JP6871659B1 - Underwater crude oil adhesion prevention paint, its preparation method and application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a paint for preventing crude oil adhesion in water, which has excellent adhesion to various substrate surfaces and can maintain ultra-leaky oil characteristics at various pHs, and a method for preparing the same. SOLUTION: A coating material for preventing crude oil adhesion in water, which is obtained by polymerizing a hydrophilic acrylic monomer, a hydrophobic acrylic monomer, an initiator and a solvent. The preparation method comprises a step of uniformly mixing and reacting a hydrophilic acrylic monomer, a hydrophobic acrylic monomer, an initiator and a solvent. The water contact angle of crude oil and other organic oils on the coating surface reaches 150 ± 10 ° C., which prevents crude oil and the like from adhering to the coating surface. [Selection diagram] Fig. 1

Description

The present invention belongs to the fields of novel polymer functional materials, high-performance polymer structural materials, and polymer coating materials, and particularly relates to paints for preventing crude oil adhesion in water, methods for preparing the same, and applications thereof.

According to a related study by the International Energy Agency (IEA), crude oil will continue to be a major source of human energy for at least the next half century. Due to the large amount of offshore oil mining and the frequent occurrence of offshore oil spills, dealing with offshore spills and oil recovery have become global issues. Therefore, many devices and methods have been developed to combat offshore spills for the purpose of recovering crude oil. However, since crude oil has a high viscosity and a hydrophobic effect, the oil adheres to the surface of the device when dealing with oil-containing wastewater or recovering the oil, and as a result, the efficiency of sewage treatment and recovery is reduced, or the device becomes It gets stuck. Therefore, it is very important to reduce the adhesion of oil to the device.

Applying a coating to the surface of the device is a simple and effective way to prevent the adhesion of crude oil. CN107779902A manufactures an antifouling coating with low adhesion of crude oil using a polymer, a cross-linking component, and a low surface energy component as raw materials. However, this coating needs to be baked at a high temperature after being applied to the surface of a base material. Therefore, it takes time and labor, the crude oil can stay on the surface of the coating for a certain period of time, and the crude oil adhesion prevention property is insufficient. In CN110484121A, polyethylene glycol, polytetramethylene ether glycol, and solvent A are uniformly mixed, isophorone diisocyanate and a catalyst are added to raise the temperature and react, and after the reaction is completed, the temperature is lowered, and then solvent B and water are used. A mixed solution is added and a polyurethane solution as an ultra-oleaic paint in water is obtained by polycondensation of polyol and isocyanate. This ultra-oleaic paint in water can effectively prevent the adhesion of crude oil, but is an iron sheet. The adhesive force to the solvent is only 131.1 kPa, and there is room for improvement. At present, a technique has not been developed in which the crude oil adhesion prevention property is close to that of CN110484121A underwater ultraoleophobic paint, and the adhesive force is stronger.

Chinese Patent Application Publication No. 110484121

The present invention belongs to the field of polyurethane materials and discloses an ultra-oleophobic paint in water and a method for preparing the same. The underwater ultraoleophobic paint can be applied onto the substrate and then by solvent exchange methods to form an underwater ultraoleophilic hydrogel coating with excellent adhesion to the substrate. The formed hydrogel coating has anti-adhesion to various oils, has an underwater contact angle of about 150 ° to various oils, and oil droplets easily roll off the hydrogel coating. Even in various harsh environments (acid immersion, alkali immersion), the ultra-oleophobic hydrogel coating in water formed by the solvent exchange method can maintain the ultra-lipophobicity in water. After soaking in water for 7 days, the polyurethane hydrogel coating did not shed and the water contact angle with peanut oil was maintained greater than 150 °.

An object of the present invention is to effectively prevent the adhesion of crude oil, and to provide a coating material for preventing the adhesion of crude oil in water having a high adhesive force, a method for preparing the same, and an application thereof.

The object of the present invention is realized by the following technical proposal.
It is a paint to prevent the adhesion of crude oil in water.
It is obtained by polymerizing a hydrophilic acrylic monomer, a hydrophobic acrylic monomer, an initiator and a hydrophilic solvent as raw materials.

