Preparation method of rose-shaped barium sulfate and application of rose-shaped barium sulfate in high-gloss cyan black master batch
Rose-shaped barium sulfate, prepared by adding a gemini surfactant to a PET matrix, solves the problem of insufficient gloss in the pre-spinning coloring method, and realizes the preparation of high-gloss bluish-black masterbatch, which is suitable for textile fabrics and clothing.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- QUANGANG PETROCHEM RES INST OF FUJIAN NORMAL UNIV
- Filing Date
- 2024-01-29
- Publication Date
- 2026-06-19
Smart Images
Figure CN118047410B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of inorganic materials technology, specifically relating to a method for preparing rose-shaped barium sulfate and its application in high-gloss bluish-black masterbatch. Background Technology
[0002] In recent years, the rapid development of the chemical fiber industry has promoted the continuous maturation of PET fiber filament production technology in my country. With the continuous improvement of social living standards, a series of functional and differentiated fiber production technologies have been industrialized, providing new high-quality fiber raw materials for textile fabrics, clothing, and home textile products. The production methods for PET black filament include post-spinning dyeing and pre-spinning coloring. Post-spinning dyeing has drawbacks such as significant environmental pollution, high equipment requirements, and fiber damage. Therefore, pre-spinning coloring is the mainstream technology for preparing black filament, and its key lies in the preparation of black masterbatch. Currently, black fabrics prepared from fiber-grade polyester black masterbatch have a dull and lackluster luster. Therefore, improving the performance of black masterbatch to produce fibers with high gloss is an urgent problem to be solved.
[0003] High-gloss bluish-black masterbatch is currently a blank area. Bluish-black masterbatch needs a certain degree of gloss to fully demonstrate its advantages, resulting in bluish-black fabrics with a glossy and vibrant color. Research results show that adding a certain amount of inorganic particulate barium sulfate (BaSO4) with a refractive index similar to that of PET matrix can improve the optical properties of PET material, thereby obtaining bluish-black masterbatch with good gloss. Summary of the Invention
[0004] The purpose of this invention is to provide a method for preparing rose-shaped barium sulfate and its application in high-gloss bluish-black masterbatch. The barium sulfate particles prepared by the method of this invention exhibit a unique rose-like shape, possessing a special multidimensional rose-shaped crystal structure and good dispersibility.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] A method for preparing rose-shaped barium sulfate includes the following steps:
[0007] 1) In a three-necked flask containing solvent 1, Na2SO4 solution is added while magnetically stirring under constant temperature conditions to obtain solution A;
[0008] 2) In a three-necked flask containing solvent 2, BaCl2 solution is added while magnetically stirring under constant temperature to obtain solution B;
[0009] 3) While stirring, slowly add solution A to solution B to obtain a mixed solution. At the same time, use a titration method to slowly add the Gemini surfactant to the mixed solution. After stirring and reacting thoroughly, let it stand for 24-28 hours. Wash the obtained white precipitate in sequence, filter it, and dry it to obtain white rose-shaped barium sulfate.
[0010] Further, in step 1), the solvent 1 is at least one of ethanol, acetone, and hexane, the concentration of the Na2SO4 solution is 0.1 to 0.5 mol / L, and the volume ratio of the solvent 1 to the Na2SO4 solution is 10 to 15:1.
[0011] Further, in step 2), the solvent 2 is at least one of ethanol, acetone, and hexane, and the concentration of the BaCl2 solution is 0.1 to 0.5 mol / L; the volume ratio of the solvent 2 to the BaCl2 solution is 10 to 15:1.
[0012] Furthermore, in steps 1) and 2), the constant temperature condition is 25–30°C, the magnetic stirring speed is 2000–4000 r / min, and the stirring time is 30–60 min.
[0013] Further, in step 3), the gemini surfactant is at least one of the following: cocamidopropyl-PG-dimethylammonium chloride phosphate sodium anionic gemini surfactant CPB-40, quaternary ammonium salt cationic gemini surfactant GC-A, and alkynyldiol gemini nonionic surfactant 104BC.
[0014] Further, in step 3), the dripping rate of the surfactant is 40-50 drops / min, the reaction temperature is 70℃-85℃, and the reaction time is 10h-12h.
[0015] Furthermore, the rose-shaped barium sulfate obtained by this invention, as characterized by SEM, has a rose-shaped crystal morphology with an average particle size of 15-30 nm, and can be used in bluish-black masterbatch to give it high gloss.
