Dispersant for dispersing heavy element single substance and compound powder and preparation method thereof

Abstract

The present invention belongs to the technical field of fine chemical industry, and discloses a dispersant for dispersing heavy element single substance and compound powder and a preparation method thereof, wherein the main function is to be used as a powder dispersant, especially suitable for dispersing heavy element powder that is easy to settle; bismuth powder, lead powder, tungsten powder, lead oxide, lead tetraoxide, bismuth oxide, tungsten oxide, lead tungstate, lead borate and other functional particles with shielding ability. The anionic dispersant containing multiple hydrophilic groups such as sulfonic acid group, ester group and hydroxyl group in the structural formula is used to disperse heavy element powder, which can neutralize the excess charge on the oxide surface and wrap the powder particles, and finally form a uniform and stable high-content heavy element powder latex system, creating conditions for preparing radiation-proof latex products.

Description

Technical Field

[0001] The invention belongs to the technical field of fine chemical industry, and in particular relates to a dispersant for dispersing heavy element simple substance and compound powder and a preparation method thereof. Background Art

[0002] In the production process of radiation-proof latex products, a large amount of heavy element single substance and compound powders need to be added to the latex, such as bismuth powder, lead powder, tungsten powder, lead oxide, lead tetraoxide, bismuth oxide, tungsten oxide, lead tungstate, lead borate and other functional particles with shielding ability. However, due to the high density of these powders, they are easy to settle in the latex and it is difficult to form a uniform dispersion system; in addition, the surface of these powder particles is often rich in charge, which is easy to destroy the double electric layer on the surface of the latex particles, thereby causing the latex to break and cause flocculation. Therefore, it is necessary to use a dispersant to modify these powder fillers, enhance their dispersibility in the latex, and neutralize their surface charge. Commonly used dispersants are coupling agents and anionic types. The former mainly includes silanes, titanates, aluminates, etc.; the latter mainly includes carboxylates, sulfonates, etc. These dispersants are effective for medium and low content (mass fraction <60%) of heavy element compound latex systems, but it is difficult to achieve a good dispersion effect for high content (mass fraction >60%) of heavy element compound latex.

[0003] Through the above analysis, the problems and defects of the prior art are: it is necessary to develop a dispersant for dispersing heavy element powders. Summary of the invention

[0004] In view of the problems existing in the prior art, the present invention provides a dispersant for dispersing heavy element single substance and compound powders and a preparation method thereof.

[0005] The present invention is achieved by using a dispersant for dispersing heavy element single substance and compound powder, wherein the dispersant is an anionic dispersant and has the following structural formula:

[0006]

[0007] Another object of the present invention is to provide a method for preparing a dispersant for dispersing heavy element simple substance and compound powder, comprising the following steps:

[0008] Step 1: weigh 50g of 1,4-dibromobutane and add it to a dry three-necked flask with a condenser, a thermometer and a stirrer, then add 0.2g of tributyltin and 30mL of chloroform to the three-necked flask, stir for 5min, increase the temperature to 50°C, reflux for 100-120min, and cool to room temperature; add 2g of phenylboric acid, stir for 5min, then heat to 50°C, reflux for 60-80min, and obtain the product.

[0009] Step 2: Add 5 g of sodium hydroxide and 30 mL of ethanol to the above product, reflux at 100 ° C for 30 min, then add 5 mL of liquid bromine, stir for 10 min, add 5 g of sodium hydroxide and 30 mL of ethanol after fading, and then reflux at 100 ° C for 30 min to obtain the product.

[0010] Step 3: Add 20 g of methyl bromoacetate and 50 mL of tetrahydrofuran to the above product, then reflux at 80 ° C for 30 min, then introduce 3 L of HBr gas, and after the reaction is completed, add 50 mL of concentrated sulfuric acid and reflux for 100 min to obtain the product.

[0011] Step 4: Add 20 g of polyethylene glycol, 5 g of sodium hydroxide and 50 mL of tetrahydrofuran to the above product, and then reflux at 100 ° C for 60 min to obtain the product

[0012] Another object of the present invention is to provide a dispersant for dispersing heavy element single substances and compound powders for dispersing functional particles with shielding capabilities such as bismuth powder, lead powder, tungsten powder, lead oxide, lead tetroxide, bismuth oxide, tungsten oxide, lead tungstate, and lead borate.

[0013] Another object of the present invention is to provide a dispersant for dispersing heavy element single substance and compound powders for preparing aqueous slurries of bismuth powder, lead powder, tungsten powder, lead oxide, lead tetroxide, bismuth oxide, tungsten oxide, lead tungstate, and lead borate.

