Alkyl potassium phosphate as well as preparation method and application thereof
By preparing alkyl phosphate potassium salts containing hydrophobic tail chains and hydrophilic head groups, the safety risks and environmental pollution problems in existing technologies have been solved, achieving low-cost and efficient antistatic fiber effects.
Patent Information
- Application Number
- CN202410862491.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-06-28
- Publication Date
- 2025-12-30
AI Technical Summary
The existing industrial preparation of potassium alkyl phosphate salts poses safety risks and environmental pollution problems. In addition, the large amount used and the high cost make it difficult to effectively reduce static electricity and prevent flyaway and breakage in the fiber spinning process.
Using aminophosphonic acid and 1,2-epoxyalkane as raw materials, potassium alkyl phosphate salts are prepared through ring-opening reaction and contact with alkaline compounds to form a molecular structure containing two or more hydrophobic tail chains and hydrophilic head groups, which enhances its adsorption capacity and electrostatic conduction efficiency on the fiber surface.
It imparts excellent antistatic properties to fibers at lower dosages, reduces the cost of fiber auxiliaries, minimizes pollution to the aquatic environment, and improves surface/interfacial activity and electrostatic conduction efficiency.
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Figure CN121226428A_ABST
Abstract
Description
Technical Field
[0001] This disclosure pertains to the field of textile auxiliaries, specifically relating to an alkyl phosphate potassium salt, its preparation method, and its uses. Background Technology
[0002] Alkyl phosphate salts are a major class of anionic surfactants, widely used in industries such as pesticides, oil extraction, textiles, and daily chemicals. These surfactants possess amphiphilic properties due to the presence of hydrophobic alkyl chains and hydrophilic phosphate esters or their salts. This structural characteristic allows them to readily adsorb onto the surfaces of fibers, skin, and crude oil, forming an adsorbed film. This enables them to reduce surface / interfacial tension, reverse surface wettability, and improve the stability of oil / water emulsions.
[0003] In the chemical fiber textile process, potassium alkyl phosphate salts are an indispensable key auxiliary agent. By adsorbing onto the fiber surface to form an adsorption film, they can promptly remove the static charge generated by friction during the textile process, thereby exerting an antistatic effect and effectively preventing phenomena such as flyaways and yarn breakage in chemical fibers during spinning.
[0004] The industrial preparation of potassium alkyl phosphates typically involves reacting alkyl alcohols with phosphating agents. The two most commonly used phosphating agents are phosphorus pentoxide and polyphosphoric acid. However, the former is flammable, and the latter is prone to producing toxic substances, making procurement inconvenient for industrial production and posing safety risks during the feeding process. Furthermore, wastewater containing potassium alkyl phosphates easily causes eutrophication, triggering explosive algal growth and severely polluting the water bodies where it is discharged. On the other hand, the use of potassium alkyl phosphates in the industrial chemical fiber and textile sector is currently extensive, costly, and prone to causing water pollution. Summary of the Invention
[0005] The purpose of this invention is to provide a potassium alkyl phosphate salt, its preparation method, and its uses. The potassium alkyl phosphate salt provided by this invention has high surface / interfacial activity and, when applied to chemical fibers, especially polyester staple fibers, can impart excellent antistatic properties to the fibers.
[0006] To achieve the above objectives, a first aspect of the present invention provides a potassium alkyl phosphate salt, wherein the potassium alkyl phosphate salt has the structure shown in formula (I) and / or formula (II):
[0007]
[0008] In formula (Ⅰ), each R1 may be the same or different and is selected from H, K or A, and at least one R1 is A; each M1 may be the same or different and is selected from H, K or A; at least one of each R1 and each M1 is K; each L1 may be the same or different and is selected from alkylene groups having 1 to 6 carbon atoms.
[0009] In formula (II), each R2 may be the same or different and is selected from H, K or A, and at least one R2 is A; each M2 may be the same or different and is selected from H, K or A; at least one of each R2 and each M2 is K; each L2 may be the same or different and is selected from alkylene groups having 1 to 4 carbon atoms; L3 is selected from alkylene groups having 1 to 6 carbon atoms.
[0010] The A has the structure shown in equation (III):
[0011]
[0012] In formula (III), R' is selected from alkyl groups having 8 to 22 carbon atoms.
[0013] Optionally, each M1 may be the same or different, and may be selected from H or K respectively; each M2 may be the same or different, and may be selected from H or K respectively.
[0014] Optionally, each L1 is a methylene group.
[0015] Optionally, each L2 is methylene and each L3 is ethylene.
