CN114349951B - Functional water-based flash rust inhibitor and preparation method thereof - Google Patents
Functional water-based flash rust inhibitor and preparation method thereof Download PDFInfo
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- CN114349951B CN114349951B CN202210047528.9A CN202210047528A CN114349951B CN 114349951 B CN114349951 B CN 114349951B CN 202210047528 A CN202210047528 A CN 202210047528A CN 114349951 B CN114349951 B CN 114349951B
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Abstract
The invention relates to the technical field of water-based paint, in particular to a functional water-based flash rust inhibitor and a preparation method thereof. The method comprises the following steps: the method comprises the following steps: under the condition of the existence of a solvent and a catalyst, a binary epoxy compound reacts with polyoxyethylene ether phosphate to prepare an intermediate 1; step two: adding excessive alcohol amine compound to react to obtain a main active compound 2; step three: distilling the organic solvent, cooling, adding deionized water and a nitrogen-containing heterocyclic organic compound according to the designed solid content, and filtering to obtain the functional water-based flash rust inhibitor finished product. A step of chain extension of dicarboxylic acid compounds can be added between the step one and the step two. The functional water-based flash rust inhibitor can comprehensively improve the flash rust prevention and corrosion inhibition capacity by multiple factors, and can be applied to the surfaces of various metals such as carbon steel, cast iron, copper, aluminum and the like.
Description
Technical Field
The invention relates to the technical field of water-based paint, in particular to a functional water-based flash rust inhibitor and a preparation method thereof.
Background
With the increasingly strict national environmental protection policy, the green environmental protection coating replaces the traditional oil coating and is becoming a great trend in the field of coating development. The water-based paint takes water as a main dispersion medium, and is one of the representatives of the green environment-friendly paint, but in the process of water-based paint construction, because the volatilization speed of water is slow, a metal substrate is easy to rust in the drying process of the paint. Therefore, the flash rust inhibitor is an essential important component in the formula design of the water-based paint, and the traditional flash rust inhibitor usually contains a toxic and harmful substance, namely nitrite, and has poor flash rust prevention effect on metal substrates such as cast iron, carbon steel and the like and welding seams of the metal substrates.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a functional water-based flash rust inhibitor and a preparation method thereof, wherein the preparation method comprises the following steps:
the method comprises the following steps: under the condition of solvent and catalyst, the binary epoxy compound reacts with polyoxyethylene ether phosphate to prepare an intermediate 1, and the intermediate 1 is a long-chain epoxy compound substituted by polyoxyethylene ether containing phosphoric acid groups.
The binary epoxy compound can be one or a mixture of more of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, p-xylylene glycol diglycidyl ether, cyclohexanol diglycidyl ether, 1,6-hexanediol diglycidyl ether and 1,5-pentanediol diglycidyl ether, and the general formula can be written as CH 2 (O)CH-R 2 -CH(O)CH 2 Wherein R is 2 Is a binary epoxy compound except epoxy group CH 2 (O) a structural group other than CH-.
The polyoxyethylene ether phosphate can be one or more of polyethylene glycol phosphate, oleic acid polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and octyl phenol polyoxyethylene ether phosphate, and the general formula can be written as R 1 -O-(CH 2 -CH 2 O) n -PO 3 H 2 Wherein R is 1 Is H (corresponding to polyethylene glycol phosphate) or a substituent group such as oleic acid group, fatty hydrocarbon chain, octylphenol group, etc. The polymerization degree n of the polyoxyethylene ether phosphate is 15-100.
The reaction process of the step one is as follows:
the general formula of intermediate 1 produced in step one may be represented as follows:
in the first step, the weight ratio of the binary epoxy compound to the polyoxyethylene ether phosphate is 1 (0.8-1.2), and the binary epoxy compound and the polyoxyethylene ether phosphate react according to the molar ratio of 1:1. The reaction temperature can be 35-110 ℃, and the reaction time can be 30-120 min.
Step two: and adding excessive alcohol amine compound for reaction, and completely opening the epoxy group in the intermediate 1 by using the amino group in the excessive alcohol amine to prepare a main active compound 2. The ammonia alcohol compound can be one or a mixture of more of monoethanolamine, diethanolamine, triethanolamine, isopropanolamine and diisopropanolamine.
The reaction temperature of the second step is 40-110 ℃, and the reaction time is 30-120 min.
Step three: distilling the organic solvent, cooling, adding deionized water and a nitrogen-containing heterocyclic organic compound according to the designed solid content, and filtering to obtain the functional water-based flash rust inhibitor finished product.