The mass ratio of the hydrophilic acrylic monomer to the hydrophobic acrylic monomer is (5: 0) to (0: 5), and the mass ratio of the hydrophilic acrylic monomer and the hydrophobic acrylic monomer is not 0. .. The mass ratio of the hydrophilic acrylic monomer to the hydrophobic acrylic monomer is preferably (2.5: 2.5) to (4: 1).

The mass ratio of the total mass of the hydrophilic acrylic monomer and the hydrophobic acrylic monomer to the hydrophilic solvent is (1: 9) to (3: 2), preferably (1: 4) to (1: 1). ).

The weight of the initiator is 0.5% to 5%, preferably 0.8% to 3% of the total mass of the hydrophilic acrylic monomer and the hydrophobic acrylic monomer.

The hydrophilic acrylic monomer is at least one selected from acrylic acid, acrylamide, hydroxyethyl acrylate and hydroxypropyl acrylate.

The hydrophobic acrylic monomer is at least one selected from methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, octadecyl acrylate, octadecyl methacrylate, isobornyl acrylate and styrene.

The initiator is at least one selected from azobisisobutyronitrile, azobisisoheptnitrile, and dimethyl azobisisobutyrate.

The hydrophilic solvent is at least one selected from N, N-dimethylacetamide, N, N-dimethylformamide and dimethyl sulfoxide.

It is a method of preparing paint for preventing crude oil adhesion in water.
The step (1) of uniformly dissolving a part of the initiator in a hydrophilic solvent to obtain a mixed solution, and
The hydrophilic acrylic monomer, the hydrophobic acrylic monomer and the remaining initiator are uniformly mixed, then dropped into the mixed solution of step (1) for reaction, and when the reaction is completed, the paint for preventing crude oil adhesion in water is applied. Including step (2) of obtaining.

In step (1), the dissolution temperature of the initiator is 70 to 100 ° C.

In step (2), the reaction temperature is 70 to 100 ° C. and the reaction time is 2 to 24 hours.

In step (1) and step (2), the weight ratio of the initiator is (0: 6) to (4: 2).

Use of the above-mentioned underwater crude oil adhesion prevention paint in oil-impregnated sewage treatment, oil-water separation, crude oil mining, crude oil transportation, crude oil storage, and crude oil processing.

A method for producing an underwater crude oil adhesion preventing coating, which comprises a step of applying the underwater crude oil adhesion preventing coating to a substrate surface and then immersing the substrate in water to obtain an underwater crude oil adhesion preventing coating.

The immersion time is 10 to 120 min, preferably 60 min.

The amount of the paint for preventing crude oil adhesion in water ^{is 0.8 to 2} g / cm 2, preferably 1 to 1.4 g / cm ² .

The base material is at least one selected from glass, wood, metal, ceramics, and polymer.

In the present invention, a hydrophilic acrylic monomer and a hydrophobic acrylic monomer are used in a specific ratio to carry out radical polymerization of a vinyl group to obtain a polyacrylate solution having both a hydrophobic polyacrylate segment and a hydrophilic polyacrylate segment. Synthesized to make a paint to prevent adhesion of crude oil in water. When the underwater crude oil adhesion prevention paint is applied to the surface of the substrate and then quickly immersed in water, the hydrophilic solvent used becomes compatible with water, so the solvent exchange process, that is, the diffusion of water into the coating ( At the same time, the hydrophilic solvent in the paint diffuses into water, but this diffusion process is negligible because the amount of hydrophilic solvent is much less than the amount of water), and at the same time, the aggregation of hydrophobic chains occurs. That is, the hydrophobic polyacrylate segment aggregates on the substrate, firmly adhering the coating to the surface of the substrate, the hydrophilic polyacrylate segment is exposed at the interface between the aqueous phase and the coating, and water. The molecules can be adsorbed on the surface of the coating to form a hydrated layer, which prevents hydrophobic substances such as crude oil from adhering to the surface of the coating.
Furthermore, the hydrophobic polyacrylate segment and the hydrophilic polyacrylate segment in the paint for preventing adhesion of crude oil in water are entangled and connected, and the hydrophobic polyacrylate segment and the hydrophilic polyacrylate segment have the property of being insoluble in acids and alkalis. Therefore, the coating formed by the underwater crude oil adhesion preventive paint is provided with excellent flexibility and acid / alkali resistance.