[0016] Optionally, R' is selected from alkyl groups having 8 to 18 carbon atoms.
[0017] Optionally, the potassium alkyl phosphate salt is selected from one or more compounds having the following structure:
[0018]
[0019]
[0020]
[0021] M3 is selected from either K or H, and at least one M3 is K.
[0022] A second aspect of the present invention provides a method for preparing potassium alkyl phosphate salts, wherein the method comprises:
[0023] S1. The aminophosphonic acid raw material is brought into contact with 1,2-epoxyalkane to carry out a ring-opening reaction to obtain alkyl phosphate ester;
[0024] S2. The alkyl phosphate ester is brought into contact with an alkaline compound for reaction; the alkaline compound is potassium hydroxide or an alkaline potassium salt;
[0025] The 1,2-epoxyalkane has the structure shown in formula (IV):
[0026]
[0027] In formula (IV), R' is selected from alkyl groups having 8 to 22 carbon atoms;
[0028] The aminophosphonic acid raw material has the structure shown in formula (V) or formula (VI):
[0029]
[0030] In formulas (V) and (VI), each L1 may be the same or different and is selected from alkylene groups having 1 to 6 carbon atoms; each L2 may be the same or different and is selected from alkylene groups having 1 to 4 carbon atoms; and L3 is selected from alkylene groups having 1 to 6 carbon atoms.
[0031] Optionally, R' is selected from alkyl groups having 8 to 18 carbon atoms.
[0032] Optionally, the 1,2-epoxyalkane is selected from one or more of 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane and 1,2-epoxyhexadecane;
[0033] The aminophosphonic acid raw material has one or more of the structures shown in the following formulas:
[0034]
[0035] Optionally, the molar ratio of phosphonic acid groups in the aminophosphonic acid raw material to the 1,2-epoxyalkane is 1:(0.1-5).
[0036] Optionally, in step 2, the aqueous solution containing the alkyl phosphate is brought into contact with the alkaline compound to react, and the pH of the resulting reaction mixture is 7.2 to 9.0.
[0037] The alkali is selected from potassium-containing alkalis; preferably, the alkali is selected from one or more of potassium hydroxide, potassium carbonate, and potassium bicarbonate.
[0038] The alkaline compound is used in an aqueous solution, wherein the mass concentration of the alkaline compound in the aqueous solution is 5-50%.
[0039] The mass concentration of the alkyl phosphate in the aqueous solution containing the potassium alkyl phosphate is 0.1% to 10%.
[0040] Optionally, in step S1, the conditions for the ring-opening reaction include: a reaction temperature of 40–90°C and a reaction time of 4–24 h;
[0041] In step S2, the reaction temperature is 10–40°C and the reaction time is 30–360 min.
[0042] A third aspect of the present invention provides a potassium alkyl phosphate salt prepared using the method described in the second aspect of the present invention.
[0043] The fourth aspect of the present invention provides the use of the potassium alkyl phosphate salt described in the first or third aspect of the present invention as an antistatic agent for chemical fibers.
[0044] Optionally, the chemical fiber antistatic agent includes a polyester staple fiber agent; the mass concentration of the alkyl phosphate potassium salt is 0.01 to 10 wt% based on the mass of the chemical fiber antistatic agent.
[0045] Through the above technical solution, this invention uses aminophosphonic acid and 1,2-epoxyalkane as reaction raw materials to prepare alkyl phosphate potassium salts. The alkyl phosphate salts provided by this invention contain two or more hydrophobic tail chains and hydrophilic head groups, which is equivalent to linking two or more single-headed, single-tailed alkyl phosphate potassium salts to the same molecule through chemical bonds. This chemical linkage shortens the spatial distance between alkyl phosphate potassium salt molecules, enhancing the synergistic effect between molecules and effectively improving their aggregation ability in aqueous solutions. They are more densely arranged in the fiber surface adsorption layer, thus exhibiting higher surface / interfacial activity. Simultaneously, the hydrophilic head groups of the phosphate potassium salts carry a negative charge and contain hydroxyl groups, easily forming intramolecular and intermolecular hydrogen bonds, resulting in better hydration and effectively improving electrostatic conduction efficiency. When the alkyl phosphate potassium salts provided by this invention are applied to chemical fibers, especially polyester staple fibers, they can impart excellent antistatic properties to the fibers at a low dosage, reducing the cost of fiber auxiliaries while also reducing pollution to the aquatic environment.
[0046] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description
[0047] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings:
[0048] Figure 1 The image shows the ESI mass spectrum of the alkyl phosphate potassium salt prepared in Example 1 of this invention. Detailed Implementation
[0049] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.
