Organic amine supramolecular ionic salt, preparation and application in hair care

Abstract

The application discloses an organic amine supramolecular ionic salt, a preparation method and application thereof in hair care, and belongs to the technical field of supramolecules. The organic amine supramolecular ionic salt is prepared by mixing organic amine (one of tetrahydroxypropyl ethylenediamine, triethylene glycol diamine and polyether amine) and organic acid (one or two of maleic acid, sorbic acid, ferulic acid, coffee acid, cinnamic acid and fumaric acid). The organic amine supramolecular ionic salt prepared by the application can repair disulfide bonds in hair from the structure, so that the hair is repaired and smooth.

Description

Technical Field

[0001] This invention relates to an organic amine supramolecular ionic salt, its preparation, and its application in hair care, belonging to the field of supramolecular technology. Background Technology

[0002] Hair, as an important part of a person's appearance, receives much attention for its health. However, daily factors such as perming and dyeing, friction from combing, environmental pollutants, and UV exposure can easily damage and break hair cuticles, leading to keratin loss, disulfide bond breakage, and consequently, dry, frizzy, less smooth, brittle, and dull hair. Simultaneously, scalp microecological imbalances and abnormal sebum secretion can also indirectly affect hair health. Therefore, developing hair care ingredients that repair damaged hair, regulate scalp condition, and provide long-lasting stability has become a research hotspot in the daily chemical industry.

[0003] Currently, commonly used active ingredients in hair care products mainly include silicone oils, cationic polymers, and proteins. While silicone oils can form a protective film on the hair surface and temporarily improve frizz, they are highly hydrophobic, difficult to disperse evenly, and prone to excessive accumulation on the scalp and hair, leading to a greasy feeling. Furthermore, they cannot fundamentally repair damaged keratin structures. Cationic polymers adhere to the negatively charged hair surface through electrostatic attraction, improving smoothness, but long-term use may damage the scalp barrier, causing allergic or irritating reactions. Although protein-based ingredients have a strong affinity for hair keratin and possess some repairing properties, they are relatively unstable, prone to denaturation during processing and storage, and difficult to precisely target damaged areas, resulting in limited repair efficiency.

[0004] The development of supramolecular chemistry has provided new directions for the innovation of hair care ingredients. Supramolecular ionic salts achieve self-assembly through intermolecular non-covalent bonds (such as electrostatic interactions, hydrogen bonds, and hydrophobic interactions), offering advantages such as controllable structure, good biocompatibility, and synergistic function. Compared to traditional covalent compounds, their preparation process does not require harsh reaction conditions or the use of toxic organic solvents, making them more environmentally friendly. Furthermore, they can achieve precise repair and long-lasting effects through intermolecular synergistic interactions, and are gradually being applied in the hair care field. For example, existing technologies have developed hair care ingredients such as silk protein-calcium ion supramolecular salt (CN 117045533 A) and organosilicon supramolecular ionic salt (CN119039339A), which achieve the repair and conditioning of damaged hair through the specific binding of supramolecular structures to hair keratin. However, these supramolecular salts still suffer from problems such as limited functionality, limited repair effects on severely damaged hair, and poor compatibility in different hair care formulations, making it difficult to meet consumers' demand for multifunctional hair care products.

[0005] Organic amines, as amino alcohols containing multiple hydroxyl and amino groups, possess excellent water solubility, biocompatibility, and chelating properties, and have been widely used in cosmetics and personal care products. However, research on the application of organic amines in supramolecular hair care is currently lacking; there are no reports of preparing them into supramolecular ionic salts and applying them to hair care products, thus failing to fully utilize their structural advantages and hair care potential.

[0006] Therefore, the preparation of a supramolecular compound based on organic amines that has good hair repair properties, can smooth hair, and is easy to store and transport has extremely high practical and economic value. Summary of the Invention

[0007] [Technical Issues] Currently, research on the application of organic amines in the field of supramolecular hair care is still in its infancy, and there are no reports on their preparation into supramolecular ionic salts and their application in hair care products.