[0014] Furthermore, bismuth powder, lead powder, tungsten powder, lead oxide, lead tetroxide, bismuth oxide, tungsten oxide, lead tungstate, and lead borate slurries are suitable for use in aqueous or latex systems and are used as protective functional fillers when preparing radiation protection products.

[0015] In combination with the above technical solutions and the technical problems solved, the advantages and positive effects of the technical solutions to be protected by the present invention are as follows:

[0016] First, based on the characteristics of heavy element powders, such as high density and rich surface charges, the present invention designs an anionic dispersant containing multiple hydrophilic groups, such as sulfonic acid group, ester group and hydroxyl group, for dispersing heavy element powders. The anionic dispersant can not only neutralize the excess charge on the powder surface, but also wrap the powder particles, and finally form a uniform and stable high-content (mass fraction > 80%) heavy element powder latex system, creating conditions for the preparation of radiation-proof latex products.

[0017] Second, heavy element single substance and compound powders, such as bismuth, lead, tungsten and their compounds, have poor dispersion in coatings, plastics and other matrices, and are prone to agglomeration and sedimentation, resulting in reduced material performance and limiting their application in radiation protection and other fields. Traditional dispersants have unsatisfactory dispersion effects on these powders and are difficult to meet the requirements of high-performance protective materials.

[0018] The present invention provides a novel anionic dispersant, whose unique molecular structure design enables it to have excellent adsorption and dispersion capabilities for heavy element powders. The hydrophilic group of the dispersant interacts with the surface of the powder to form a stable adsorption layer, effectively preventing the agglomeration of powder particles and improving dispersion stability.

[0019] The present invention also provides a simple and efficient method for preparing a dispersant, and the target product can be obtained through a few steps of reaction. The method has readily available raw materials, is simple to operate, and has low cost, is suitable for industrial production, and provides technical support for the large-scale application of heavy element powder dispersants.

[0020] The dispersant of the present invention exhibits excellent performance in the preparation of aqueous slurries, can effectively disperse heavy element powders, and prepare aqueous slurries with high solid content, low viscosity, and good stability. These slurries can be widely used in radiation protection coatings, plastics, rubber and other materials, significantly improving the shielding performance and processing performance of the materials, and expanding the application range of heavy element powders.

[0021] Third, the expected benefits and commercial value of the technical solution of the present invention after transformation are:

[0022] The patent of the present invention solves the problem that powders of bismuth, lead, tungsten and their compounds are easy to settle in an aqueous / latex system due to their high density, and promotes these powders to form a homogenous system in the aqueous / latex system, so that products such as radiation-proof clothing and radiation-proof gloves can be prepared. Moreover, this homogenous system uses water as a solvent, which is very environmentally friendly compared to an organic solvent system; the product has low cost and high commercial value.

[0023] The technical solution of the present invention solves a technical problem that people have been eager to solve but have never been successful: powders of bismuth, lead, tungsten and their compounds with high solid content are very easy to settle in aqueous / latex systems and it is difficult to form a homogeneous water-soluble system, which has always been a problem that people have been eager to solve; the modified and prepared by the invention can well coat these powders and disperse them in the aqueous phase / latex system to form a homogeneous system.

[0024] Fourth, the present invention solves the technical problems of the prior art and achieves significant technical progress.

[0025] 1. Difficulties in dispersing heavy element single substance and compound powders in existing technologies

[0026] In the prior art, heavy element single substance and compound powders have poor dispersibility and are prone to agglomeration, which results in their inability to fully exert their functionality in practical applications. Especially in water-based systems, due to the high density and high surface energy of heavy element powders, traditional dispersants are difficult to effectively disperse these powders evenly, thus affecting the quality and performance of the product.

[0027] 2. Solution of the present invention

[0028] The present invention provides a novel anionic dispersant, which is synthesized by multi-step chemical reactions. The molecular structure of the dispersant is reasonably designed, has strong dispersing ability and good chemical stability, and can effectively solve the problem that heavy element single substance and compound powder are easy to agglomerate during the dispersion process. The specific steps include the reaction of 1,4-dibromobutane and tributyltin in chloroform, followed by multiple reflux and reaction steps, introducing chemical substances such as phenylboric acid, liquid bromine, methyl bromoacetate, polyethylene glycol, etc., and finally obtaining an anionic dispersant.