[0050] The first aspect of this disclosure provides a potassium alkyl phosphate salt, wherein the potassium alkyl phosphate salt has the structure shown in formula (I) and / or formula (II):
[0051]
[0052]
[0053] In formula (Ⅰ), each R1 may be the same or different, and is selected from H, K or A, and at least one R1 is A; each M1 may be the same or different, and is selected from H, K or A; at least one of each R1 and each M1 is K; each L1 may be the same or different, and is selected from alkylene groups having 1 to 6 carbon atoms, preferably having 1 carbon atom.
[0054] In formula (II), each R2 may be the same or different, and is selected from H, K or A, and at least one R2 is A; each M2 may be the same or different, and is selected from H, K or A; at least one of each R2 and each M2 is K; each L2 may be the same or different, and is selected from alkylene groups having 1 to 4 carbon atoms, preferably having 1 carbon atom; L3 is selected from alkylene groups having 1 to 6 carbon atoms, preferably having 2 carbon atoms;
[0055] The A has the structure shown in equation (III):
[0056]
[0057] In formula (III), R' is selected from alkyl groups having 8 to 22 carbon atoms.
[0058] The alkyl phosphate salts disclosed herein contain two or more hydrophobic tail chains and hydrophilic head groups, which is equivalent to linking two or more single-headed and single-tailed alkyl phosphate potassium salts into the same molecule through chemical bonds. This enhances the synergistic effect between molecules, effectively improving their aggregation ability in aqueous solutions and resulting in a more compact arrangement in the fiber surface adsorption layer, thus exhibiting higher surface / interfacial activity. Simultaneously, the hydrophilic head groups of the phosphate potassium salts carry a negative charge and contain hydroxyl groups, readily forming intramolecular and intermolecular hydrogen bonds, resulting in better hydration and effectively improving electrostatic conduction efficiency. When the alkyl phosphate potassium salts provided by this invention are applied to synthetic fibers, especially polyester staple fibers, they can impart excellent antistatic properties to the fibers at relatively low dosages, reducing the cost of fiber auxiliaries while also reducing pollution to the aquatic environment.
[0059] In one specific embodiment, each M1 may be the same or different, and is selected from H or K respectively; each M2 may be the same or different, and is selected from H or K respectively.
[0060] In one specific embodiment, each L1 is a methylene group.
[0061] In one specific embodiment, each L2 is a methylene group and L3 is an ethylene group.
[0062] In a preferred embodiment, R' is selected from alkyl groups having 8 to 18 carbon atoms. In the above embodiments, controlling the number of carbon atoms in the alkyl chain within the preferred range of this disclosure ensures the solubility of the molecule in water while enabling the molecule to possess excellent amphiphilic properties.
[0063] In a preferred embodiment, the alkyl phosphate potassium salt is selected from one or more compounds having the structure shown in the following formula:
[0064]
[0065] M3 is selected from either K or H, and at least one M3 is K.
[0066] In another preferred embodiment, the potassium alkyl phosphate salt is selected from one or more compounds having the following structure:
[0067]
[0068] M3 is selected from either K or H, and at least one M3 is K.
[0069] In another preferred embodiment, the potassium alkyl phosphate salt is selected from one or more compounds having the following structure:
[0070]
[0071] M3 is selected from either K or H, and at least one M3 is K.
[0072] In another preferred embodiment, the potassium alkyl phosphate salt is selected from one or more compounds having the following structure:
[0073]
[0074] M3 is selected from either K or H, and at least one M3 is K.
[0075] In another preferred embodiment, the potassium alkyl phosphate salt is selected from one or more compounds having the following structure:
[0076]
[0077] M3 is selected from either K or H, and at least one M3 is K.
[0078] A second aspect of this disclosure provides a method for preparing potassium alkyl phosphate salts, wherein the method includes:
[0079] S1. The aminophosphonic acid raw material is brought into contact with 1,2-epoxyalkane to carry out a ring-opening reaction to obtain alkyl phosphate ester;
[0080] S2. The alkyl phosphate ester is brought into contact with an alkaline compound for reaction; the alkaline compound is potassium hydroxide or an alkaline potassium salt;
[0081] The 1,2-epoxyalkane has the structure shown in formula (IV):
[0082]
[0083] In formula (IV), R' is selected from alkyl groups having 8 to 22 carbon atoms;
[0084] The aminophosphonic acid raw material has the structure shown in formula (V) or formula (VI):
[0085]
[0086] In formulas (V) and (VI), each L1 may be the same or different and is selected from alkylene groups having 1 to 6 carbon atoms, preferably having 1 carbon atom; each L2 may be the same or different and is selected from alkylene groups having 1 to 4 carbon atoms, preferably having 1 carbon atom; L3 is selected from alkylene groups having 1 to 6 carbon atoms, preferably having 2 carbon atoms.