[0008] [Technical Solution] To address the aforementioned problems, this invention provides an organic amine supramolecular ionic salt, its preparation, and its application in hair care. Specifically, this invention involves mixing an organic amine (one of tetrahydroxypropyl ethylenediamine, triethylene glycol diamine, or polyetheramine) and an organic acid (one or two of maleic acid, sorbic acid, ferulic acid, caffeic acid, cinnamic acid, or fumaric acid) to prepare the organic amine supramolecular ionic salt. The organic amine supramolecular ionic salt prepared by this invention can structurally repair disulfide bonds in hair, thereby repairing hair strands and making them smooth.

[0009] The first objective of this invention is to provide an organic amine supramolecular ionic salt, the structural formula of which is as follows:

[0010] Formula I

[0011] Formula II

[0012] Formula III

[0013] Formula IV R1 and R2 can be the same or different, and the specific structural formula can be any of the following:

[0014] or

[0015] or

[0016] or

[0017] or

[0018] or

[0019] In Equation III, x is 1-50; In Equation IV, x is 1-50, y is 1-80, and z is 1-50.

[0020] A second objective of this invention is to provide a method for preparing organic amine supramolecular ionic salts, comprising the following steps: Organic amines and organic acids are mixed to obtain organic amine supramolecular ionic salts; Among them, the organic acid is any one or two of maleic acid, sorbic acid, ferulic acid, caffeic acid, cinnamic acid, and fumaric acid; The organic amine is one of tetrahydroxypropylethylenediamine, triethylene glycol diamine, or polyether amine; Polyetheramines include one or both of MA-2200 and MA2203ED.

[0021] The mixing is carried out under the protection of an inert gas, which includes either nitrogen or helium.

[0022] In one embodiment of the present invention, when the organic acid is one type, the method for preparing an organic amine supramolecular ionic salt includes the following steps: Organic amines and organic acids were stirred at 55-95℃ and 200-800 rpm for 3-10 h to obtain organic amine supramolecular ionic salts. The molar ratio of organic amines to organic acids is 1:2.

[0023] In one embodiment of the present invention, when two organic acids are present, the method for preparing an organic amine supramolecular ionic salt includes the following two methods: Method 1: The first and second acids are ground at 15-35℃ for 20-60 min to form an organic acid mixture powder with a particle size controlled at 5-100 μm. Then, the organic acid mixture powder and organic amine are stirred at 55-95℃ and 350-800 rpm for 2-8 h to obtain an organic amine supramolecular ionic salt. The molar ratio of organic amine to the first and second acids is 1:1:1. Method 2: The first organic acid and the organic amine are mixed and stirred at 55-95℃ and 200-800 rpm for 2-4 h; then the second organic acid is added and stirred at 55-95℃ and 200-800 rpm for 1-6 h to obtain the organic amine supramolecular ionic salt; wherein the molar ratio of the organic amine to the first acid and the second acid is 1:1:1.

[0024] In one embodiment of the present invention, after the reaction is completed, purification can be performed by washing with anhydrous ethanol and drying.

[0025] The third objective of this invention is the application of the organic amine supramolecular ionic salt described herein in the preparation of daily chemical products or pharmaceuticals.

[0026] In one embodiment of the present invention, the daily chemical products include: hair care cosmetics, detergents, etc.

[0027] In one embodiment of the present invention, hair care cosmetics include: hair conditioner, hair oil, hair lotion, hair wax, hair gel, after-wash sunscreen lotion, no-steam hair lotion, sunscreen shampoo, medicated hair lotion, conditioning shampoo, hair fragrance, aftershave, etc.

[0028] A fourth objective of this invention is to provide a hair care product containing the organic amine supramolecular ionic salt described herein.

[0029] In one embodiment of the present invention, the mass concentration of the organic amine supramolecular ionic salt in the hair care product is 0.01-20%.

