CN111944596A

CN111944596A - Antirust emulsion for workpieces

Info

Publication number: CN111944596A
Application number: CN202010895784.4A
Authority: CN
Inventors: 郑祥康
Original assignee: Individual
Current assignee: Individual
Priority date: 2020-08-31
Filing date: 2020-08-31
Publication date: 2020-11-17

Abstract

The invention discloses a workpiece antirust emulsion. The workpiece antirust emulsion is prepared from the following raw materials in percentage by weight: 12-18% of pentaerythritol tetraoleate; 0.5 to 2.5 percent of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate; 3-7% of organic boron surfactant; 3-6% of polyvinyl alcohol; 2-4% of triethanolamine; 2-5% of liquid paraffin; the balance being water. The workpiece antirust emulsion can form an effective protective film on the surface of metal, so that the workpiece is prevented from being corroded by surrounding media, and the workpiece antirust emulsion has a good antirust effect on the metal workpiece.

Description

Antirust emulsion for workpieces

Technical Field

The invention relates to the field of emulsion, in particular to antirust emulsion for workpieces.

Background

The surfactant is a substance which is added in a small amount and can cause the interface state of a solution system to change obviously. Has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution. The molecular structure of the surfactant has an amphoteric nature: one end is a hydrophilic group, and the other end is a hydrophobic group; the hydrophilic group is often a polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amino groups and salts thereof, hydroxyl, amide, ether linkages, and the like may also be used as the polar hydrophilic group; and the hydrophobic group is often a non-polar hydrocarbon chain, such as a hydrocarbon chain of 8 or more carbon atoms. The surfactant is divided into cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, compound surfactant, other surfactants and the like.

Boron is a non-active element which is non-toxic and nuisanceless and has the functions of sterilization, corrosion prevention, wear resistance and flame retardance. Therefore, the boron-containing special surfactant has the advantage that other surfactants cannot replace the boron-containing special surfactant. Research on boron-containing surfactants is of practical significance.

In the mechanical field, the work pieces are usually metal, in particular iron, and are very susceptible to rusting. Prevention of metal components is generally achieved by surface treatment, electroplating, chemicals, cathodic rust prevention, and the like. These methods are relatively complex and costly.

In the field, the work piece antirust emulsion is adopted for rust prevention, and although the cost is reduced and the operation is simpler, the antirust effect is not ideal.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to be realized by the following technical scheme:

the workpiece antirust emulsion is prepared from the following raw materials in percentage by weight:

12-18% of pentaerythritol tetraoleate;

0.5 to 2.5 percent of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

3-7% of organic boron surfactant;

3-6% of polyvinyl alcohol;

2-4% of triethanolamine;

2-5% of liquid paraffin;

the balance being water.

Preferably, the workpiece antirust emulsion is prepared from the following raw materials in percentage by weight:

13-17% of pentaerythritol tetraoleate;

1-2% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

4-6% of organic boron surfactant;

3-6% of polyvinyl alcohol;

2-4% of triethanolamine;

2-5% of liquid paraffin;

the balance being water.

The preparation method of the workpiece antirust emulsion comprises the following steps:

(1) uniformly stirring and mixing liquid paraffin, pentaerythritol tetraoleate, N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate, triethanolamine and an organic boron surfactant at 60-80 ℃ to obtain an organic mixed solution;

(2) dissolving polyvinyl alcohol in water at 85-95 ℃; cooling to 40-60 deg.C, adding the above organic mixture, stirring, and mixing.

Cooling to room temperature to obtain the workpiece antirust emulsion. When in use, the workpiece antirust emulsion is dipped, brushed or sprayed on a workpiece to obtain the workpiece antirust effect.

In the invention, pentaerythritol tetraoleate is an active ingredient, N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate is used as an oily antirust corrosion inhibitor of pentaerythritol tetraoleate, liquid paraffin is used as a cosolvent of the pentaerythritol tetraoleate and the N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate, and triethanolamine and a high-efficiency emulsifier organic boron surfactant synergistically play an emulsification role; polyvinyl alcohol as an effective binder; the raw materials have comprehensive synergistic effect and play a role in workpiece rust prevention.