Compared with the prior art, in the present invention, the underwater crude oil adhesion preventing paint prepared by utilizing the raw materials and the reaction mechanism having different characteristics has the following technical effects.
(1) The paint for preventing adhesion of crude oil in water has an excellent ultra-sparse oil ability in water, and the contact angle of crude oil and other organic oils in water on the coating surface reaches 150 ± 10 ° C. It cannot adhere to the coating surface.
(2) The underwater crude oil adhesion preventive paint has excellent adhesion to various substrate surfaces.
(3) Since the coating formed by the underwater crude oil adhesion preventing paint has excellent flexibility, the influence of the deformation of the base material on the underwater crude oil adhesion preventing performance is extremely small.
(4) Since the coating formed by the paint for preventing adhesion of crude oil in water has excellent acid / alkali resistance, it can maintain ultra-oleophobicity in water in aqueous solutions of various pHs.
(5) The underwater crude oil adhesion preventive paint has a simple preparation method, low energy consumption, and is suitable for industrial production.

Of n-hexane (a), hexadecane (b), toluene (c), pump oil (d), peanut oil (e) and crude oil (f) on the surface of the oil-in-water crude oil adhesion prevention coating prepared in Example 1. Underwater contact angle. It is a figure which shows the process of bending (a) the iron sheet which formed the underwater crude oil adhesion prevention coating on the surface in Example 2, then pouring crude oil (b) into the coating, and rinsing cleanly with water (c and d). It is a schematic diagram of the adhesion test, FIG. A is a process of preparing a measurement sample, and FIG. B is a process of a bond test. It is a figure which shows the data of the adhesive force to the iron sheet of the underwater crude oil adhesion prevention coating formed by exchanging a solvent with the underwater crude oil adhesion prevention paint prepared in Example 2 and Comparative Example 1.

Hereinafter, the technical proposal of the present invention will be further described with reference to specific examples.

Example 1 This example provides a coating material for preventing crude oil adhesion in water, which is obtained by polymerizing a hydrophilic acrylic monomer, a hydrophobic acrylic monomer, an initiator and a solvent as raw materials.
The hydrophilic acrylic monomer is selected from a mixture of acrylic acid and hydroxyethyl acrylate, the hydrophobic acrylic monomer is selected from a mixture of styrene, butyl acrylate and methyl methacrylate, and the initiator is azobisisobutyro. It is selected from nitrile and the solvent is selected from N, N dimethylacetamide.
The method for preparing the paint for preventing crude oil adhesion in water of this example includes the following steps.
(1) Add 0.2 g of azobisisobutyronitrile and 50 g of N, N dimethylacetamide to a dry three-necked flask equipped with a mechanical stirrer and a coagulation tube, mix and stir uniformly, and raise the temperature to 80 ° C. (The azobisisobutyronitrile was previously decomposed to generate radicals so that it would subsequently undergo radical polymerization with the monomer), and the mixture was kept warm until use.
(2) 20 g of hydrophobic acrylic monomer (including 3 g of styrene, 12 g of butyl acrylate and 5 g of methyl methacrylate), 30 g of hydrophilic acrylic monomer (including 10 g of acrylic acid and 20 g of hydroxyethyl acrylate), and azobisiso A mixture of 0.3 g of butyl nitrile was uniformly added dropwise to the mixed solution of step (1) over 1.5 hours, and the mixture was kept warm (80 ° C.) and reacted for 4 hours. After completion of the reaction, the temperature was lowered to obtain a paint for preventing crude oil adhesion in water, which is a polyacrylic acid ester solution.
As a result of measurement, the solid content of the polyacrylic acid ester solution was 50.2%.
The above-mentioned paint for preventing crude oil adhesion in water ^{was applied to the surface of an iron sheet at an amount of 1 g / cm 2} of the paint, and then immersed in water for 60 minutes to form a coating for preventing adhesion of crude oil in water on the surface of the iron sheet. ..