[0030] In one embodiment of the present invention, the hair care product comprises the following components by mass percentage: Phase A: 0.05% disodium EDTA, 4.5% cetearyl alcohol, 0.5% cetyl alcohol, 1.5% Fentacare 1831 70 (stearyltrimethylammonium chloride and ethanol), and 1.3% Fentacare 2231 EF (behenryltrimethylammonium chloride and isopropanol); Phase B: 5% water, 0.3% hydroxyethyl cellulose; C phase: 2% C13-15 alkyl, 2% polydimethylsiloxane, 0.5% bis-aminopropyl polydimethylsiloxane; Phase D: PE 9010 (phenoxyethanol, ethylhexylglycerin) 0.7%, hair oil TC-2115 (ammonia-terminated polydimethylsiloxane (and) lauryl ether-7 (and) isolauryl ether-6 (and) glycerin) 3%, organic amine supramolecular ion salt 0.3%, fragrance 0.3%; Phase E: Citric acid.

[0031] In one embodiment of the present invention, the specific preparation method of the hair care product includes the following steps: (1) Add phase A raw material to the tank in sequence, stir and heat to 80-90℃, homogenize for 5 minutes until the material is uniform; (2) After pre-dispersing the B phase raw material, put it into the tank, homogenize for 3-6 minutes, keep warm for 10-20 minutes, until the material is uniform; (3) Cool down to 45°C, mix the C phase raw materials evenly, add them to the tank, homogenize for 3-6 minutes until the material is uniform; (4) After adding the D phase raw materials to the tank in sequence, stir for 5-20 minutes until the material is uniform; (5) If the pH is not within the range, adjust it with phase E; after passing the test, the hair care product is obtained.

[0032] The fifth objective of this invention is to provide a method for improving hair care products to repair damaged hair and improve hair smoothness, which employs the organic amine supramolecular ionic salt described in this invention.

[0033] [Beneficial Effects] (1) The organic amine supramolecular ionic salt described in this invention can reduce the static and dynamic friction coefficients of hair and reduce dry combing work; its repair and smoothing effects on damaged hair loss are significantly better than those of existing compounds (diaminopropyl diethylene glycol dimaleate).

[0034] (2) The organic amine supramolecular ionic salt described in this invention is a supramolecular ionic salt with high reaction rate and yield, mild reaction conditions, simple operation, and is suitable for industrial production. Attached Figure Description

[0035] Figure 1 The image shows the NMR spectrum of the organic amine supramolecular ion salt in Example 1.

[0036] Figure 2 The images show fluorescence detection of hair strands; (a) untreated damaged hair; (b) reduced hair treated with thioglycolic acid; and (c) hair treated with the organic amine supramolecular ion salt of Example 1.

[0037] Figure 3 The images are scanning electron micrographs of hair strands; (a) untreated damaged hair; (b) reduced hair treated with thioglycolic acid; and (c) hair treated with the organic amine supramolecular ion salt of Example 1.

[0038] Figure 4 The image shows the infrared spectrum of the organic amine supramolecular ionic salt in Example 12.

[0039] Figure 5 The image shows the infrared spectrum of the organic amine supramolecular ionic salt in Example 13.

[0040] Figure 6Scanning electron micrographs of damaged hair treated with ionic salts obtained in Example 1 and Comparative Examples 1-4. Detailed Implementation

[0041] The preferred embodiments of the present invention are described below. It should be understood that the embodiments are for better explanation of the present invention and are not intended to limit the present invention.

[0042] Test method: 1. Nuclear magnetic resonance (NMR) test: Using deuterated DMSO as the deuteration reagent, 10 mg of sample was dissolved in an NMR tube and tested using an R1VR1NCE Ⅲ HD400 MHz NMR spectrometer to obtain the results.

[0043] 2. Repair effect test: When hair is damaged, the disulfide bonds in the hair keratin are broken, resulting in loss of elasticity and shine, and making the hair dry and brittle. The breaking of disulfide bonds yields two free sulfhydryl groups, so measuring the sulfhydryl content in damaged hair can provide a relatively direct assessment of the degree of hair damage.

[0044] Rhodamine R2 (RB) is one of the most commonly used fluorescent dyes, and iodine solution (I 3- The reaction of I with RB can quench its fluorescence and reduce its fluorescence intensity, while the thiol group can reduce I. 3- Restore to I - This enhances fluorescence intensity. Through the fluorescent interaction between iodine solution and rhodamine R2, residual thiol groups in the hair can be reduced to I... 3- Then, the fluorescence intensity of the hair strands is observed under a fluorescence microscope. If the repair process is successful, the fluorescence intensity on the repaired hair strands should be much lower than that on the damaged hair strands, thus visualizing the repair effect of thiol groups. The concentration is 10. -3 10 mol / L iodine standard solution (solvent is water), concentration -4 Prepare mol / L Rhodamine B solution (water as solvent) and acetate-sodium acetate buffer (pH 7).

