1. The secondary rust remover for the ships is characterized by comprising the following raw materials in parts by weight:

20-40 parts of citric acid

15-25 parts of organic silicon modified phosphate

5-10 parts of acrylic emulsion

60-80 parts of water;

the organic silicon modified phosphate is prepared by esterifying polyether modified trisiloxane through a phosphorylation reagent.

2. The secondary rust remover for ships according to claim 1, characterized in that: the preparation process of the organic silicon modified phosphate ester comprises the following steps: preheating polyether modified trisiloxane to 70-90 ℃, adding a phosphorylation reagent into the polyether modified trisiloxane, wherein the weight ratio of the polyether modified trisiloxane to the phosphorylation reagent is 1 (10-12), stirring to obtain a mixed solution, continuously adding p-toluenesulfonic acid into the mixed solution, keeping the temperature for reacting for 4-8 h, and purifying to obtain the organic silicon modified phosphate after the reaction is finished.

3. The secondary rust remover for ships according to claim 2, characterized in that: the phosphorylating agent is P₂O₅、H₃PO₄、H₄P₂O₇、Na₃PO₄One or more of (a).

4. The secondary rust remover for ships according to claim 1, characterized in that: the particle diameter of the acrylic emulsion is 0.3-0.4 μm.

5. The secondary rust remover for ships according to claim 1, characterized in that: the raw materials also comprise pyrogallol derivatives, and the weight portion of the pyrogallol derivatives is 1-3.

6. The secondary rust remover for ships according to claim 5, characterized in that: the pyrogallol derivative is one or more of gallic acid, tannic acid and catechin.

7. The secondary rust remover for ships according to claim 6, characterized in that: the weight ratio of gallic acid, tannic acid and catechin in the pyrogallol derivatives is 1 (5-6) to 3-4.

8. The secondary rust remover for ships according to claim 1, characterized in that: and an acrylic monomer is also added into the raw materials, wherein the weight part of the acrylic monomer is 3-4.

9. A secondary ship rust removal process is characterized by comprising the following steps:

the secondary rust remover for the ship is used for spraying and drying the rust layer of the ship section to finish secondary rust removal.

10. The secondary derusting process for ships according to claim 9, wherein: the spraying step comprises the following specific operations: and preheating the rust layer of the ship section to 40-50 ℃, and then coating a secondary ship rust remover.

Background

The steel plates used for ship construction are subjected to surface pretreatment and workshop primer coating, and then are subjected to marking, blanking, processing, assembling, welding and other procedures to be assembled into sections or areas of the ship body. In the processing procedure, a paint film on the surface of the steel plate is damaged, so that the surface of the steel is rusted again, secondary treatment needs to be carried out on the steel, and the treatment procedure is a secondary ship rust removal process.

In the related technology, the early secondary rust removal process adopts means such as manual rust removal and sand blasting rust removal, rust on the surface of steel is removed by polishing through mechanical external force, but only under the action of the mechanical external force, the rust removal efficiency is low, the labor cost is high, and gravel is difficult to recycle.

The later stage of secondary rust removal process adopts a steel rust remover to perform soaking treatment, for example, the patent with the application number of 85104742 discloses a steel rust removal and passivation process, wherein hydrochloric acid rust removal liquid containing an activating agent is firstly used for treatment, so that a rust layer and an oxide skin on the surface of steel are rapidly dissolved and peeled off, and then passivation liquid containing quicklime and sodium nitrite is used for treatment, so that a passivation film is generated on the surface of metal.

Aiming at the related technologies, the inventor considers that the volume of the ship section is large, a corresponding derusting pool and a corresponding passivation pool need to be established according to the size of the ship section, and the treatment process is complicated.

Disclosure of Invention

In order to simplify the secondary derusting process of the ship, the application provides a secondary derusting agent for the ship and a secondary derusting process for the ship.