Example 2
The present embodiment provides a coating material for preventing crude oil adhesion in water, which is obtained by polymerizing a hydrophilic acrylic monomer, a hydrophobic acrylic monomer, an initiator and a solvent as raw materials.
Hydrophilic acrylic monomers are selected from a mixture of acrylic acid and acrylamide, hydrophobic acrylic monomers are selected from a mixture of styrene, butyl acrylate and methyl methacrylate, and initiators are selected from azobisisobutyronitrile. The solvent is selected from N, N dimethylacetamide.
The method for preparing the paint for preventing the adhesion of crude oil in water of this example includes the following steps.
(1) Add 0.2 g of azobisisobutyronitrile and 60 g of N, N dimethylacetamide to a dry three-necked flask equipped with a mechanical stirrer and an agglutinating tube, mix and stir uniformly, and raise the temperature to 85 ° C. Then, it was kept warm until it was used.
(2) Hydrophobic acrylic monomer (including 2 g of styrene, 5 g of butyl acrylate, 3 g of methyl methacrylate) 10 g, hydrophilic acrylic monomer (including 10 g of acrylic acid and 20 g of acrylamide) 30 g and azobisisobutyronitrile 0 .2 g of the mixture was uniformly added dropwise to the mixed solution of step (1) over 1 hour, and the mixture was kept warm (85 ° C.) and reacted for 4 hours. After completion of the reaction, the temperature was lowered to obtain a paint for preventing crude oil adhesion in water, which is a polyacrylic acid ester solution.
As a result of measurement, the solid content of the polyacrylic acid ester solution was 40.2%.
The above-mentioned paint for preventing crude oil adhesion in water ^{is applied to the surface of an iron sheet in an amount of 1 g / cm 2} of the paint, and then immersed in water for 60 minutes to form a coating for preventing adhesion of crude oil in water on the surface of the iron sheet. It was.

Comparative Example 1
This comparative example provides a coating material for preventing crude oil adhesion in water, which is obtained by polymerizing a hydrophilic acrylic monomer, an initiator and a solvent as raw materials.
The hydrophilic acrylic monomer is selected from a mixture of acrylic acid and acrylamide, the initiator is selected from azobisisobutyronitrile, and the solvent is selected from N, N dimethylacetamide.
The method for preparing the paint for preventing the adhesion of crude oil in water of this example includes the following steps.
(1) Add 0.2 g of azobisisobutyronitrile and 60 g of N, N dimethylacetamide to a dry three-necked flask equipped with a mechanical stirrer and an agglutinating tube, mix and stir uniformly, and raise the temperature to 85 ° C. Then, it was kept warm until it was used.
(2) A mixture of 40 g of a hydrophilic acrylic monomer (including 15 g of acrylic acid and 25 g of acrylamide) and 0.2 g of azobisisobutyronitrile is uniformly added dropwise to the mixed solution of step (1) over 1 hour to keep it warm. The reaction was carried out at (85 ° C.) for 4 hours. After completion of the reaction, the temperature was lowered to obtain a paint for preventing crude oil adhesion in water, which is a polyacrylic acid ester solution.
As a result of measurement, the solid content of the polyacrylic acid ester solution was 40.2%.
The above-mentioned paint for preventing crude oil adhesion in water ^{is applied to the surface of an iron sheet in an amount of 1 g / cm 2} of the paint, and then immersed in water for 60 minutes to form a coating for preventing adhesion of crude oil in water on the surface of the iron sheet. It was.

図１及び表１から分かるように、ｎ−ヘキサン、ヘキサデカン、トルエン、落花生油、ポンプオイル、及び原油はすべて、水中原油付着防止コーティングの表面で１５０±１０°と大きい接触角を持っており、このことから、本発明の水中原油付着防止コーティングが良好な水中疎油性を有することを示している。
さらに、実験したところ、表面にコーティングを形成した鉄シートを曲げた後、コーティングにクラックが発生することがなく、次にコーティングの表面に原油を注ぎ、その後、水でリンスすると、原油を簡単に洗い落とせることを見出した。このプロセスを図２のａ→ｄに示し、それは、コーティングは優れた柔軟性を有し、基材の変形によるその水中原油付着防止性への影響が極めて少ないことを示している。 Performance test (1) Lipophobicity and flexibility in water The iron sheet with the coating formed on the surface in Example 1 was immersed in water, and n-hexane, hexadecane, toluene, peanut oil, and pump oil on the surface of the crude oil adhesion prevention coating in water. , The water contact angle of crude oil was measured, and the results are shown in FIG. 1 and Table 1.