[0087] This disclosure uses aminophosphonic acid and 1,2-epoxyalkane as reactants to prepare alkyl phosphate potassium salts containing two or more hydrophobic tail chains and hydrophilic head groups. These salts exhibit strong aggregation ability in aqueous solutions and a more compact arrangement in the fiber surface adsorption layer, demonstrating higher surface / interfacial activity and effectively improving electrostatic conductivity. When the alkyl phosphate potassium salts provided by this invention are applied to chemical fibers, especially polyester staple fibers, they can impart excellent antistatic properties to the fibers at relatively low dosages, reducing the cost of fiber auxiliaries while also reducing pollution to the aquatic environment.
[0088] In this disclosure, the mixture obtained after reacting the alkyl phosphate with the alkaline compound in step S2 can be used directly as an antistatic agent for chemical fibers, or the mixture can be separated to obtain one or more compounds with different structures, and these compounds can be used as antistatic agents for chemical fibers.
[0089] In a preferred embodiment, R' is selected from alkyl groups having 8 to 18 carbon atoms.
[0090] In a preferred embodiment, the aminophosphonic acid raw material has the structure shown in the following formula:
[0091]
[0092] In a preferred embodiment, the aminophosphonic acid raw material is selected from aminotrimethylenephosphonic acid or ethylenediaminetetramethylenephosphonic acid.
[0093] In a preferred embodiment, the 1,2-epoxyalkane is selected from one or more of 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, and 1,2-epoxyhexadecane.
[0094] In one specific embodiment, the molar ratio of phosphonic acid groups to 1,2-epoxyalkane in the aminophosphonic acid raw material is 1:(0.1-5), preferably 1:(0.3-1.5). In the above embodiment, selecting the preferred amounts of aminophosphonic acid raw material and 1,2-epoxyalkane can further enhance the surface / interfacial activity and electrostatic conductivity of the alkyl phosphate potassium salt, resulting in superior antistatic properties in polyester staple fibers after application.
[0095] In one specific embodiment, in step S2, the alkali is selected from potassium-containing alkalis; preferably, the alkali is selected from one or more of potassium hydroxide, potassium carbonate and potassium bicarbonate, and more preferably, the alkali is potassium hydroxide.
[0096] In one specific embodiment, in step 2, an aqueous solution containing the alkyl phosphate is brought into contact with the alkaline compound to react, and the pH of the resulting reaction mixture is 7.2 to 9.0.
[0097] In one specific embodiment, the alkali is selected from potassium-containing alkalis; preferably, the alkali is selected from one or more of potassium hydroxide, potassium carbonate, and potassium bicarbonate; the alkaline compound is used in an aqueous solution, wherein the mass concentration of the alkaline compound in the aqueous solution is 5-50%, preferably 10-20%.
[0098] In one specific embodiment, the mass concentration of the alkyl phosphate in the aqueous solution containing the potassium alkyl phosphate is 0.01–10%, preferably 0.01–1%.
[0099] In one specific embodiment, in step S1, the conditions for the ring-opening reaction include: a reaction temperature of 40–90°C, preferably 70–80°C; and a reaction time of 4–24 h, preferably 8–12 h. In the above embodiment, the ring-opening reaction can be carried out in the presence of a solvent or in the absence of a solvent. The solvent is selected from one or more of methanol, ethanol, isopropanol, and water. When the reaction temperature is controlled within the preferred range (70–80°C), both the aminophosphonic acid raw material and the 1,2-epoxyalkane are in a liquid state, allowing the ring-opening reaction to proceed under solvent-free conditions.
[0100] In one specific embodiment, in step S2, the reaction temperature is 10–40°C, preferably 20–30°C; the reaction time is 30–360 min, preferably 60–240 min.
[0101] This disclosure provides, in a third aspect, alkyl phosphate potassium salts prepared using the method described in the second aspect of the invention.
[0102] The potassium alkyl phosphate salts provided in this disclosure have high surface / interfacial activity. When applied to chemical fibers, especially polyester staple fibers, they can impart excellent antistatic properties to the fibers.
[0103] This fourth aspect of the disclosure provides the use of the potassium alkyl phosphate salt described in the first or third aspect of the invention as an antistatic agent for synthetic fibers, and in particular as an antistatic agent for polyester staple fibers.