[0029] 3. Significant technological advances in industrial applications

[0030] The anionic dispersant of the present invention can significantly improve the dispersibility of heavy element single substance and compound powder in an aqueous system, and is suitable for the dispersion of functional particles with shielding ability such as bismuth powder, lead powder, tungsten powder, lead oxide, lead tetraoxide, bismuth oxide, tungsten oxide, lead tungstate, lead borate, etc. The aqueous slurry prepared by using the dispersant of the present invention has greatly improved the protective performance in radiation protection products, ensuring the uniform distribution and effective effect of the protective functional filler.

[0031] 4. Practical application effects and advantages

[0032] The dispersant of the present invention exhibits excellent dispersing effect in practical applications, can form a stable dispersed state in an aqueous phase or latex system, significantly reduce the agglomeration of powders, and improve the stability and uniformity of the slurry. The protective functional filler prepared using the dispersant of the present invention not only improves the protective effect in radiation protection products, but also simplifies the production process, reduces the production cost, and has broad application prospects and economic benefits. These significant technical advances and advantages make the present invention have important practical value and innovative significance in industrial applications.

[0033] Fifth, the main parameters of the present invention, the existing technical problems solved and the significant technical progress achieved.

[0034] 1. Main parameters of the present invention

[0035] The invention provides an anionic dispersant for dispersing heavy element single substance and compound powders, which specifically comprises the following main parameters: in a dry three-necked flask, 50g of 1,4-dibromobutane, 0.2g of tributyltin and 30mL of chloroform are used to reflux at 50°C for 100-120 minutes; 2g of phenylboric acid is added and the reflux is continued for 60-80 minutes; 5g of sodium hydroxide and 30mL of ethanol are added and the mixture is refluxed at 100°C for 30 minutes, 5mL of liquid bromine is added and the mixture is stirred until discoloration occurs, and 5g of sodium hydroxide and 30mL of ethanol are added again and the mixture is refluxed for 30 minutes; 20g of methyl bromoacetate and 50mL of tetrahydrofuran are added and the mixture is refluxed at 80°C for 30 minutes, 3L of HBr gas is introduced and 50mL of concentrated sulfuric acid is added and the mixture is refluxed for 100 minutes; finally, 20g of polyethylene glycol, 5g of sodium hydroxide and 50mL of tetrahydrofuran are added and the mixture is refluxed at 100°C for 60 minutes to obtain the anionic dispersant.

[0036] 2. Existing technical problems solved

[0037] In the prior art, heavy element single substance and compound powders have poor dispersibility in aqueous systems and are prone to agglomeration, which greatly affects their performance and effects in industrial applications. Traditional dispersants cannot effectively solve the high density and high surface energy problems of these powders, resulting in poor stability and insufficient uniformity of the prepared aqueous slurry, thus affecting product quality and application effects. In addition, the preparation process of existing dispersants is complex and costly, making it difficult to achieve large-scale industrial applications.

[0038] 3. Significant technological progress achieved

[0039] The present invention successfully prepares an anionic dispersant with strong dispersibility and good chemical stability by introducing specific chemical reaction steps and optimized reaction conditions. The dispersant effectively solves the dispersibility problem of heavy element single substance and compound powder in an aqueous system, significantly improves the dispersion effect of the powder and the stability of the aqueous slurry. By using the dispersant of the present invention, a stable dispersion state can be formed in an aqueous phase or latex system, reducing the agglomeration of the powder, and improving the protective performance and quality of the product.

[0040] 4. Practical application effects and advantages

[0041] The present invention has demonstrated significant technological progress and practical effects in industrial applications. The protective functional filler prepared using the dispersant of the present invention exhibits excellent protective effect and uniformity in radiation protection products, and improves the performance and reliability of the products. In addition, the preparation process of the dispersant of the present invention is relatively simple, the cost is low, and it is easy to achieve large-scale production and application. In general, the present invention not only solves the key problems in the prior art, but also significantly improves the dispersion effect and product quality of heavy element single substances and compound powders in industrial applications, and has broad application prospects and economic benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments of the present invention. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0043] Figure 1 This is a flow chart of a method for preparing a dispersant for dispersing heavy element single substance and compound powders provided in an embodiment of the present invention;

[0044] Figure 2 It is the hydrogen spectrum of the product provided in the embodiment of the present invention.

[0045] Figure 3 (a) The dispersibility of bismuth powder in latex without using the modifier of the present invention (easy to separate), (b) The dispersibility of bismuth powder in latex with using the modifier of the present invention (no separation).

[0046] Figure 4 A scanning electron microscope photograph of a cross section of a sample prepared using bismuth powder latex using the dispersant of the present invention. DETAILED DESCRIPTION

[0047] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0048] The following are two specific examples for illustrating how to prepare and use the anionic dispersant as described in claim 1 to disperse heavy element single substance and compound powders and prepare corresponding aqueous slurries.