Preferably, the organoboron surfactant is prepared by the following method: reacting boric acid diglyceride, tetracosanoic acid, octadecanoyl chloride and methyl arachinate at the temperature of 230 ℃ for 4-6 hours in a nitrogen environment, adjusting the pH value to 7.0-7.5 by using an aqueous solution of sodium hydroxide, and distilling water and methanol to obtain the surfactant.

Preferably, the first and second electrodes are formed of a metal,

the mass solubility of the sodium hydroxide aqueous solution is 25-35 wt%.

The mass ratio of the boric acid diglyceride to the tetracosanoic acid to the octadecanoyl chloride to the arachidic acid methyl ester is 100 (50-70) to 40-60 to 50-70.

Further, the mass ratio of the boric acid diglyceride to the tetracosanoic acid to the octadecanoyl chloride to the arachidic acid methyl ester is 100:59:53: 57.

In the invention, the organic boron surfactant is prepared by adopting a brand-new thought and process, and the brand-new raw materials are adopted, and most of the raw materials are applied for the first time. Specifically, diglycerol borate, tetracosanoic acid, octadecanoyl chloride and methyl arachidate are used as main materials for reaction, free hydroxyl contained in the diglycerol borate molecule is utilized to further react with the tetracosanoic acid, the octadecanoyl chloride and the methyl arachidate, and specifically, esterification reaction, ester exchange reaction and fatty acyl halide reaction are involved, and nitrogen is used as protective gas.

Preferably, the preparation method of the organoboron surfactant comprises the following steps: reacting boric acid diglyceride, tetracosanoic acid, octadecanoyl chloride, methyl arachinate and boron trifluoride butyl ether complex at the temperature of 210 ℃ and 230 ℃ for 4-6 hours in a nitrogen environment, adjusting the pH value to 7.0-7.5 by using an aqueous solution of sodium hydroxide, and distilling water and methanol to obtain the surfactant.

The addition amount of the boron trifluoride butyl ether complex is 0.1-0.9 wt% of the boric acid diglyceride. In the invention, boron trifluoride butyl ether complex is used as a catalyst, so that the reaction can be further improved, and the obtained product has more excellent performance.

The N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate and the organic boron surfactant can be effectively adsorbed on the surface of metal, so that the metal is prevented from contacting with a corresponding medium, and the effect of slowing down the corrosion of the metal is achieved.

The workpiece antirust emulsion can form an effective protective film on the surface of metal, so that the workpiece is prevented from being corroded by surrounding media, and the workpiece antirust emulsion has a good antirust effect on the metal workpiece.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a corrosion test chart of a workpiece antirust emulsion cast iron sheet.

FIG. 2 is a test chart of corrosion test of red copper in antirust emulsion for workpieces.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.

12-18% of pentaerythritol tetraoleate;

3-7% of organic boron surfactant;

3-6% of polyvinyl alcohol;

2-4% of triethanolamine;

2-5% of liquid paraffin;

the balance being water.

13-17% of pentaerythritol tetraoleate;

1-2% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

4-6% of organic boron surfactant;

3-6% of polyvinyl alcohol;

2-4% of triethanolamine;

2-5% of liquid paraffin;

the balance being water.

Name of raw materials	CAS number
		Pentaerythritol tetraoleate	19321-40-5
N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate	105832-38-0
		Polyvinyl alcohol	9002-89-5
Triethanolamine	102-71-6
		Liquid paraffin	8012-95-1

In a specific embodiment, polyvinyl alcohol is used

Polyvinyl alcohol 1788 type. Liquid paraffin is supplied by Haoyi petrochemical Co., Ltd, Cinjin.