In a first aspect, the application provides a secondary rust remover for ships, which adopts the following technical scheme:

a secondary rust remover for ships comprises the following raw materials in parts by weight:

20-40 parts of citric acid

15-25 parts of organic silicon modified phosphate

5-10 parts of acrylic emulsion

60-80 parts of water;

the organic silicon modified phosphate is prepared by esterifying polyether modified trisiloxane through a phosphorylation reagent.

By adopting the technical scheme, the end of the polyether modified trisiloxane contains hydroxyl which can be subjected to esterification reaction with phosphoric acid in a phosphorylation reagent, and the generated organic silicon modified phosphate contains phosphate radical with negative electricity.

The organic silicon modified phosphate and the citric acid act together, and have a synergistic effect in the aspect of rust removal, so that when the prepared secondary rust remover for ships sprays rust layers of ship sections at normal temperature, rust automatically disappears, and possible reasons are as follows: the organic silicon modified phosphate ester has strong surface activity, and the citric acid solution can fully permeate and wet the rust layer on the surface of the steel under the action of the organic silicon modified phosphate ester, so that the metal oxide in the rust layer is converted into Fe²⁺、Fe³⁺、Cu⁺、Cu²⁺、Zn²⁺And (2) metal ions are subjected to ionization, citric acid contains one hydroxyl group and contains three carboxyl coordination functional groups, citric acid serving as a tetradentate ligand can be chelated with the metal ions to generate a stable complex, and meanwhile, the organic silicon modified phosphate contains a phosphate radical group with negative electricity and can also be chelated with the metal ions to generate the complex. The rust layer is wettedThen, the organic silicon modified phosphate and the citric acid react with the rust, and the rust is automatically converted into a complex compound, so that the aim of removing rust is fulfilled.

In addition, carboxyl contained in the acrylic emulsion promotes the dissolution of metal oxide, accelerates the disappearance of a rust layer and the generation of a complex, the acrylic emulsion can be self-crosslinked at normal temperature, and the acrylic emulsion and the complex act together to generate a compact protective film at a steel rust position, so that the antirust effect can be achieved.

The acrylic emulsion and the organic silicon modified phosphate ester act together, the macromolecular chain segment of the organic silicon modified phosphate ester is embedded with the acrylate chain segment in the acrylic emulsion, so that the adhesive property of the protective film at the rust position of steel is enhanced, and meanwhile, the surface of the protective film contains hydrophobic siloxane (derived from the organic silicon modified phosphate ester), so that the protective film has better waterproof property, and the antirust capacity of the protective film is further enhanced.

Preferably, the preparation process of the organic silicon modified phosphate ester comprises the following steps:

preheating polyether modified trisiloxane to 70-90 ℃, adding a phosphorylation reagent into the polyether modified trisiloxane, wherein the weight ratio of the polyether modified trisiloxane to the phosphorylation reagent is 1 (10-12), stirring to obtain a mixed solution, continuously adding p-toluenesulfonic acid into the mixed solution, keeping the temperature for reacting for 4-8 h, and purifying to obtain the organic silicon modified phosphate after the reaction is finished.

By adopting the technical scheme, the organic silicon modified phosphate prepared by the method has higher ester content, and is beneficial to improving the derusting capacity and the rust prevention capacity of the secondary deruster for ships.

Preferably, the phosphorylating agent is P₂O₅、H₃PO₄、H₄P₂O₇、Na₃PO₄One or more of (a). More specifically, it is preferred herein that the phosphorylating agent is H₃PO₄The polyether modified trisiloxane is polyether modified dimethyl trisiloxane and/or polyether modified heptamethyl trisiloxane.

Preferably, the particle diameter of the acrylic emulsion is 0.3-0.4 μm.

By adopting the technical scheme, within the particle diameter range, the bonding strength of the acrylic emulsion is better, and the rust prevention capability of the secondary rust remover for ships is improved.

Preferably, the raw material also comprises 1-3 parts by weight of pyrogallol derivatives.