The functional water-based anti-flash rust agent comprises the intermediate 1 and a nitrogen-containing heterocyclic compound, wherein the nitrogen-containing heterocyclic compound can be one or a mixture of morpholine, benzotriazole, methyl benzotriazole and hydroxy benzotriazole.
The solvent is one or a mixture of more of ethyl acetate, butyl acetate, toluene, xylene, dioxane and tetrahydrofuran.
In the above method, a dicarboxylic acid compound may be added to the intermediate 1 between the first step and the second step to perform a ring-opening reaction of a carboxyl group and an epoxy group, and a part of the intermediate 1 may be chain-extended. The dicarboxylic acid compound is one or a mixture of oxalic acid, malonic acid, adipic acid, glutaric acid, phthalic acid and maleic acid, and has a general formula of HOOC-R 3 -COOH, wherein R 3 Are structural groups other than carboxyl groups. The specific reaction process is as follows:
the reaction temperature of the intermediate 1 and the dicarboxylic acid compound is 80-160 ℃, the reaction time is 30-120 min, and the mass ratio of the intermediate 1 to the dicarboxylic acid compound is 1: (0.25 to 0.3) to leave a certain amount of intermediate 1 having an epoxy group which has not reacted with the dicarboxylic acid compound, and the epoxy group in these unreacted intermediate 1 is completely opened by the alcohol amine in the second step.
In the method, the required catalyst is one or a mixture of more of boron trifluoride diethyl etherate, ammonium persulfate, potassium persulfate, sodium persulfate, triphenylphosphine, p-toluenesulfonic acid, benzoic acid, glacial acetic acid, oxalic acid and phosphoric acid; wherein one or more of boron trifluoride diethyl etherate, ammonium persulfate, potassium persulfate, sodium persulfate, triphenylphosphine and the like are used for the reaction in the step one, and one or more of p-toluenesulfonic acid, benzoic acid, glacial acetic acid, oxalic acid and phosphoric acid are used for the reaction of the intermediate 1 and the dicarboxylic acid compound.
The prepared functional water-based flash rust inhibitor product comprises the following two components: the component 1 is a product obtained by the ring-opening reaction of the epoxy group in the intermediate 1 and the amino group in the alcohol amine and the complete ring-opening of the epoxy group; the component 2 is a nitrogen-containing heterocyclic compound. If a dicarboxylic acid compound is added between the first step and the second step for reaction, the reaction product also comprises a component 3, namely the structural general formula is as follows:
the solvent of the functional water-based flash rust inhibitor is deionized water, and the solid content is 25-85%.
The principle and the beneficial effects of the functional water-based flash rust inhibitor are as follows: the functional water-based flash rust inhibitor prepared by the invention is environment-friendly and nontoxic, has a large molecular weight, and can be adsorbed on the surface of metal for a long time. The hydrophilic phosphate group contained in the molecular structure has phosphorization and passivation effects on the metal surface, and the adhesion and corrosion resistance are enhanced; when the binary epoxy compound or/and the dicarboxylic acid compound containing the benzene ring structure are/is adopted, the benzene ring structure contained in the binary epoxy compound or/and the dicarboxylic acid compound has an oxygen blocking effect, and the benzene ring structure has affinity with the nitrogen-containing heterocyclic compound, so that a certain synergistic effect is generated, and a better oxygen blocking effect is achieved. The polyoxyethylene chain segment has high surface activity and can greatly reduce the surface tension of the coating. Active hydroxyl generated after the ring opening of the epoxy group can improve the capability of the aqueous flash rust inhibitor to be attached to the metal surface. Therefore, the functional water-based flash rust inhibitor can comprehensively improve the flash rust prevention and corrosion inhibition capacity by multiple factors, and can be applied to the surfaces of various metals such as carbon steel, cast iron, copper, aluminum and the like.
Drawings
FIG. 1 is a comparison of the effect of the coating of example 1 of the present invention added with the flash rust inhibitor of the present invention on the surface of cast iron, with the coating not added.
Detailed Description
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to the following examples.