As can be seen from FIGS. 1 and 1, n-hexane, hexadecane, toluene, peanut oil, pump oil, and crude oil all have a large contact angle of 150 ± 10 ° on the surface of the oil-in-water crude oil adhesion prevention coating. This indicates that the oil-in-water crude oil adhesion prevention coating of the present invention has good under-water oleophobicity.
Furthermore, in the experiment, after bending the iron sheet with the coating on the surface, the coating did not crack, and then the crude oil was poured on the surface of the coating and then rinsed with water to easily remove the crude oil. I found that it could be washed off. This process is shown in FIGS. 2a → d, indicating that the coating has excellent flexibility and that deformation of the substrate has very little effect on its ability to prevent crude oil adhesion in water.

表２に示すように、各ｐＨ値の溶液環境において、水中原油付着防止コーティングの表面における原油の水中接触角は約１５０°であり、これは、本発明の水中原油付着防止コーティングが優れた酸・アルカリ耐性を有し、ｐＨによるその疎油性への影響が極めて小さいことを示している。 (2) Acid / Alkali Resistance The iron sheet whose surface was coated in Example 2 was immersed in an acid or alkali solution having a pH of 1 to 14, and at each pH, the contact angle of crude oil on the coated surface in water was measured, and the results were obtained. It is shown in Table 2.

As shown in Table 2, in the solution environment of each pH value, the underwater contact angle of crude oil on the surface of the underwater crude oil adhesion prevention coating is about 150 °, which is the acid excellent for the underwater crude oil adhesion prevention coating of the present invention. -It has alkali resistance and shows that the influence of pH on its oleophobicity is extremely small.

により水中原油付着防止用塗料が溶剤を交換して形成した水中原油付着防止コーティングの付着力を算出し、ここで、Ｆは付着力、ｋｇｆは重量キログラム、Ｓは２枚の鉄シートの貼着面積であった。
ステップ５、ステップ１〜４に従って、比較例１で調製された水中原油付着防止コーティングの付着力をテストした。
図４は、実施例２及び比較例１で調製された水中原油付着防止用塗料が溶剤を交換して形成した水中原油付着防止コーティングの鉄シートに対する付着力を示す図である。図４に示すように、親水性アクリル系モノマーと疎水性アクリル系モノマーの両方を使用して調製された水中原油付着防止用塗料（実施例２）が溶剤を交換して形成した水中原油付着防止コーティングは、付着力が１５６．２ｋＰａであり、従来技術のＣＮ１１０４８４１２１Ａの付着力１３１．１ｋＰａより高く、また、親水性アクリル系モノマーのみで調製された水中原油付着防止用塗料（比較例１）が溶剤を交換して形成した水中原油付着防止コーティングの付着力（３０．５ｋＰａ）よりも高かった。このことから、疎水性アクリル系モノマーを追加して合成された水中原油付着防止用塗料が溶剤を交換して形成した水中原油付着防止コーティングは、鉄シートへの付着力が向上することを示している。 (3) Adhesiveness The adhesiveness of the coating was tested in the next step.
The paint for preventing crude oil adhesion in water having a solid content of 40.2% prepared in Step 1 and Example 2 was applied to 1/2 of the area of the iron sheet.
In step 2, half the area of another same iron sheet was attached to the portion of the iron sheet described in step 1 coated with the oil-in-water crude oil adhesion-preventing paint having a solid content of 40.2%.
The iron sheet coated with one layer of the underwater crude oil adhesion preventive paint of steps 3 and (2) was quickly put into water and immersed for 60 minutes (see FIG. 3a for a schematic diagram).
Step 4, a tensile test was performed using a universal testing machine (a schematic diagram of the test method is shown in FIG. 3b). Obtain the value of maximum kilogram-force (kgf) in the tensile process of the coating and formulate