Preferably, the pyrogallol derivative is one or more of gallic acid, tannic acid and catechin.

By adopting the technical scheme, the gallic acid, the tannic acid and the catechin contain both phenolic hydroxyl and carboxyl, so that the pyrogallol derivatives can promote the conversion of a rust layer and further improve the rust removing and preventing capabilities of the secondary ship rust remover.

Preferably, the weight ratio of the gallic acid to the tannic acid to the catechin in the pyrogallol derivative is 1 (5-6) to (3-4).

By adopting the technical scheme, three pyrogallol substances are compounded, and the rust removing and preventing capabilities of the secondary rust remover for the ships are optimal under the weight ratio.

Preferably, an acrylic acid monomer is further added into the raw materials, and the weight part of the acrylic acid monomer is 3-4.

By adopting the technical scheme, the acrylic acid monomer contains a large amount of carboxyl, so that the conversion of the rust layer is further promoted.

In a second aspect, the application provides a secondary derusting process for ships, which adopts the following technical scheme:

a secondary ship rust removal process comprises the following steps: and (3) spraying and drying the rust layer of the ship section by using the secondary rust remover for the ship, and finishing rust removal.

By adopting the technical scheme, the secondary rust remover for ships can achieve the rust removing effect by spraying at normal temperature, and can generate a compact protective film while removing rust, thereby achieving a better rust preventing effect.

Preferably, the spraying step comprises the following specific operations: and preheating the rust layer of the ship section to 40-50 ℃, and then coating a secondary ship rust remover.

By adopting the technical scheme, in the temperature range, the derusting rate of the secondary deruster for the ship is accelerated, and the rate of generating the protective film is accelerated, so that the derusting and antirust effects are further improved.

The application has the following beneficial effects:

1. the polyether modified trisiloxane and the phosphorylation reagent are subjected to esterification reaction to obtain the organic silicon modified phosphate, the organic silicon modified phosphate and the citric acid act together, the synergistic effect is achieved in the aspect of rust removal, and the organic silicon modified phosphate and the acrylic emulsion act together to accelerate the removal of rust and the generation of a protective film and achieve an excellent rust prevention effect.

2. In the application, the pyrogallol derivative is preferably added, and the pyrogallol derivative contains both phenolic hydroxyl and carboxyl, has a promotion effect on the transformation of the rust layer, and accelerates the removal of the rust layer and the generation of a protective film.

3. In the application, an acrylic acid monomer is preferably added, and the acrylic acid monomer plays a role in further improving the capabilities of rust removal and rust prevention.

Detailed Description

Unless otherwise specified, the sources of the raw materials of the examples of the present application and comparative examples are shown in table 1 below.

TABLE 1 sources of raw materials

Preparation example

Preparation example 1

An organic silicon modified phosphate is prepared by the following steps:

1kg of polyether modified heptamethyltrisiloxane (H-350) was heated to 70 ℃ with stirring, and 10kg of orthophosphoric acid (H) was weighed₃PO₄) Slowing down orthophosphoric acidAdding the mixture into polyether modified heptamethyltrisiloxane to obtain a mixed solution; and weighing 0.1g of p-toluenesulfonic acid, adding the p-toluenesulfonic acid into the mixed solution, reacting for 4 hours at the temperature of 70 ℃, and distilling under reduced pressure at the temperature of 50 ℃ to remove low-boiling-point substances to obtain the organic silicon modified phosphate.

Preparation examples 2 to 3

An organosilicon-modified phosphoric acid ester was prepared in a different manner from that in production example 1, 11kg of orthophosphoric acid was used in production example 2, and 12kg of orthophosphoric acid was used in production example 3.

Preparation examples 4 to 5

An organosilicon-modified phosphoric acid ester was prepared in a manner different from that of preparation example 3 in that the polyether-modified heptamethyltrisiloxane in preparation example 4 was heated at 80 ℃ and that in preparation example 5 was heated at 90 ℃.