[0104] In this disclosure, when the same mass concentration of the alkyl phosphate potassium salt provided in this disclosure and conventional alkyl phosphate potassium salt are applied simultaneously to chemical fibers (especially polyester staple fibers), the alkyl phosphate potassium salt provided in this disclosure can more effectively reduce the resistivity of chemical fibers (especially polyester staple fibers); when achieving the same degree of resistivity reduction, the amount of alkyl phosphate potassium salt provided in this disclosure used is lower.
[0105] In this disclosure, immersing polyester staple fibers in an aqueous solution containing the potassium alkyl phosphate salt provided herein can effectively reduce the resistivity of the synthetic fiber (especially polyester staple fiber) and effectively improve the antistatic properties of the fiber in subsequent textile processes. Specifically, the aqueous solution containing the potassium alkyl phosphate salt provided herein can be separated to obtain one or more compounds with different structures. Immersing the synthetic fiber (especially polyester staple fiber) in an aqueous solution containing one or more compounds with different structures reduces the resistivity of the synthetic fiber (especially polyester staple fiber) and effectively improves the antistatic properties of the fiber in subsequent textile processes.
[0106] In one specific embodiment, the mass concentration of the alkyl phosphate potassium salt is 0.01–10 wt%, preferably 0.01–5 wt%, and more preferably 0.01–1 wt%, based on the mass of the chemical fiber antistatic agent.
[0107] The present invention will be further illustrated by the following examples, but the invention is not limited thereto. All raw materials used in the following examples are commercially available. The main sources of the raw materials are shown in Table 1.
[0108] Example 1
[0109] a) 59.9 g (0.1 mol) of aminotrimethylenephosphonic acid (50 wt% aqueous solution) was mixed with 70.1 g (0.33 mol) of 1,2-epoxytetradecane, and the mixture was heated to 75 °C for a ring-opening reaction. After stirring for 10 h, the mixture was cooled to room temperature and filtered to obtain a solid crude product. The solid crude product was purified by silica gel column chromatography using dichloromethane as the eluent to obtain 70.6 g of alkyl phosphate ester, denoted as ATMP-C12P. The molar ratio of the phosphate group in aminotrimethylenephosphonic acid to 1,2-epoxytetradecane was 1:1.1.
[0110] b. Mix 1g of alkyl phosphate (ATMP-C12P) with 99g of distilled water in a beaker, then add 10% potassium hydroxide aqueous solution and stir. Adjust the pH to 8.0, the reaction temperature is 25℃, and the reaction time is 1h to obtain an aqueous solution containing alkyl phosphate potassium (ATMP-C12PK).
[0111] The reaction equation for step a is as follows:
[0112]
[0113] The ESI mass spectrometry analysis results after the reaction in step a are attached. Figure 1 As shown in the figure, the peak with a mass-to-charge ratio of 510.17913 corresponds to the molecular ion peak ([MH)) formed after the compound with the structure shown in formula (1-1) of ATMP-C12P loses a proton. - The peak with a mass-to-charge ratio of 722.39358 corresponds to the molecular ion peak ([MH)) formed after the compound with the structure shown in formula (1-2) of ATMP-C12P loses a proton. - The peak with a mass-to-charge ratio of 934.60874 corresponds to the compound with the structure shown in formula (1-3) of ATMP-C12P.
[0114] Example 2
[0115] a) 4.36 g (0.01 mol) of ethylenediaminetetramethylenephosphonic acid (EDTA) was mixed with 12.7 g (0.06 mol) of 1,2-epoxytetradecane. The mixture was heated to 80 °C for a ring-opening reaction. After stirring for 12 h, the mixture was cooled to room temperature and filtered to obtain a solid crude product. The solid crude product was purified by silica gel column chromatography using dichloromethane as the eluent to obtain 6.98 g of alkyl phosphate ester, designated EDTMP-C12P. The molar ratio of the phosphate group in EDTA to 1,2-epoxytetradecane was 1:1.5.
[0116] b. Mix 1g of alkyl phosphate (EDTMP-C12P) with 99g of distilled water in a beaker, then add 20% potassium hydroxide aqueous solution and stir. Adjust the pH to 8.0, the reaction temperature is 30℃, and the reaction time is 3h to obtain an aqueous solution containing alkyl phosphate potassium (EDTMP-C12PK).
[0117] The reaction equation for step a is as follows:
[0118]
[0119] ESI mass spectrometry analysis revealed that the prepared alkyl phosphate ester (EDTMP-C12P) contained compounds with structures shown in formulas (2-1), (2-2), (2-3), and (2-4).