Calculates the adhesive force of the underwater crude oil adhesion prevention coating formed by exchanging the solvent with the underwater crude oil adhesion prevention paint. Here, F is the adhesive force, kgf is the weight kilogram, and S is the attachment of two iron sheets. It was an area.
According to Step 5 and Steps 1 to 4, the adhesive strength of the crude oil adhesion prevention coating in water prepared in Comparative Example 1 was tested.
FIG. 4 is a diagram showing the adhesive force of the underwater crude oil adhesion preventing coating formed by exchanging the solvent with the underwater crude oil adhesion preventing coating prepared in Example 2 and Comparative Example 1 to the iron sheet. As shown in FIG. 4, the underwater crude oil adhesion prevention paint (Example 2) prepared by using both the hydrophilic acrylic monomer and the hydrophobic acrylic monomer is formed by exchanging the solvent to prevent the adhesion of the crude oil in water. The coating has an adhesive force of 156.2 kPa, which is higher than the adhesive force of CN110484121A of the prior art, which is 131.1 kPa, and a paint for preventing adhesion of crude oil in water (Comparative Example 1) prepared only with a hydrophilic acrylic monomer is used as a solvent. It was higher than the adhesive force (30.5 kPa) of the underwater crude oil adhesion preventive coating formed by exchanging. From this, it was shown that the underwater crude oil adhesion prevention coating formed by exchanging the solvent with the underwater crude oil adhesion prevention paint synthesized by adding the hydrophobic acrylic monomer improves the adhesion to the iron sheet. There is.

As described above, the coating formed in water using the underwater crude oil adhesion prevention coating material of the present invention has ultra-lipophobicity and flexibility, and the in-water contact angle of crude oil and other organic oils on the coating surface is 150. It reaches ± 10 ° C, has an extremely small effect of pH on its lipophobicity, and has high adhesiveness, and can be applied to fields such as oil-containing sewage treatment, oil-water separation, crude oil mining, transportation, storage, and processing.

The above-described embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment and is made without departing from the spirit and principle of the present invention. , Combinations and simplifications are all equivalent substitution methods and are all within the scope of the invention.

Claims (8)

It is a paint to prevent the adhesion of crude oil in water.
Hydrophilic acrylic monomer which is a composition containing acrylic acid, hydroxyethyl acrylate or acrylamide as a raw material, hydrophobic acrylic monomer which is a composition containing styrene, butyl acrylate, methyl methacrylate, initiator and hydrophilic By polymerizing the solvent, the water contact angle of the crude oil and other organic oils on the coating surface formed by the underwater crude oil adhesion prevention paint reaches 150 ± 10 degrees, and the crude oil and the like adhere to the coating surface. A paint for preventing the adhesion of crude oil in water, which is characterized by being unable to do so. The mass ratio of the hydrophilic acrylic monomer to the hydrophobic acrylic monomer is (5: 0) to (0: 5), and the mass of both the hydrophilic acrylic monomer and the hydrophobic acrylic monomer is not 0. The coating material for preventing adhesion of crude oil in water according to claim 1, wherein the coating material is characterized by the above. The first aspect of claim 1, wherein the mass ratio of the total mass of the hydrophilic acrylic monomer and the hydrophobic acrylic monomer to the hydrophilic solvent is (1: 9) to (3: 2). Paint for preventing adhesion of crude oil in water. The coating material for preventing crude oil adhesion in water according to claim 1, wherein the weight of the initiator is 0.5% to 5% of the total mass of the hydrophilic acrylic monomer and the hydrophobic acrylic monomer. The coating material for preventing crude oil adhesion in water according to claim 1, wherein the initiator is at least one selected from azobisisobutyronitrile, azobisisoheptnitrile, and dimethyl azobisisobutyrate. The method for preparing a coating material for preventing crude oil adhesion in water according to any one of claims 1 to 5 , wherein a part of the initiator is uniformly dissolved in a hydrophilic solvent to obtain a mixed solution (1). When,
The hydrophilic acrylic monomer, the hydrophobic acrylic monomer and the remaining initiator are uniformly mixed, then dropped into the mixed solution of step (1) for reaction, and when the reaction is completed, the paint for preventing crude oil adhesion in water is applied. A preparation method comprising the step (2) of obtaining. Use of the underwater crude oil adhesion prevention paint according to any one of claims 1 to 5 in oil-impregnated sewage treatment, oil-water separation, crude oil mining, crude oil transportation, crude oil storage or crude oil processing. A method for manufacturing an underwater crude oil adhesion prevention coating.
A production method comprising the step of applying the underwater crude oil adhesion preventing paint according to any one of claims 1 to 5 to the surface of a base material and then immersing the substrate in water to obtain an underwater crude oil adhesion preventing coating. ..

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