Example 1:
(1) Mixing 0.1mol of dehydrated oleic acid polyoxyethylene ether phosphate and 300ml of toluene, adding 0.2g of boron trifluoride diethyl etherate, stirring and adding 0.1mol of ethylene glycol diglycidyl ether under the condition of keeping the temperature at 55 ℃, controlling the reaction temperature to be 85 ℃, and reacting for 30min to obtain an intermediate 1;
(2) Adding 0.2mol of diethanolamine, and reacting at 80 ℃ for 60min to obtain a main active compound 2;
(3) Distilling the organic solvent, cooling to 60 ℃, stirring, adding 0.15mol of morpholine and deionized water, adding deionized water according to the solid content of 80%, keeping the temperature for 3-10h, filtering and discharging to obtain the functional aqueous flash rust inhibitor product containing phosphate groups.
(4) The water-based flash rust inhibitor prepared by the invention is added into the water-based epoxy coating, the addition amount is 1.5%, then the coating is sprayed on the surface of cast iron, and compared with the cast iron surface sprayed with the coating without the flash rust inhibitor, the comparison effect is shown in figure 1, after the water-based epoxy coating is sprayed, obvious rust can be seen on the cast iron surface without the flash rust inhibitor on the left side, and no rust point is generated on the cast iron surface after the flash rust inhibitor in the invention is added in an amount of 1.5% on the right side.
The flash rust prevention of the weld surface of cast iron and submerged arc welding is always a difficult problem in the industry, and the flash rust prevention agent can effectively solve the problem of flash rust prevention of the weld surface of cast iron and submerged arc welding.
Example 2:
basically the same as example 1, except that the following steps are also included between steps (1) and (2): adding 0.03mol of oxalic acid and 0.005mol of p-toluenesulfonic acid into the intermediate 1, and reacting at 80 ℃ for 120min; and (3) carrying out the reaction in the step (2).
Example 3:
(1) Mixing 0.1mol of dehydrated octyl phenol polyoxyethylene ether phosphate and 300ml of dioxane, adding 0.2g of ammonium persulfate, stirring and adding 0.08mol of 1, 4-butanediol diglycidyl ether under the condition of keeping the temperature at 55 ℃, controlling the reaction temperature to be 110 ℃, and reacting for 40min to obtain an intermediate 1;
(2) Adding 0.025mol of succinic acid and 0.005mol of p-toluenesulfonic acid into the intermediate 1, and reacting at 110 ℃ for 30min;
(3) Adding 0.2mol of monoethanolamine, and reacting at 40 ℃ for 120min to obtain a main active compound 2;
(4) Distilling the organic solvent, cooling to 60 ℃, stirring, adding 0.15mol of methylbenzotriazole and deionized water, adding the deionized water according to the solid content of 25%, preserving the heat for 3-10h, filtering and discharging to obtain the functional aqueous anti-flash rust agent product containing phosphate groups.
Example 4:
(1) Mixing 0.1mol of dehydrated polyethylene glycol phosphate with 300ml of butyl acetate, adding 0.2g of triphenylphosphine, stirring and adding 0.12mol of p-xylylene glycol diglycidyl ether under the condition of keeping the temperature at 55 ℃, controlling the reaction temperature at 40 ℃, and reacting for 120min to obtain an intermediate 1;
(2) Adding 0.03mol of phthalic acid and 0.005mol of phosphoric acid into the intermediate 1, and reacting for 60min at 160 ℃;
(3) Adding 0.2mol of triethanolamine, and reacting at 110 ℃ for 30min to obtain a main active compound 2;
(4) Distilling the organic solvent, cooling to 60 ℃, adding 0.15mol of benzotriazole and deionized water under stirring, adding the deionized water according to the solid content of 40%, filtering and discharging to obtain the phosphate-group-containing functional aqueous flash rust inhibitor product.
Claims (10)
1. A functional water-based flash rust inhibitor is characterized by comprising the following components:
component 1: has the general formula
The epoxy group in the compound is subjected to ring-opening reaction with the amino group in the alcohol amine, and the epoxy group is completely subjected to ring-opening reaction to obtain a product;
wherein R is 1 Is H or oleic acid group, fatty hydrocarbon chain, octylphenol group, R 2 Is one or a mixture of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, terephthalyl alcohol diglycidyl ether, cyclohexanol diglycidyl ether, 1,6-hexanediol diglycidyl ether and 1,5-pentanediol diglycidyl ether to remove epoxy CH 2 (O) structural groups other than CH-; the polymerization degree n is 15-100;
component 2: a nitrogen-containing heterocyclic compound.