[0016] The present invention has the following beneficial effects:
[0017] (1) This invention employs a two-component reaction method, adding Gemini surfactants to prepare barium sulfate under certain conditions. Traditional surfactants tend to dissolve in aqueous solutions due to their hydrophilic head groups, while their hydrophobic groups inhibit the dissolution of surfactant molecules in water. Unlike traditional surfactants, Gemini surfactants are "dimers" linked together by spacer groups, resulting in higher surface activity, lower critical micelle concentration, better wetting properties, and stronger emulsifying and antibacterial capabilities. This can more effectively reduce the surface tension of water and the oil / water interfacial tension, which is beneficial for barium sulfate crystal growth, forming a special multidimensional rose-shaped crystal structure. This barium sulfate possesses a special multidimensional rose-shaped crystal structure and good dispersibility. Compared to ordinary barium sulfate particles, the rose-shaped barium sulfate, when applied to bluish-black masterbatch, can give the masterbatch a higher gloss.
[0018] (2) The rose-shaped barium sulfate prepared in this invention has a similar refractive index to the PET matrix. When added to the PET matrix, it can improve the optical properties of the PET material, thereby obtaining a bluish-black masterbatch with good gloss.
[0019] (3) The raw materials of this invention are readily available, the reaction process is simple, and it is easier to achieve industrial production. Attached Figure Description
[0020] Figure 1 This is a SEM image of the rose-shaped barium sulfate prepared in Example 1 of the present invention.
[0021] Figure 2 This is a SEM image of barium sulfate prepared in Comparative Example 1 of the present invention.
[0022] Figure 3 This is a SEM image of barium sulfate prepared in Comparative Example 2 of the present invention. Detailed Implementation
[0023] The present invention will be described in more detail below through specific embodiments, but the scope of protection of the present invention is not limited to these embodiments.
[0024] Example 1
[0025] A method for preparing rose-shaped barium sulfate includes the following steps:
[0026] 1) In a three-necked flask containing a mixture of 5 ml ethanol and 40 ml hexane, 3 ml of 0.15 mol / L Na2SO4 solution was added while stirring magnetically at a constant temperature of 25 °C and a stirring speed of 2500 r / min. The mixture was stirred for 45 min to obtain solution A.
[0027] 2) In a three-necked flask containing a mixture of 5 ml acetone and 35 ml hexane, 3.5 ml of 0.1 mol / L BaCl2 solution was added while stirring magnetically at a constant temperature of 26 °C and a stirring speed of 3000 r / min. The mixture was stirred for 45 min to obtain solution B.
[0028] 3) While stirring, slowly add solution A to solution B. At the same time, use a titration method to slowly add the acetylacetonate gemini nonionic surfactant 104BC to the mixed solution at a rate of 40 drops / min. Stir the reaction thoroughly at 70℃ for 10 hours. After standing for 24 hours, a white precipitate is obtained. After washing, filtration and drying, a white rose-shaped barium sulfate powder is obtained.
[0029] Example 2
[0030] A method for preparing rose-shaped barium sulfate includes the following steps:
[0031] 1) In a three-necked flask containing a mixture of 4.5 ml acetone and 35 ml hexane, 3.5 ml of 0.1 mol / L Na2SO4 solution was added while stirring magnetically at a constant temperature of 26 °C and a stirring speed of 2000 r / min. The mixture was stirred for 40 min to obtain solution A.
[0032] 2) In a three-necked flask containing a mixture of 4 ml ethanol and 30 ml hexane, 2.5 ml of 0.15 mol / L BaCl2 solution was added while stirring magnetically at a constant temperature of 25 °C and a stirring speed of 2500 r / min. The mixture was stirred for 40 min to obtain solution B.
[0033] 3) While stirring, solution A was slowly added to solution B. At the same time, the anionic gemini surfactant CPB-40, sodium cocamidopropyl-PG-dimethylammonium chloride phosphate, was slowly added to the mixed solution at a rate of 45 drops / min using a titration method. The mixture was stirred thoroughly at 75°C for 10.5 hours. After standing for 24 hours, a white precipitate was obtained. This precipitate was washed, filtered, and dried to obtain white rose-shaped barium sulfate powder.
[0034] Example 3
[0035] A method for preparing rose-shaped barium sulfate includes the following steps:
[0036] 1) In a three-necked flask containing a mixture of 5 ml acetone and 45 ml hexane, 4.5 ml of 0.125 mol / L Na2SO4 solution was added while stirring magnetically at a constant temperature of 28 °C and a stirring speed of 3500 r / min. The mixture was stirred for 60 min to obtain solution A.