A process for preparing an organoboron surfactant comprising the steps of: reacting boric acid diglyceride, tetracosanoic acid, octadecanoyl chloride and methyl arachinate at the temperature of 230 ℃ for 4-6 hours in a nitrogen environment, adjusting the pH value to 7.0-7.5 by using an aqueous solution of sodium hydroxide, and distilling water and methanol to obtain the surfactant.

Preferably, the first and second electrodes are formed of a metal,

the mass solubility of the sodium hydroxide aqueous solution is 25-35 wt%.

Preferably, the method for preparing the organoboron surfactant comprises the steps of: reacting boric acid diglyceride, tetracosanoic acid, octadecanoyl chloride, methyl arachinate and boron trifluoride butyl ether complex at the temperature of 210 ℃ and 230 ℃ for 4-6 hours in a nitrogen environment, adjusting the pH value to 7.0-7.5 by using an aqueous solution of sodium hydroxide, and distilling water and methanol to obtain the surfactant.

The addition amount of the boron trifluoride butyl ether complex is 0.1-0.9 wt% of the boric acid diglyceride.

In the invention, boron trifluoride butyl ether complex is used as a catalyst, so that the reaction can be further improved, and the obtained product has more excellent performance. In the invention, boron trifluoride butyl ether complex is used as a catalyst for esterification reaction, ester exchange reaction and fatty acyl halide reaction for the first time, and good effect is obtained.

In the specific embodiment, the boric acid diglyceride is prepared by the following method: 60g of boric acid and 180g of glycerol react for 3 hours at 140 ℃ in a nitrogen environment, and ethanol is distilled to obtain colorless transparent liquid, namely boric acid diglyceride.

The boric acid diglyceride contains active hydroxyl in molecules, and can continuously react with different functional groups to obtain different types of surfactants. Under the protection of nitrogen, boric acid diglyceride is sequentially subjected to esterification reaction and fatty acyl halide reaction with tetracosanoic acid and octadecanoyl chloride to prepare a mono-ditetradecanoate pentan acid glyceride mono octadecanoyl ester nonionic surfactant, NaOH aqueous solution is added, so that the rest boric acid diglyceride, methyl arachinate and the prepared mono-ditetran acid glyceride mono octadecanoyl ester nonionic surfactant are subjected to ester exchange reaction under an alkaline condition to obtain a novel boron spiro-structure surfactant, meanwhile, a boron trifluoride butyl ether complex is added as a catalyst, and as the alkyl molecular weight of butyl ether in the boron trifluoride butyl ether complex is large, the adhesion is not firm, the stability is poor, the boron trifluoride butyl ether complex is favorable for dissociating boron in a reaction system, so that the boron trifluoride butyl ether complex is more easily reacted with reaction substances and generates more activation centers, the reaction rate is accelerated. The novel boron spiro structure has stable covalent bond B-O, so that the boron spiro structure can exist stably, long carbon chain carboxyl is introduced to the structure for modification, the rigidity of a branched chain is enhanced, the structure is close to the boron spiro main chain, the extension degree of long chain molecules is increased, the winding degree of coils in molecules or among molecules is reduced, the trend of generating macromolecular micelles is weakened, and the novel boron spiro structure has higher surface activity and emulsifying power.

The specific reaction mechanism is as follows:

example 1

The preparation method of the organic boron surfactant comprises the following steps:

reacting boric acid diglyceride, tetracosanoic acid, octadecanoyl chloride and methyl arachinate at 220 ℃ for 5 hours in a nitrogen environment, adjusting the pH value to 7.2 by using 30 wt% of sodium hydroxide aqueous solution, and distilling water and methanol to obtain the surfactant.

The mass ratio of the boric acid diglyceride to the tetracosanoic acid to the octadecanoyl chloride to the arachidic acid methyl ester is 100:59:53: 57.

Example 2

The mass ratio of the boric acid diglyceride to the tetracosanoic acid to the octadecanoyl chloride to the arachidic acid methyl ester is 100:50:40: 70.