Preparation examples 6 to 7

A silicone-modified phosphoric acid ester which is different from preparation example 5 in that the reaction time for holding the temperature in preparation example 6 was 6 hours and the reaction time for holding the temperature in preparation example 7 was 8 hours.

Examples

Example 1

A secondary rust remover for ships is prepared by the following steps:

200g of citric acid, 150g of organic silicon modified phosphate, 50g of acrylic emulsion (ZS-9890H) and 800g of water are weighed, stirred and mixed uniformly to obtain the secondary ship rust remover, wherein the organic silicon modified phosphate is from preparation example 1, and the particle diameter of the acrylic emulsion is 0.3-0.4 mu m.

Examples 2 to 7

A secondary rust remover for ships is different from that in example 1 in that the sources of organic silicon modified phosphate ester are different:

the silicone-modified phosphate ester of example 2 was derived from preparation example 2;

the silicone-modified phosphate ester of example 3 was derived from preparation example 3;

the silicone-modified phosphate ester of example 4 was derived from preparation 4;

the silicone-modified phosphate ester of example 5 was derived from preparation example 5;

the silicone-modified phosphate ester of example 6 was derived from preparation 6;

the silicone-modified phosphate ester in example 7 was derived from preparation example 7.

Examples 8 to 13

A secondary rust remover for ships is different from the secondary rust remover in example 7 in that the weight of each component is different, and the specific weight is shown in the following table 2.

TABLE 2 weight of each of the feedstocks in examples 8-13

Examples 14 to 18

A secondary rust remover for ships, which is different from the secondary rust remover in example 13 in that the compositions of raw materials are different: in each of examples 14 to 18, pyrogallol derivatives were added;

the specific operation is as follows: adding pyrogallol derivatives into a mixed solution consisting of 400g of citric acid, 250g of organic silicon modified phosphate, 100g of acrylic emulsion (ZS-9890H) and 600g of water, and uniformly stirring to obtain a secondary ship rust remover;

wherein the composition and the addition amount of the pyrogallol derivatives added in the examples 14 to 18 are shown in the following Table 3.

TABLE 3 composition and amount of pyrogallol derivative in examples 14 to 18

Composition of	Example 14	Example 15	Example 16	Example 17	Example 18
						Gallic acid/g	10	20	30	3	3
Tannic acid/g	/	/	/	15	18
						Catechin/g	/	/	/	12	9

Examples 19 to 20

A secondary rust remover for ships, which is different from the secondary rust remover in example 18 in that the compositions of raw materials are different: in each of examples 19 to 20, an acrylic monomer was added;

the specific operation is as follows: adding an acrylic acid monomer into a mixed solution consisting of 400g of citric acid, 250g of organic silicon modified phosphate, 100g of acrylic emulsion (ZS-9890H), 3g of gallic acid, 18g of tannic acid, 9g of catechin and 600g of water, and uniformly stirring to obtain a secondary ship rust remover;

the amount of the acrylic monomer added in example 19 was 30g, and the amount of the acrylic monomer added in example 20 was 40 g.

Comparative example

Comparative example 1

A secondary rust remover for ships is different from the secondary rust remover in example 1 in that organic silicon modified phosphate ester is replaced by citric acid with equal mass.

Comparative example 2

A secondary rust remover for ships is different from the rust remover in example 1 in that acrylic emulsion is replaced by citric acid with equal mass.

Comparative example 3

A secondary rust remover for ships is different from the secondary rust remover in example 1 in that organic silicon modified phosphate ester is replaced by orthophosphoric acid with equal mass.

Application example

A secondary ship rust removal process comprises the following steps: rust layer (1 m specification) of ship section at normal temperature by using ship secondary rust remover prepared in the above embodiment²) Spraying is carried out, and the spraying amount of the secondary rust remover for the ship is 0.4kg/m²And waiting for the surface of the rust layer to be completely dried to finish rust removal.