[0037] 2) In a three-necked flask containing a mixture of 5 ml ethanol and 50 ml hexane, 3.5 ml of 0.125 mol / L BaCl2 solution was added while stirring magnetically at a constant temperature of 27 °C and a stirring speed of 3500 r / min. The mixture was stirred for 60 min to obtain solution B.
[0038] 3) While stirring, slowly add solution A to solution B. At the same time, use a titration method to slowly add quaternary ammonium salt cationic gemini surfactant GC-A to the mixed solution at a rate of 50 drops / min. Stir the reaction thoroughly at 80℃ for 11 hours. After standing for 24 hours, a white precipitate is obtained. After washing, filtration and drying, a white rose-shaped barium sulfate powder is obtained.
[0039] Example 4
[0040] A method for preparing high-gloss bluish-black masterbatch using rose-shaped barium sulfate includes the following steps:
[0041] 1) In a three-necked flask containing a mixture of 6 ml ethanol and 48 ml hexane, 5 ml of 0.175 mol / L Na2SO4 solution was added while stirring magnetically at a constant temperature of 30 °C and a stirring speed of 4000 r / min. The mixture was stirred for 55 min to obtain solution A.
[0042] 2) In a three-necked flask containing a mixture of 5.5 ml acetone and 47 ml hexane, 5 ml of 0.175 mol / L BaCl2 solution was added while stirring magnetically at a constant temperature of 27 °C and a stirring speed of 4000 r / min. The mixture was stirred for 55 min to obtain solution B.
[0043] 3) While stirring, slowly add solution A to solution B. At the same time, use a titration method to slowly add the amphoteric Gemini surfactant to the mixed solution at a rate of 50 drops / min. Stir the reaction thoroughly at a reaction temperature of 85℃ for 12 hours. After standing for 24 hours, a white precipitate is obtained. After washing, filtration and drying, a white rose-shaped barium sulfate powder is obtained.
[0044] Comparative Example 1
[0045] A method for preparing barium sulfate, comprising the following steps:
[0046] 1) In a three-necked flask containing a mixture of 5 ml ethanol and 40 ml hexane, 3 ml of 0.15 mol / L Na2SO4 solution was added while stirring magnetically at a constant temperature of 25 °C and a stirring speed of 2500 r / min. The mixture was stirred for 45 min to obtain solution A.
[0047] 2) In a three-necked flask containing a mixture of 5 ml acetone and 35 ml hexane, 3.5 ml of 0.1 mol / L BaCl2 solution was added while magnetically stirring at a stirring speed of 3000 r / min under constant temperature of 26 °C to obtain solution B;
[0048] 3) While stirring, slowly add solution A to B. At the same time, use a titration method to slowly add the sodium sulfonate surfactant of fatty acid methyl ester ethoxylate at a rate of 40 drops / min to the mixed solution. Stir the reaction thoroughly at 70℃ for 10 hours. After standing for 24 hours, the white precipitate obtained is washed, filtered, and dried to obtain white barium sulfate powder.
[0049] The difference between Comparative Example 1 and Example 1 is that the surfactant used in step 3) is sodium sulfonate of fatty acid methyl ester ethoxylate.
[0050] Comparative Example 2
[0051] 1) In a three-necked flask containing a mixture of 5 ml ethanol and 40 ml hexane, 3 ml of 0.15 mol / L Na2SO4 solution was added while stirring magnetically at a constant temperature of 25 °C and a stirring speed of 2500 r / min. The mixture was stirred for 45 min to obtain solution A.
[0052] 2) In a three-necked flask containing a mixture of 5 ml acetone and 35 ml hexane, 3.5 ml of 0.1 mol / L BaCl2 solution was added while magnetically stirring at a stirring speed of 3000 r / min under constant temperature of 26 °C to obtain solution B;
[0053] 3) While stirring, slowly add solution A to B, and simultaneously use a titration method to slowly add the organosilicon surfactant to the mixed solution at a rate of 40 drops / min. Stir the reaction thoroughly at 70℃ for 10 hours. After standing for 24 hours, the white precipitate obtained is washed, filtered, and dried to obtain white barium sulfate powder.
[0054] Step 3: While stirring, slowly add solution A obtained in Step 1 to solution B obtained in Step 2. At the same time, use a titration method to slowly add the organosilicon surfactant to the mixed solution at a rate of 40 drops / min. Stir the reaction thoroughly at a reaction temperature of 70℃ for 10 hours. After standing for 24 hours, the white precipitate obtained is washed, filtered, and dried to obtain white barium sulfate powder.