[0049] Embodiment 1:

[0050] Preparation of anionic dispersants: Prepare anionic dispersants according to the method described in claim 2.

[0051] 1. Mix 50 g of 1,4-dibromobutane, 0.2 g of tributyltin and 30 mL of chloroform in a three-necked flask, stir for 5 min, then heat to 50 °C and reflux for 100 min.

[0052] 2. After cooling to room temperature, add 2 g of phenylboric acid, stir again for 5 min, then heat to 50 °C and reflux for 60 min.

[0053] 3. Add 5 g of sodium hydroxide and 30 mL of ethanol to the reaction mixture and reflux at 100°C for 30 min. Then add 5 mL of liquid bromine, stir until it fades, then add 5 g of sodium hydroxide and 30 mL of ethanol and continue to reflux for 30 min.

[0054] 4. Next, add 20 g of methyl bromoacetate and 50 mL of tetrahydrofuran to the reaction mixture and reflux at 80°C for 30 min. Then, introduce 3 L of HBr gas, and after the reaction is complete, add 50 mL of concentrated sulfuric acid and reflux for 100 min.

[0055] 5. Finally, add 20 g of polyethylene glycol, 5 g of sodium hydroxide and 50 mL of tetrahydrofuran, and reflux at 100°C for 60 min to obtain the desired anionic dispersant.

[0056] Preparation of aqueous bismuth powder slurry:

[0057] 1. Mix the prepared anionic dispersant and bismuth powder in a certain proportion, add an appropriate amount of deionized water, and stir and disperse in a stirrer.

[0058] 2. Continue stirring until the bismuth powder is evenly dispersed in the water to form a stable aqueous bismuth powder slurry.

[0059] Embodiment 2:

[0060] Preparation of anionic dispersant (same steps as previous example)

[0061] (The repeated steps are omitted here, which is the same as the previous example)

[0062] Preparation of aqueous lead oxide slurry:

[0063] 1. Mix the prepared anionic dispersant and lead oxide powder in a certain proportion, add an appropriate amount of deionized water and an appropriate amount of dispersing aid (such as ethylene glycol, etc.) to improve the stability and dispersibility of the slurry.

[0064] 2. Stir at high speed in a blender to evenly disperse the lead oxide powder in the water.

[0065] 3. During the stirring process, the stirring speed and the amount of dispersant can be adjusted appropriately to achieve the best dispersion effect.

[0066] 4. After the stirring is completed, a stable aqueous slurry of lead oxide is obtained, which can be used for the preparation of radiation protection products and other applications.

[0067] These two examples show how to prepare anionic dispersants and use them to disperse bismuth powder and lead oxide powder respectively to form stable aqueous slurries. These slurries can be used to prepare various radiation protection products or other applications requiring heavy element single substance and compound powders.

[0068] The dispersant for dispersing heavy element single substance and compound powder provided in the embodiment of the present invention is an anionic dispersant, and the structural formula is as follows:

[0069]

[0070] like Figure 1 As shown, a method for preparing a dispersant for dispersing heavy element single substance and compound powder provided in an embodiment of the present invention comprises the following steps:

[0071] Step 1: weigh 50g of 1,4-dibromobutane and add it to a dry three-necked flask with a condenser, a thermometer and a stirrer, then add 0.2g of tributyltin and 30mL of chloroform to the three-necked flask, stir for 5min, increase the temperature to 50°C, reflux for 100-120min, and cool to room temperature; add 2g of phenylboric acid, stir for 5min, then heat to 50°C, reflux for 60-80min, and obtain the product.

[0072] Step 2: Add 5 g of sodium hydroxide and 30 mL of ethanol to the above product, reflux at 100 ° C for 30 min, then add 5 mL of liquid bromine, stir for 10 min, add 5 g of sodium hydroxide and 30 mL of ethanol after fading, and then reflux at 100 ° C for 30 min to obtain the product.

[0073] Step 3: Add 20 g of methyl bromoacetate and 50 mL of tetrahydrofuran to the above product, then reflux at 80 ° C for 30 min, then introduce 3 L of HBr gas, and after the reaction is completed, add 50 mL of concentrated sulfuric acid and reflux for 100 min to obtain the product.

[0074] Step 4: Add 20 g of polyethylene glycol, 5 g of sodium hydroxide and 50 mL of tetrahydrofuran to the above product, and then reflux at 100 ° C for 60 min to obtain the product

[0075] The hydrogen spectrum of the product is as follows Figure 2 shown.