2. The functional aqueous flash rust inhibitor according to claim 1, further comprising the following components:
component 3:
has the general formula
Wherein R is 3 Is a structural group except carboxyl in one or a mixture of more of oxalic acid, malonic acid, adipic acid, glutaric acid, phthalic acid and maleic acid;
R 1 is H or oleic acid group, fatty hydrocarbon chain, octylphenol group, R 2 Is 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, p-xylylene glycol diglycidyl ether, cyclohexanol diEpoxy CH is removed from one or a mixture of more of glycidyl ether, 1,6-hexanediol diglycidyl ether and 1,5-pentanediol diglycidyl ether 2 (O) structural groups other than CH-; the polymerization degree n is 15 to 100.
3. The functional aqueous flash rust inhibitor according to claim 1, wherein the solvent of the functional aqueous flash rust inhibitor is deionized water, and the solid content of the solvent is 25-85%.
4. The functional aqueous anti-flash rust agent according to claim 1, wherein the nitrogen-containing heterocyclic compound is one or a mixture of morpholine, benzotriazole, tolyltriazole and hydroxybenzotriazole.
5. The method for preparing the functional water-based flash rust inhibitor according to claim 1, comprising the steps of:
the method comprises the following steps: under the condition of the existence of a solvent and a catalyst, a binary epoxy compound reacts with polyoxyethylene ether phosphate to prepare an intermediate 1;
step two: adding excessive alcohol amine compound to react to obtain a main active compound 2;
step three: distilling the organic solvent, cooling, adding deionized water and a nitrogen-containing heterocyclic organic compound according to the designed solid content, and filtering to obtain the functional water-based flash rust inhibitor finished product.
6. The method of claim 5, wherein:
the method also comprises the following steps between the first step and the second step: adding a dicarboxylic acid compound into the intermediate 1 to perform a ring-opening reaction of a carboxyl group and an epoxy group.
7. The production method according to claim 5 or 6, characterized in that:
the binary epoxy compound is one or a mixture of more of 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, cyclohexanol diglycidyl ether, 1,6-hexanediol diglycidyl ether and 1,5-pentanediol diglycidyl ether;
the polyoxyethylene ether phosphate is one or a mixture of more of polyethylene glycol phosphate, oleic acid polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and octyl phenol polyoxyethylene ether phosphate;
the alcohol amine compound is one or a mixture of more of monoethanolamine, diethanolamine, triethanolamine, isopropanolamine and diisopropanolamine;
the catalyst in the preparation method is one or a mixture of more of boron trifluoride ether complex, ammonium persulfate, potassium persulfate, sodium persulfate, triphenylphosphine, p-toluenesulfonic acid, benzoic acid, glacial acetic acid, oxalic acid and phosphoric acid;
the solvent is one or a mixture of more of ethyl acetate, butyl acetate, toluene, xylene, dioxane and tetrahydrofuran.
8. The method of manufacturing according to claim 6, characterized in that: the dicarboxylic acid compound is one or a mixture of more of oxalic acid, malonic acid, adipic acid, glutaric acid, phthalic acid and maleic acid.
9. The method of claim 5, wherein: in the first step, the weight ratio of the binary epoxy compound to the polyoxyethylene ether phosphate is 1 (0.8-1.2), the reaction temperature is 35-110 ℃, and the reaction time is 30-120 min; in the second step, the reaction temperature is 40-110 ℃, and the reaction time is 30-120 min.
10. The method of claim 6, wherein: the mass ratio of the intermediate 1 to the dicarboxylic acid compound is 1: (0.25-0.3), the reaction temperature is 80-160 ℃, and the reaction time is 30-120 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192088A (en) * | 2017-12-29 | 2018-06-22 | 岳阳凯门水性助剂有限公司 | A kind of anti-flash rusting agent and its preparation method and application |
| CN112961574A (en) * | 2021-03-18 | 2021-06-15 | 珠海展辰新材料股份有限公司 | Aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion and preparation method thereof |
| CN113461948A (en) * | 2021-07-12 | 2021-10-01 | 武汉辰语达科技有限公司 | Flash rust prevention agent and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192088A (en) * | 2017-12-29 | 2018-06-22 | 岳阳凯门水性助剂有限公司 | A kind of anti-flash rusting agent and its preparation method and application |
| CN112961574A (en) * | 2021-03-18 | 2021-06-15 | 珠海展辰新材料股份有限公司 | Aqueous nonionic phosphorus-containing epoxy anticorrosive emulsion and preparation method thereof |
| CN113461948A (en) * | 2021-07-12 | 2021-10-01 | 武汉辰语达科技有限公司 | Flash rust prevention agent and preparation method and application thereof |
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