[0055] The difference between Comparative Example 2 and Example 1 is that the surfactant used in step 3) is organosilicon.
[0056] The barium sulfate obtained in Examples 1-4 and Comparative Examples 1-2 was used to prepare bluish-black masterbatch. The specific method was as follows: barium sulfate, PET raw material, compatibilizer, antioxidant, and lubricant were melt-extruded and granulated according to the formula ratio to obtain bluish-black masterbatch. The particle size, crystal morphology, oil absorption value, and gloss of the barium sulfate obtained in Examples 1-4 and Comparative Examples 1-2 were analyzed, and the test results are shown in Table 1.
[0057] Table 1. Test results of Examples 1-4 and Comparative Examples 1-2
[0058]
[0059] As shown in Table 1, the barium sulfate crystals prepared in Examples 1-4 exhibit a rose-like morphology, while the barium sulfate prepared in Comparative Examples 1-2 shows a non-petal-like morphology. The barium sulfate particles prepared in the comparative examples show significant agglomeration. Furthermore, the oil absorption value of the barium sulfate prepared in Examples 1-4 and the gloss of the prepared bluish-black masterbatch are significantly better than those in Comparative Examples 1-2. This is because the present invention uses a gemini surfactant to prepare barium sulfate under certain conditions. Traditional surfactants tend to dissolve in aqueous solutions due to their hydrophilic head groups, while their hydrophobic groups inhibit the dissolution of surfactant molecules in water. Unlike traditional surfactants, gemini surfactants are "dimers" that link traditional surfactants together through spacer groups. Therefore, they exhibit higher surface (interfacial) activity, lower critical micelle concentration, better wetting properties, and stronger emulsifying and antibacterial capabilities. It can more effectively reduce the surface tension of water and the oil / water interfacial tension, which is conducive to the growth of barium sulfate crystals and the formation of a special multidimensional rose-shaped crystal structure. This barium sulfate has a special multidimensional rose-shaped crystal structure and good dispersibility. Compared with ordinary barium sulfate particles, the rose-shaped barium sulfate has a larger specific surface area and higher gloss when applied to bluish-black masterbatch.
[0060] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.
Claims
1. A method for preparing rose-shaped barium sulfate, characterized in that, Includes the following steps: 1) In a three-necked flask containing solvent 1, Na2SO4 solution is added while magnetically stirring under constant temperature conditions to obtain solution A; 2) In a three-necked flask containing solvent 2, BaCl2 solution is added while magnetically stirring under constant temperature conditions to obtain solution B; 3) While stirring, slowly add solution A to solution B to obtain a mixed solution. At the same time, use a titration method to slowly add the Gemini surfactant to the mixed solution. After stirring and reacting thoroughly, let it stand. Wash the obtained white precipitate in sequence, filter it, and dry it to obtain white rose-shaped barium sulfate. Solvent 1 is at least one of ethanol, acetone, and hexane; solvent 2 is at least one of ethanol, acetone, and hexane; and the gemini surfactant is at least one of cocamidopropyl-PG-dimethylammonium chloride phosphate sodium anionic gemini surfactant CPB-40, quaternary ammonium salt cationic gemini surfactant GC-A, and alkynyldiol gemini nonionic surfactant 104BC.
2. The method for preparing rose-shaped barium sulfate according to claim 1, characterized in that, In step 1), the concentration of the Na2SO4 solution is 0.1~0.5 mol / L, and the volume ratio of solvent 1 to Na2SO4 solution is 10~15:
1.
3. The method for preparing rose-shaped barium sulfate according to claim 1, characterized in that, In step 2), the concentration of the BaCl2 solution is 0.1~0.5 mol / L; the volume ratio of solvent 2 to BaCl2 solution is 10~15:
1.
4. The method for preparing rose-shaped barium sulfate according to claim 1, characterized in that, In steps 1) and 2), the constant temperature condition is 25~30℃, the magnetic stirring speed is 2000~4000r / min, and the stirring time is 30~60min.
5. The method for preparing rose-shaped barium sulfate according to claim 1, characterized in that, In step 3), the surfactant is added at a rate of 40-50 drops / min, the reaction temperature is 70℃-85℃, the reaction time is 10-12h, and the settling time is 24-28h.
6. A rose-shaped barium sulfate obtained by the preparation method according to any one of claims 1 to 5.
7. The application of rose-shaped barium sulfate obtained by the preparation method according to any one of claims 1 to 5 in bluish-black masterbatch.