[0076] The embodiments of the present invention have achieved some positive effects in the process of research and development or use, and have great advantages over the prior art. The following content is described in combination with the data, charts, etc. of the test process. Bismuth powder is evenly dispersed in the latex system ( Figure 3 ), and after drying, a uniform composite material ( Figure 4 ); Figure 3 (a) The dispersibility of bismuth powder in latex without using the modifier of the present invention (easy to separate), (b) The dispersibility of bismuth powder in latex with using the modifier of the present invention (no separation). Figure 4A scanning electron microscope photograph of a cross section of a sample prepared using bismuth powder latex using the dispersant of the present invention.

[0077] The above description is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Any modifications, equivalent substitutions and improvements made by any technician familiar with the technical field within the technical scope disclosed by the present invention and within the spirit and principle of the present invention should be covered by the protection scope of the present invention.

Claims

1. An anionic dispersant for dispersing heavy element single substance and compound powder, characterized in that: The dispersant is prepared by the following steps: Step 1: 50 g of 1,4-dibromobutane, 0.2 g of tributyltin and 30 mL of chloroform are mixed in a three-necked flask, heated to 50° C. and refluxed for 100 to 120 minutes under stirring; Step 2, after the reaction mixture is cooled to room temperature, 2 g of phenylboric acid is added, stirred again and heated to 50° C. and refluxed for 60 to 80 minutes; Step 3: add 5 g of sodium hydroxide and 30 mL of ethanol to the above mixture, reflux at 100° C. for 30 minutes, then add 5 mL of liquid bromine, stir until discoloration, then add 5 g of sodium hydroxide and 30 mL of ethanol, and continue to reflux for 30 minutes; Step 4: add 20 g of methyl bromoacetate and 50 mL of tetrahydrofuran to the product obtained in step 3, reflux at 80° C. for 30 minutes, then introduce 3 L of HBr gas, and after the reaction is completed, add 50 mL of concentrated sulfuric acid and reflux for 100 minutes; Step 5. Finally, add 20 g of polyethylene glycol, 5 g of sodium hydroxide and 50 mL of tetrahydrofuran to the product obtained in step 4, and reflux at 100° C. for 60 minutes to obtain the anionic dispersant.

2. A method for preparing an anionic dispersant for dispersing heavy element single substance and compound powder as claimed in claim 1, characterized in that: The following steps are involved: Step 1: weigh 50g of 1,4-dibromobutane and add it to a dry three-necked flask with a condenser, a thermometer and a stirrer, then add 0.2g of tributyltin and 30mL of chloroform to the three-necked flask, stir for 5min, increase the temperature to 50°C, reflux for 100-120min, and cool to room temperature; add 2g of phenylboric acid, stir for 5min, then heat to 50°C, reflux for 60-80min, and obtain the product. Step 2: Add 5 g of sodium hydroxide and 30 mL of ethanol to the above product, reflux at 100 ° C for 30 min, then add 5 mL of liquid bromine, stir for 10 min, add 5 g of sodium hydroxide and 30 mL of ethanol after fading, and then reflux at 100 ° C for 30 min to obtain the product. Step 3: add 20 g of methyl bromoacetate and 50 mL of tetrahydrofuran to the above product, then reflux at 80° C. for 30 min, then introduce 3 L of HBr gas, and after the reaction is completed, add 50 mL of concentrated sulfuric acid and reflux for 100 min. Get the product Step 4: Add 20 g of polyethylene glycol, 5 g of sodium hydroxide and 50 mL of tetrahydrofuran to the above product, and then reflux at 100 ° C for 60 min to obtain the product 3. An anionic dispersant for dispersing heavy element single substance and compound powders as claimed in claim 1 is used to disperse functional particles with shielding ability such as bismuth powder, lead powder, tungsten powder, lead oxide, lead tetroxide, bismuth oxide, tungsten oxide, lead tungstate, and lead borate.

4. An application of the anionic dispersant for dispersing heavy element single substance and compound powders as claimed in claim 1 for preparing aqueous slurries of bismuth powder, lead powder, tungsten powder, lead oxide, lead tetroxide, bismuth oxide, tungsten oxide, lead tungstate, and lead borate.

5. An aqueous slurry of heavy element simple substance and compound powder prepared by using the anionic dispersant for dispersing heavy element simple substance and compound powder as claimed in claim 1, characterized in that: The aqueous slurry is obtained by mixing heavy element single substance or compound powder with the anionic dispersant in a certain proportion, adding appropriate amount of deionized water and dispersing aid, and uniformly dispersing under stirring conditions; the aqueous slurry is suitable for use in an aqueous phase or latex system as a protective functional filler when preparing radiation protection products.

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