The difference between the application examples 1-20 and the comparative application examples 1-3 is that the sources of the secondary rust remover for ships used are different, and the specific sources are shown in the following table 4:

TABLE 4 sources of secondary rust remover for ships

Application examples 21 to 22

A secondary rust removal process for ships is different from the application example 20 in that rust layers of ship sections are preheated, and then spraying is carried out by using a secondary rust remover for ships under the condition of heat preservation;

wherein the preheating temperature of application example 21 was 40 ℃ and the preheating temperature of application example 22 was 50 ℃.

Comparative application example 4

A steel rust removal and passivation process comprises the following steps:

preparation of a rust removing liquid:

s1, preparing raw materials: 10 wt% hydrochloric acid, urotropine, sodium dodecyl sulfate, emulsifier TX-10, detergent 6501 and water; s2, calculating, weighing and uniformly stirring the raw materials according to a certain weight percentage to obtain the rust removing liquid with the following formula: 15 wt% of hydrogen chloride, 1 wt% of urotropine, 0.2 wt% of sodium dodecyl sulfate, 100.2 wt% of emulsifier TX, 65010.2 wt% of detergent and the balance of water;

preparing a passivation solution:

s1, preparing raw materials: quick lime, sodium nitrite, urotropine and water;

s2, calculating, weighing and uniformly stirring the raw materials according to a certain weight percentage to obtain the passivation solution with the following formula: 4 wt% of quicklime, 1.5 wt% of sodium nitrite, 0.15 wt% of urotropine and the balance of water.

Derusting and passivating:

rust layer (specification of 0.001 m) of ship section²) Soaking in a rust removing solution at normal temperature for 1h, washing the ship section with clean water for 2 times after soaking, and drying at 100 ℃ to obtain a clean ship section;

and soaking the clean ship section in the passivation solution at 50 ℃ for 1h, washing the ship section with clean water for 2 times after soaking, and drying at 100 ℃ to obtain the passivated ship section.

Performance test

Detection method

1. Rust removal capacity: the rust layers of the ship sections are treated by using the ship rust removing processes of the application examples 1-22 and the comparative examples 1-4;

observing whether the surface of the rust layer of the ship section has rust spots under the same spraying amount (except for comparative application example 4, the dosage of the rust remover is limited by the comparative application example 4);

the time at which the surface rust of the rust layer of the ship section completely disappeared was observed.

2. Antirust capacity: using the ship derusting processes of the application examples 1 to 22 and the comparative examples 1 to 4 to treat 52 ship sections (the specification of the ship sections is 1m multiplied by 0.01m), wherein two samples are treated in each treatment mode (the coating amount is increased compared with the application example 1 and the application example 3 until rust spots on the samples completely disappear);

taking 26 samples which are respectively subjected to the ship rust removal process treatment of application examples 1-22 and comparative examples 1-4, partially soaking each sample in river water, electrifying the river water (with the current of 0.5A and the alternating voltage of 2V), accelerating the occurrence of rust, and observing the time for generating rust at an interface;

and taking another 26 samples which are respectively subjected to the ship rust removal process treatment of the application examples 1-22 and the comparative examples 1-4, partially soaking each sample in seawater, electrifying the samples in the seawater (with the current of 0.5A and the alternating voltage of 2V), accelerating the occurrence of corrosion, and observing the time for generating the corrosion at the interface.

Detecting data

TABLE 5 derusting ability of derusting process of ship

TABLE 6 Rust protection ability of Rust removal Process for ships

Data analysis

By combining the application example 1 and the comparative application examples 1 and 3 and combining the table 5, it can be seen that the comparative application example 1 does not contain the organic silicon modified phosphate, and after the same spraying treatment is performed on the rust layer of the ship section, the rust is not completely removed, and the rust residue still exists; and the comparison application example 3 shows that the orthophosphoric acid and the citric acid with the rust removal effect are compounded, and the rust spots have trace traces after the rust layers of the ship sections are subjected to the same spraying treatment: when the same spraying amount is used for spraying treatment, the organic silicon modified phosphate and the citric acid have synergistic effect in the aspect of rust removal.