[0120] Example 3
[0121] a) 59.9 g (0.1 mol) of aminotrimethylenephosphonic acid (50 wt% aqueous solution) was mixed with 15.6 g (0.1 mol) of 1,2-epoxydecane, and the mixture was heated to 70 °C for a ring-opening reaction. After stirring for 8 h, the mixture was cooled to room temperature and filtered to obtain a solid crude product. The solid crude product was purified by silica gel column chromatography using dichloromethane as the eluent to obtain 75.2 g of alkyl phosphate ester, denoted as ATMP-C8P. The molar ratio of the phosphate group in aminotrimethylenephosphonic acid to 1,2-epoxydecane was 1:0.33.
[0122] b. Mix 1g of novel alkyl phosphate (ATMP-C8P) with 99g of distilled water in a beaker, then add 12% potassium hydroxide aqueous solution and stir. Adjust the pH to 8.0, the reaction temperature is 20℃, and the reaction time is 0.5h. The aqueous solution containing potassium alkyl phosphate (ATMP-C8PK) is obtained by ESI mass spectrometry analysis.
[0123] Example 4
[0124] a) 59.9 g (0.1 mol) of aminotrimethylenephosphonic acid (50 wt% aqueous solution) was mixed with 44.2 g (0.24 mol) of 1,2-epoxydodecane, and the mixture was heated to 70 °C for a ring-opening reaction. After stirring for 10 h, the mixture was cooled to room temperature and filtered to obtain a solid crude product. The solid crude product was purified by silica gel column chromatography using dichloromethane as the eluent to obtain 72.0 g of alkyl phosphate ester, denoted as ATMP-C10P. The molar ratio of the phosphate group in aminotrimethylenephosphonic acid to 1,2-epoxydodecane was 1:0.8.
[0125] b. Mix 1g of alkyl phosphate (ATMP-C10P) with 99g of distilled water in a beaker, then add 15% potassium hydroxide aqueous solution and stir. Adjust the pH to 8.0, the reaction temperature is 25℃, and the reaction time is 1h. The aqueous solution containing alkyl phosphate potassium (ATMP-C10PK) is obtained by ESI mass spectrometry analysis.
[0126] Example 5
[0127] a) 59.9 g (0.1 mol) of aminotrimethylenephosphonic acid (50 wt% aqueous solution) was mixed with 72.1 g (0.3 mol) of 1,2-epoxyhexadecane, and the mixture was heated to 80 °C for a ring-opening reaction. After stirring for 16 h, the mixture was cooled to room temperature and filtered to obtain a solid crude product. The solid crude product was purified by silica gel column chromatography using dichloromethane as the eluent to obtain 66.3 g of alkyl phosphate ester, denoted as ATMP-C14P. The molar ratio of the phosphate group in aminotrimethylenephosphonic acid to 1,2-epoxyhexadecane was 1:1.
[0128] b. Mix 1g of alkyl phosphate (ATMP-C14P) with 99g of distilled water in a beaker, then add 20% potassium hydroxide aqueous solution and stir. Adjust the pH to 8.0, the reaction temperature is 40℃, and the reaction time is 6h. The aqueous solution containing alkyl phosphate potassium (ATMP-C14PK) is obtained by ESI mass spectrometry analysis.
[0129] Example 6
[0130] The method of Example 1 was used, except that the molar ratio of the phosphonic acid group to 1,2-epoxytetradecane in aminotrimethylenephosphonic acid was 1:0.05. The resulting product was designated ATMP-C12PK-2.
[0131] Comparative Example 1
[0132] 1g of dodecyl phosphate was mixed with 99g of distilled water in a beaker, followed by the addition of a 20% potassium hydroxide aqueous solution and stirring. The pH was adjusted to 8.0, the mixing temperature was 25℃, and the stirring time was 2h to obtain an aqueous solution containing potassium dodecyl phosphate (C12PK).
[0133] Comparative Example 2
[0134] The method of Comparative Example 1 was used, except that R' was selected from an alkyl group with 4 carbon atoms. The resulting product was denoted as ATMP-C4PK.
[0135] Comparative Example 3
[0136] The method of Example 1 is used, except that R' is selected from an alkyl group having 24 carbon atoms. ATMP-C24PK.
[0137] Test Example 1
[0138] The surface tension and critical micelle concentration (CMC) of the alkyl phosphate potassium salts prepared in Examples 1-6 and Comparative Examples 1-3 were measured using a surface tension meter (KRUSS K100, Germany) via the pendant method at a temperature of 25°C. The test results are shown in Table 2.