Example 3

The mass ratio of the boric acid diglyceride to the tetracosanoic acid to the octadecanoyl chloride to the arachidic acid methyl ester is 100:70:60: 50.

Example 4

reacting boric acid diglyceride and tetracosanoic acid for 5 hours at 220 ℃ in a nitrogen environment, adjusting the pH value to 7.2 by using 30 wt% of sodium hydroxide aqueous solution, and distilling out water to obtain the surfactant.

The mass ratio of the boric acid diglyceride to the tetracosanoic acid is 100: 169.

Example 5

reacting the boric acid diglyceride and the octadecanoyl chloride for 5 hours at 220 ℃ in a nitrogen environment, and adjusting the pH value to 7.2 by using a 30 wt% sodium hydroxide aqueous solution to obtain the surfactant.

The mass ratio of the boric acid diglyceride to the octadecanoyl chloride is 100: 169.

Example 6

reacting the diglyceride borate and the methyl arachinate at 220 ℃ for 5 hours in a nitrogen environment, adjusting the pH value to 7.2 by using 30 wt% of sodium hydroxide aqueous solution, and distilling out methanol to obtain the surfactant.

The mass ratio of the boric acid diglyceride to the arachidic acid methyl ester is 100: 169.

Example 7

reacting boric acid diglyceride, tetracosanoic acid and octadecanoyl chloride for 5 hours at 220 ℃ in a nitrogen environment, adjusting the pH value to 7.2 by using 30 wt% of sodium hydroxide aqueous solution, and distilling out water to obtain the surfactant.

The mass ratio of the boric acid diglyceride to the tetracosanoic acid to the octadecanoyl chloride is 100:84.5: 84.5.

Example 8

reacting the boric acid diglyceride, the octadecanoyl chloride and the arachidic acid methyl ester for 5 hours at 220 ℃ in a nitrogen environment, adjusting the pH value to 7.2 by using 30 wt% of sodium hydroxide aqueous solution, and distilling out methanol to obtain the surfactant.

The mass ratio of the boric acid diglyceride to the octadecanoyl chloride to the arachidic acid methyl ester is 100:84.5: 84.5.

Example 9

reacting the boric acid diglyceride, the tetracosanoic acid and the arachidic acid methyl ester for 5 hours at 220 ℃ in a nitrogen environment, adjusting the pH value to 7.2 by using a 30 wt% sodium hydroxide aqueous solution, and distilling water and methanol to obtain the surfactant.

The mass ratio of the boric acid diglyceride to the tetracosanoic acid to the arachidic acid methyl ester is 100:84.5: 84.5.

Example 10

reacting boric acid diglyceride, tetracosanoic acid, octadecanoyl chloride, methyl arachinate and boron trifluoride butyl ether complex at 220 ℃ for 5 hours in a nitrogen environment, adjusting the pH value to 7.2 by using 30 wt% of sodium hydroxide aqueous solution, and distilling water and methanol to obtain the surfactant.

The addition amount of the boron trifluoride butyl ether complex is 0.5 wt% of the boric acid diglyceride.

Example 11

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 1;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

(1) uniformly stirring and mixing liquid paraffin, pentaerythritol tetraoleate, N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate, triethanolamine and organic boron surfactant at 70 ℃ to obtain an organic mixed solution;

(2) dissolving polyvinyl alcohol in water at 90 ℃; cooling to 50 deg.C, adding the above organic mixture, stirring, and mixing. Cooling to room temperature to obtain the workpiece antirust emulsion.

Example 12

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 4;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

Example 13

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 5;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

Example 14

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 6;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

Example 15

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 7;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

Example 16

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 8;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

Example 17

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 9;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

Example 18

15% of pentaerythritol tetraoleate;

1.5% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

5% of the organoboron surfactant of example 10;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

Example 19

15% of pentaerythritol tetraoleate;

5% of the organoboron surfactant of example 1;

17884.5% of polyvinyl alcohol;

3% of triethanolamine;

2.5 percent of liquid paraffin;

the balance being water.