It can be seen by combining application example 1 with comparative application example 1, comparative application example 2, and combining table 6: the comparative application example 1 does not contain organic silicon modified phosphate ester, the sample treated by the comparative application example 1 is subjected to accelerated corrosion detection in river water, the time for corrosion to appear at the interface is 17 days, the accelerated corrosion detection is carried out in seawater, and the sample is easier to form a micro-battery due to higher salt content in the seawater, and the time for corrosion to appear is shortened to 4 days;

the comparative application example 2 does not contain acrylic emulsion, the sample treated by the comparative application example 2 is subjected to accelerated corrosion detection in river water, the time for the interface to generate corrosion is 7 days, the accelerated corrosion detection is performed in seawater, and the time for the interface to generate corrosion is shortened to 2 days;

and the sample treated by the application example 1 is subjected to accelerated corrosion detection in river water, the time for the interface to generate corrosion is up to 27 days, and the time for the interface to generate corrosion can be still prolonged to 19 days when the sample is subjected to accelerated corrosion detection in seawater, so that the joint action of the acrylic emulsion and the organic silicon modified phosphate ester is demonstrated to enhance the rust prevention capability of the secondary rust removal process for the ship.

It can be seen by combining application examples 1 to 22 and comparative application example 4 and combining tables 5 to 6 that application examples 1 to 22 can achieve a good rust removal effect and the rust prevention capability is superior to that of the rust removal method described in the related art.

The combination of application examples 1-7 and tables 5-6 show that the weight ratio of the polyether modified trisiloxane to the phosphorylation reagent is 1:12, the reaction temperature is 90 ℃, the reaction time is 8 hours, the esterification reaction of the polyether modified trisiloxane and the phosphorylation reagent is sufficient, after the sample is treated by the ship secondary rust remover, rust spots on the sample completely disappear within 13 hours, the rust prevention time of the sample in river water is prolonged to 35 days, and the rust prevention time of the sample in seawater is prolonged to 30 days.

Combining application examples 7-13 and tables 5-6, it can be seen that when the concentration of citric acid is 29.6 wt%, the concentration of organosilicon modified phosphate ester is 18.5 wt%, and the concentration of acrylic emulsion is 7.4 wt%, the disappearance time of rusty spots of the treated sample is accelerated, and the rust prevention time is prolonged, thus proving that the rust removal and rust prevention performance of the secondary rust prevention treatment process for ships is superior.

Combining application examples 13-18 with tables 5-6, it can be seen that when pyrogallol derivatives are added into the secondary rust remover for ships, rust spots of samples treated by application examples 14-18 completely disappear within 10 hours, the samples are subjected to accelerated corrosion detection in river water, the time for corrosion to appear at the interface is not less than 43 days, the time for corrosion to appear at the interface is not less than 38 days;

and gallic acid, tannic acid and catechin in the pyrogallol derivatives are compounded according to the weight ratio of 1:6:3, a sample is treated, rust spots of the sample completely disappear within 8 hours, the sample is subjected to accelerated rust detection in river water, the time for rusting at an interface is as high as 59 days, the accelerated rust detection is carried out in seawater, and the time for rusting at the interface is as high as 54 days, so that the pyrogallol derivatives added into the secondary rust remover for the ships have good rust removing and preventing effects.

As can be seen by combining application examples 18-20 and tables 5-6, when the acrylic acid monomer is added into the secondary rust remover for the ship, rust spots of samples treated by the application examples 19-20 completely disappear within 6 hours, the samples are subjected to accelerated rust detection in river water, the time for rusting at the interface is not less than 59 days, the time for rusting at the interface is not less than 54 days, and the acrylic acid monomer has good rust removal and rust prevention promoting effects.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.