[0045] The hair was placed in a reducing agent, mercaptoacetic acid aqueous solution (8% by mass, pH 8.5), and shaken at 50°C for 30 min in a constant temperature shaking incubator. After being removed, dried, and stored in nitrogen, the hair was reduced.

[0046] A suitable amount of hair was cut and soaked in different repair solutions (prepared in the examples or comparative examples) at 50°C with shaking for 30 minutes. After removal, the hair was dried in a nitrogen atmosphere to obtain the repaired hair.

[0047] Several strands of repaired hair from each group were placed in 2 mL of iodine standard solution and vortexed at 25°C for 5 min. Then, 3 mL of rhodamine B solution and 5 mL of acetate-sodium acetate buffer were added. After standing for 10 min, the hair was removed and soaked in deionized water. After vortexing at 25°C for 5 min, the hair was removed and rinsed several times with deionized water to remove residual rhodamine B. The hair was then dried and observed under a 360 nm fluorescence microscope.

[0048] After processing and drying, the hair was cut into small segments of about 0.3 cm, fixed on the electron microscope stage with conductive adhesive, and the hair morphology was observed using a Hitachi S-4800 field emission scanning electron microscope.

[0049] 3. The formula for calculating yield is:

[0050] Among them, M X —Actual output; M t —Theoretical output.

[0051] The room temperature mentioned in this invention is 15-35°C; within the above range, parameter changes will not affect the product synthesis.

[0052] 4. Elemental analysis test The mass percentage of each element in the sample was tested according to the "General Rules for Elemental Analyzer Analysis Methods" (JY / T 0580—2020).

[0053] Raw materials used in the examples: Tetrahydroxypropylethylenediamine: CAS (102-60-3); Maleic acid: CAS (110-16-7). Sorbic acid: CAS (110-44-1); Ferulic acid: CAS (537-98-4); Caffeic acid: CAS (331-39-5); Cinnamic acid: CAS (140-10-3); Fumaric acid: CAS (110-17-8); Triethylene glycol diamine: Huntsman EDR 148; Polyetheramine MA-2200: Purchased from Wuxi Akoli Technology Co., Ltd.; Polyetheramine MA2203ED: Purchased from Wuxi Akoli Technology Co., Ltd.; All of the above-mentioned raw materials can be purchased commercially.

[0054] Example 1: Sorbic Acid Only An organic amine supramolecular ionic salt has the following structural formula:

[0055] Its preparation method is as follows: Tetrahydroxypropylethylenediamine and sorbic acid were mixed and stirred at 65°C and 400 rpm for 4 hours to obtain an organic amine supramolecular ionic salt. The molar ratio of tetrahydroxypropylethylenediamine to sorbic acid is 1:2.

[0056] NMR spectra of organic amine supramolecular ion salts are as follows Figure 1 The NMR data are as follows: 1 H NMR (400 MHz, DMSO) δ 6.84~6.79 (m, 4H), 6.67~5.88 (m, 12H), ,5.82~5.55 (m, 4H), 3.65~3.24 (m, 12H), 2.87~2.62 (m, 4H), 1.9~1.64 (m, 12H). Theoretical element content (%) C 26 H 48 N2O8: C, 60.47; H, 9.3; N, 5.43; Measured elemental content (%): C, 60.34; H, 9.55; N, 5.37.

[0057] Example 1 demonstrates that the organic amine supramolecular ionic salt with the structure shown was synthesized.