[0139] Test Example 2
[0140] The potassium alkyl phosphate salts prepared in Examples 1-6 and Comparative Examples 1-3 were used in polyester staple fibers to test the antistatic properties of the polyester staple fibers. The specific test methods are as follows:
[0141] Soak polyester staple fibers in hot water for 1 hour, then wash them 10 times with laundry detergent, 5 times with clean water, and 3 times with distilled water. Next, spin-dry the washed polyester staple fibers for 5 minutes, and then dry them in a 50°C oven for 4 hours until they are completely dry to a constant weight.
[0142] 15g of dried polyester staple fiber was immersed in 500mL of potassium alkyl phosphate aqueous solution of different mass concentrations for 30min until the fiber was completely submerged. The fiber was then removed and dehydrated again in a spin dryer for 5min. Subsequently, the fiber was dried in an oven at 50℃ for 4h. Finally, the dried polyester staple fiber sample was placed in an equilibration chamber for 12h before testing.
[0143] The average resistivity of the fiber was measured using a YG321D fiber resistivity meter, following the method in GB / T 14342-2015. The fiber was equilibrated for 15 minutes at 25℃ and 65% relative humidity (RH). The measurement results are shown in Table 3.
[0144] Table 1
[0145] Product Name CAS number source Item number 1,2-Epoxytetradecane 3234-28-4 TCI E0314 Aminotrimethylenephosphonic acid (50% aqueous solution) 6419-19-8 Innochem A13654 EDTA-TEMA-TEM-Phosphate 1429-50-1 Innochem A82791 1,2-Epoxyhexadecane 7320-37-8 Aladdin E477016 1,2-Epoxyoctadecane 7390-81-0 Aladdin E156382 dodecyl phosphate 2627-35-2 TCI M3548 hexadecyl phosphate 17026-85-6 Macklin P905784
[0146] Table 2
[0147] Chemical agents <![CDATA[γ CMC / (mN / m)]]> CMC / (ppm) Example 1 ATMP-C12PK 25.1 90 Example 2 EDTMP-C12PK 25.6 150 Example 3 ATMP-C8PK 27.0 500 Example 4 ATMP-C10PK 26.8 350 Example 5 ATMP-C14PK 23.7 68 Example 6 ATMP-C12PK-2 26.9 780 Comparative Example 1 C12PK 27.5 6100 Comparative Example 2 ATMP-C4PK 45.0 46300 Comparative Example 3 ATMP-C24PK Insoluble Insoluble
[0148] Table 3
[0149]
[0150] As can be seen from the test results in Table 2, the alkyl phosphate potassium salts provided in this disclosure, compared with the comparative examples, contain two or more hydrophobic tail chains and hydrophilic head groups. This is equivalent to linking two or more single-headed and single-tailed alkyl phosphate potassium salts into the same molecule through chemical bonds, thereby enhancing the synergistic effect between molecules and effectively improving their aggregation ability in aqueous solutions. They are more densely arranged in the fiber surface adsorption layer, reducing the surface tension of water to 23.7–27.0 mN / m, resulting in a CMC of 68–780 mM. Comparing the examples of this disclosure with Comparative Example 1 shows that the CMC range is reduced by one order of magnitude. Comparing Example 1 with Comparative Example 2 shows that when the number of carbon atoms in the alkyl chain is outside the range defined in this application, the performance of the prepared product is significantly reduced. In Comparative Example 2, when the number of carbon atoms in the alkyl chain is too small, the surface activity and aggregation ability are significantly reduced; in Comparative Example 3, when the number of carbon atoms in the alkyl chain is too large, the product has very poor water solubility and cannot be used.
[0151] As shown in Table 3, when the mass concentration is 10000 ppm, the resistivity of the fiber samples treated with the alkyl phosphate potassium salt provided in this disclosure is lower than that of the comparative example. When the mass concentration is reduced to 1000 ppm, the resistivity of the fibers treated with the C12PK and ATMP-C4PK aqueous solutions in the comparative example increases by 1 to 2 orders of magnitude, and the antistatic performance decreases significantly. In contrast, the resistivity of the fibers treated with the alkyl phosphate potassium salt prepared in the embodiments of this disclosure remains at 10 ppm. 7 ~10 8 The resistivity of the fibers treated with the aqueous solutions of comparative C12PK and ATMP-C4PK continued to increase as the mass concentration decreased to 100 ppm, reaching the order of Ω·cm. In contrast, the resistivity of the fibers treated with ATMP-C12PK and ATMP-C14PK prepared in Examples 1 and 5 of this disclosure remained at around 10 Ω·cm. 8 The range is on the order of Ω·cm. Therefore, the alkyl phosphate potassium salts provided in this disclosure can be used as highly efficient antistatic agents for polyester staple fibers. They can impart excellent antistatic properties to fibers at relatively low dosages (1-10% of the dosage of existing single-chain alkyl phosphate potassium salts), making the antistatic performance of the fibers significantly better than that of existing single-head and single-tail alkyl phosphate potassium salts. This greatly reduces the cost of fiber auxiliaries while also reducing pollution to the aquatic environment.