(1) stirring and mixing liquid paraffin, pentaerythritol tetraoleate, triethanolamine and organic boron surfactant uniformly at 70 ℃ to obtain an organic mixed solution;

Test example 1:

reference is made to the test method of the research on the synthesis, properties and applications of boron-containing surfactants (li bin, university of physical engineering, tokyo, 2005).

The method for measuring the emulsifying force of the surfactant on the liquid organic matter (toluene or liquid paraffin) by a measuring cylinder method comprises the following steps: the surfactant prepared by the present invention was added with water to prepare a sample solution of 0.6 g/L.

A pipette was used to pipette 40mL of the sample solution into a glass stoppered flask, and then 40mL of toluene or liquid paraffin (chemical grade) was pipetted into the same flask. Closing the stopper, vibrating vigorously up and down for 5 min, standing for 1min, vibrating for 5 min, standing for 1min, and repeating the above steps for 5 times. The emulsion was poured into a 100mL graduated cylinder and the time was immediately recorded on a stopwatch, whereupon the water phase and the oil phase gradually separated and the aqueous phase appeared slowly, and the separation time (unit: s) was recorded until the aqueous phase separated 10mL, the greater the emulsifying power, the longer the time. Each sample experiment was repeated three times and the arithmetic mean was taken.

Surfactant emulsifying power test meter

The surfactant disclosed by the invention has good surface activity and emulsifying property, is non-toxic and non-corrosive, has a high boiling point, is not easy to volatilize, and has good bactericidal property and good antistatic property; it can be used as additive for gas drying agent, lubricating oil and compressor working medium, and also can be used as antistatic agent and antidrip agent of polyvinyl chloride, polyethylene and polymethyl acrylate, and dispersing agent and emulsifying agent of various substances.

Test example 2:

the antirust performance test of the workpiece antirust emulsion is carried out by referring to the national standard GB/T6144-2010 synthetic cutting fluid.

Corrosion test, coupon size: 25X 50X 3(mm), the test piece is fully soaked in the workpiece rust-proof emulsion of the examples 11-18, and the total soaking time of the cast iron piece/red copper when the cast iron piece/red copper is converted from the grade A to the grade B is observed once every half hour, namely the effective rust-proof time.

Test meter for corrosion test of workpiece antirust emulsion

	Cast iron sheetRust-proofing time h	Rust-proof time of red copper h
			Example 11	54.5	24
Example 12	47.5	21.5
			Example 13	42	19
Example 14	36	14.5
			Example 15	45.5	21
Example 16	39.5	17.5
			Example 17	45	19.5
Example 18	58	25.5
			Example 19	32.5	11.5

The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that are not thought of through the inventive work should be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.

Claims

1. The workpiece antirust emulsion is prepared from the following raw materials in percentage by weight:

12-18% of pentaerythritol tetraoleate;

3-7% of organic boron surfactant;

3-6% of polyvinyl alcohol;

2-4% of triethanolamine;

2-5% of liquid paraffin;

the balance being water.

2. The workpiece antirust emulsion is prepared from the following raw materials in percentage by weight:

13-17% of pentaerythritol tetraoleate;

1-2% of N, N, N ', N' -tetramethyl-O- (N-succinimide) urea tetrafluoroborate;

4-6% of organic boron surfactant;

3-6% of polyvinyl alcohol;

2-4% of triethanolamine;

2-5% of liquid paraffin;

the balance being water.

3. The rust inhibitive emulsion for workpieces according to claim 1 or 2, wherein said organoboron surfactant is prepared by the following method: reacting boric acid diglyceride, tetracosanoic acid, octadecanoyl chloride and methyl arachinate at the temperature of 230 ℃ for 4-6 hours in a nitrogen environment, adjusting the pH value to 7.0-7.5 by using an aqueous solution of sodium hydroxide, and distilling water and methanol to obtain the surfactant.

4. A method for preparing a rust inhibiting emulsion for workpieces according to any one of claims 1 to 3, characterized by comprising the steps of: