% of base oil, 12% of calcium sulfonate, 2% of surfactant and 3% of antirust agent into a reaction kettle, heating to 110 ℃, stirring for 20min, continuing to add 2% of soap into the reaction kettle, keeping the temperature at 110 ℃, continuing to stir for 30min, cooling to 50 ℃, adding 0.6% of antioxidant, continuing to stir for 30min, and filtering to obtain the barium-free cold-rolled steel sheet antirust oil.

Wherein: base oil: 150SN base oil;

calcium sulfonate: high base number calcium sulfonate;

surfactant (b): polyoxyethylene fatty alcohol ethers

Antirust agent: polyethylene wax

Soaps: calcium soap of petroleum sulfonic acid

Antioxidant: phenolic antioxidants

Oxidized ester R23 is from Rickett Luck, Guangzhou, a highly carbon oxidized fatty acid ester

Example 3:

step 1: carrying out condensation reaction on 0.4% of lauric acid and 0.4% of diethanol amine under the protection of nitrogen, wherein the reaction temperature is 80 ℃, and lauroyl diethanol amine is generated for later use;

step 2: putting the lauroyl diethanol amine prepared in the step 1 and 2% of oxidation ester into a reaction kettle, mixing, and stirring the mixture at the stirring speed of 300r/min for 20 min;

and step 3: adding 73.6% of base oil, 15% of calcium sulfonate, 2% of surfactant and 4% of antirust agent into a reaction kettle, heating to 120 ℃, stirring for 20min, continuing to add 2% of soap into the reaction kettle, keeping the temperature at 120 ℃, continuing to stir for 30min, cooling to 60 ℃, adding 0.6% of antioxidant, continuing to stir for 30min, and filtering to obtain the barium-free cold-rolled steel sheet antirust oil.

Wherein: base oil: 150SN base oil;

calcium sulfonate: high base number calcium sulfonate;

surfactant (b): polyoxyethylene fatty alcohol ethers

Antirust agent: polyethylene wax

Soaps: calcium soap of petroleum sulfonic acid

Antioxidant: phenolic antioxidants

Oxidized ester R23 is from Rickett Luck, Guangzhou, a highly carbon oxidized fatty acid ester

Example 4:

step 1: carrying out condensation reaction on 0.5% of lauric acid and 0.5% of diethanol amine under the protection of nitrogen, wherein the reaction temperature is 75 ℃, and lauroyl diethanol amine is generated for later use;

step 2: putting the lauroyl diethanol amine prepared in the step 1 and 3% of the oxidation ester into a reaction kettle, and stirring the mixture at the stirring speed of 300r/min for 20 min;

and step 3: adding 64.4% of base oil, 22% of calcium sulfonate, 2% of surfactant and 5% of antirust agent into a reaction kettle, heating to 110 ℃, stirring for 20min, continuing to add 2% of soap into the reaction kettle, keeping at 120 ℃, continuing to stir for 30min, cooling to 50 ℃, adding 0.6% of antioxidant, continuing to stir for 30min, and filtering to obtain the barium-free cold-rolled steel sheet antirust oil.

Wherein: base oil: 150SN base oil;

calcium sulfonate: high base number calcium sulfonate;

surfactant (b): polyoxyethylene fatty alcohol ethers

Antirust agent: polyethylene wax

Soaps: calcium soap of petroleum sulfonic acid

Antioxidant: phenolic antioxidants

Oxidized ester R23 is from Rickett Luck, Guangzhou, a highly carbon oxidized fatty acid ester

Example 5:

step 1: carrying out condensation reaction on 0.6% of lauric acid and 0.6% of diethanol amine under the protection of nitrogen, wherein the reaction temperature is 80 ℃, and lauroyl diethanol amine is generated for later use;

step 2: putting the lauroyl diethanol amine prepared in the step 1 and 4% of the oxidation ester into a reaction kettle, and stirring the mixture at the stirring speed of 300r/min for 20 min;

and step 3: adding 56.8% of base oil, 25% of calcium sulfonate, 3% of surfactant and 6% of antirust agent into a reaction kettle, heating to 120 ℃, stirring for 20min, continuing to add 3% of soap into the reaction kettle, keeping the temperature at 120 ℃, continuing to stir for 30min, cooling to 60 ℃, adding 1% of antioxidant, continuing to stir for 30min, and filtering to obtain the barium-free cold-rolled steel sheet antirust oil.