[0152] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.
[0153] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.
[0154] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.
Claims
1. A potassium salt of an alkylphosphonate, wherein, The alkyl phosphate potassium salt has a structure shown in the following formula (I) and / or formula (II): In the formula (I), each R1 is the same or different, and is selected from H, K or A, and at least one R1 is A; each M1 is the same or different, and is selected from H, K or A; at least one of each R1 and each M1 is K; each L1 is the same or different, and is selected from an alkylene group with 1-6 carbon atoms; In the formula (II), each R2 is the same or different, and is selected from H, K or A, and at least one R2 is A; each M2 is the same or different, and is selected from H, K or A; at least one of each R2 and each M2 is K; each L2 is the same or different, and is selected from an alkylene group with 1-4 carbon atoms; L3 is selected from an alkylene group with 1-6 carbon atoms; The A has a structure shown in the following formula (III): In the formula (III), R' is selected from an alkyl group with 8-22 carbon atoms.
2. The potassium alkyl phosphate ester salt of claim 1, wherein, Each M1 is the same or different, and is selected from H or K; each M2 is the same or different, and is selected from H or K.
3. The potassium alkyl phosphate ester salt of claim 1, wherein, Each L1 is a methylene group.
4. The potassium alkyl phosphate ester salt of claim 1, wherein, Each L2 is a methylene group, and L3 is an ethylene group.
5. The potassium alkyl phosphate ester salt of claim 1, wherein, The R' is selected from an alkyl group with 8-18 carbon atoms.
6. The potassium alkyl phosphate ester salt of claim 1, wherein, The alkyl phosphate potassium salt is selected from one or more of the following compounds with the structures shown below: In the formula (IV), R' is selected from an alkyl group with 8-22 carbon atoms.
7. A process for the preparation of a potassium alkyl phosphate ester salt, wherein, The aminophosphonic acid raw material has a structure shown in the following formula (V) or formula (VI): In the formula (V) and formula (VI), each L1 is the same or different, and is selected from an alkylene group with 1-6 carbon atoms; each L2 is the same or different, and is selected from an alkylene group with 1-4 carbon atoms; L3 is selected from an alkylene group with 1-6 carbon atoms. R' is selected from an alkyl group with 8-18 carbon atoms. The 1,2-alkylene oxide is selected from one or more of 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane and 1,2-epoxyhexadecane; The aminophosphonic acid raw material has one or more of the structures shown in the following formula: The molar ratio of the phosphonic acid group in the aminophosphonic acid raw material to the 1,2-alkylene oxide is 1:(0.1-5). In step 2, the aqueous solution containing the alkyl phosphate is contacted with the basic compound, and the pH of the obtained reaction mixture is 7.2-9.0; 8. The method of claim 7, wherein, The base is selected from potassium-containing bases; preferably, the base is selected from one or more of potassium hydroxide, potassium carbonate and potassium bicarbonate; 9. The method of claim 7, wherein, The basic compound is used in an aqueous solution, and the mass concentration of the basic compound in the aqueous solution is 5-50%; The mass concentration of the alkyl phosphate in the aqueous solution containing the alkyl phosphate potassium salt is 0.1-10%.
10. The method of claim 7, wherein, 11. The method of claim 7, wherein, 12. The method of claim 7, wherein, In step S1, the conditions of the ring-opening reaction include a reaction temperature of 40-90°C and a reaction time of 4-24 h. In step S2, the reaction temperature is 10-40°C and the reaction time is 30-360 min.
13. The potassium alkyl phosphate salt prepared by the method of any one of claims 7-12.
14. Use of the potassium alkyl phosphate salt of any one of claims 1-6 and 13 as a chemical fiber antistatic agent.
15. Use according to claim 14, wherein, The chemical fiber antistatic agent includes polyester staple fiber agent, and the mass concentration of the potassium alkyl phosphate salt in the chemical fiber antistatic agent is 0.01-10 wt%.