Wherein: base oil: 150SN base oil;

calcium sulfonate: high base number calcium sulfonate;

surfactant (b): polyoxyethylene fatty alcohol ethers

Antirust agent: polyethylene wax

Soaps: calcium soap of petroleum sulfonic acid

Antioxidant: phenolic antioxidants

Oxidized ester R23 is from Rickett Luck, Guangzhou, a highly carbon oxidized fatty acid ester

The barium-free type cold-rolled steel sheet rust preventive oils prepared in examples 1 to 5 were subjected to the relevant physicochemical tests, and the results were as follows:

item	Index (I)
		Appearance of antirust oil coating film	Colorless transparent oil film
Flash point (closed mouth), deg.C	195 (mean value)
		Salt spray test (10# steel plate, h)	72(A)

Note: salt spray test A grade is rust-free and bright as before, and B grade is rust-free but slightly dull

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. The barium-free type rust preventive oil for the cold-rolled steel sheet is characterized by comprising the following components in parts by weight: the composition comprises the following components in percentage by mass: 10 to 25 percent of calcium sulfonate, 1 to 4 percent of oxidized ester, 0.1 to 0.6 percent of lauric acid, 0.1 to 0.6 percent of diethanolamine, 2 to 6 percent of antirust agent, 1 to 3 percent of surfactant, 1 to 3 percent of soap, 0.1 to 1 percent of antioxidant and the balance of base oil.

2. The barium-free type rust preventive oil for cold-rolled steel sheets according to claim 1, characterized in that: the composition comprises the following components in percentage by mass: 12 to 22 percent of calcium sulfonate, 1.5 to 3 percent of oxidized ester, 0.2 to 0.5 percent of lauric acid, 0.2 to 0.5 percent of diethanolamine, 3 to 5 percent of antirust agent, 2 percent of surfactant, 2 percent of soap, 0.6 percent of antioxidant and the balance of base oil.

3. The barium-free cold-rolled steel sheet rust preventive oil according to claim 2, characterized in that: the composition comprises the following components in percentage by mass: 15% of calcium sulfonate, 2% of oxidized ester, 0.4% of lauric acid, 0.4% of diethanolamine, 4% of antirust agent, 2% of surfactant, 2% of soap, 0.6% of antioxidant and the balance of base oil.

4. The barium-free cold-rolled steel sheet rust preventive oil according to any one of claims 1 to 3, characterized in that: the calcium sulfonate is high-base-number calcium sulfonate.

5. The barium-free cold-rolled steel sheet rust preventive oil according to claim 4, characterized in that: the surfactant is polyoxyethylene fatty alcohol ether.

6. The barium-free cold-rolled steel sheet rust preventive oil according to claim 4, characterized in that: the soap is one or a mixture of more than two of calcium soap of petroleum sulfonic acid, sodium soap of petroleum sulfonic acid or potassium soap of petroleum sulfonic acid.

7. A preparation method of barium-free cold-rolled steel sheet anti-rust oil is characterized by comprising the following steps: the preparation method comprises the following steps:

step 1: carrying out condensation reaction on lauric acid and diethanol amine under the protection of nitrogen at the reaction temperature of 70-80 ℃ to generate lauroyl diethanol amine for later use;

step 2: putting the lauroyl diethanol amine prepared in the step 1 and the oxidation ester into a reaction kettle, mixing, and stirring the mixture at the stirring speed of 300r/min for 15-20 min;

and step 3: adding base oil, calcium sulfonate, a surfactant and an antirust agent into a reaction kettle, heating to 100-.