[0058] Organic amine supramolecular ionic salt and water were dissolved at a mass ratio of 1:99 and stirred at 20℃ and 500rpm for 3 minutes. After complete dissolution, the pH was adjusted to 8 with 1M NaOH aqueous solution to obtain the repair solution. The repair effect was tested according to test method "2, Repair Effect Test". The test results are as follows. Figure 2 , Figure 3 ; from Figure 2 It can be seen that untreated damaged hair exhibits significant fluorescence and clear cuticle gaps, indicating that the open cuticles expose the internal keratin structures containing thiol groups. Reduced hair treated with thioglycolic acid shows strong fluorescence, with further enlargement of cuticle gaps and the appearance of fluorescent patches formed by localized peeling, indicating structural damage and an increase in free thiol groups due to disulfide bond breakage. In contrast, reduced hair treated with organic amine supramolecular ion salts shows significantly reduced fluorescence and virtually invisible cuticle gaps, indicating that this treatment effectively reduces free thiol groups, fills the cuticle gaps, and makes the surface smoother.

[0059] Figure 3Macroscopic morphological observations showed that untreated damaged hair had a rough surface and raised cuticles; hair treated with thioglycolic acid suffered more damage and cuticle peeling was more obvious; while hair treated with organic amine supramolecular ionic salts had reduced surface damage and smoother cuticle arrangement, which directly confirmed that the treatment can effectively repair the macroscopic structure of hair and improve its damaged condition.

[0060] Example 2 Maleic acid and sorbic acid An organic amine supramolecular ionic salt has the following structural formula:

[0061] Its preparation method is as follows: Maleic acid and sorbic acid were ground at 25°C for 40 min to form an organic acid mixture powder with a particle size controlled at 50 μm. Then, the organic acid mixture powder and tetrahydroxypropylethylenediamine were stirred at 75°C and 600 rpm for 6 h. After washing with anhydrous ethanol and air drying, an organic amine supramolecular ionic salt was obtained. The molar ratio of tetrahydroxypropylethylenediamine, maleic acid and sorbic acid was 1:1:1.

[0062] Theoretical element content (%) C 24 H 44 N2O 10 :C, 55.38; H, 8.46; N, 5.38; Measured elemental content (%): C, 55.44; H, 8.55; N, 5.26.

[0063] The above characterization demonstrates that Example 2 successfully carried out the proton exchange reaction of tetrahydroxypropylethylenediamine with maleic acid and sorbic acid, and successfully synthesized an organic amine supramolecular ionic salt containing a diene bond structure.

[0064] Example 3: Sorbic acid and cinnamic acid An organic amine supramolecular ionic salt has the following structural formula:

[0065] The preparation method of organic amine supramolecular ionic salts is as follows: Sorbic acid and cinnamic acid were ground at 35°C for 25 min to form an organic acid mixture powder with a particle size controlled at 40 μm. Then, the organic acid mixture powder and tetrahydroxypropylethylenediamine were stirred at 65°C and 500 rpm for 7 h to obtain an organic amine supramolecular ionic salt. After washing with anhydrous ethanol and air drying, the molar ratio of tetrahydroxypropylethylenediamine, sorbic acid and cinnamic acid was 1:1:1.

[0066] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 29 H 48 N2O8: C, 63.04; H, 8.70; N, 5.07; Measured elemental content (%): C, 63.16; H, 8.75; N, 5.13.

[0067] The above characterization demonstrates that Example 3 successfully carried out the proton exchange reaction of tetrahydroxypropylethylenediamine with sorbic acid and cinnamic acid, and successfully synthesized an organic amine supramolecular ionic salt containing a diene bond structure.

[0068] Example 4: Sorbic acid and caffeic acid An organic amine supramolecular ionic salt has the following structural formula:

[0069] The preparation method of organic amine supramolecular ionic salts is as follows: Sorbic acid and caffeic acid were ground at 25°C for 35 min to form an organic acid mixture powder with a particle size controlled at 60 μm. Then, the organic acid mixture powder and tetrahydroxypropylethylenediamine were stirred at 85°C and 700 rpm for 4 h to obtain an organic amine supramolecular ionic salt. The mixture was then washed with anhydrous ethanol and air-dried. The molar ratio of tetrahydroxypropylethylenediamine, sorbic acid and caffeic acid was 1:1:1.

[0070] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 29 H 48 N2O 10 :C, 59.59; H, 8.22; N, 4.79; Measured elemental content (%): C, 59.46; H, 8.15; N, 4.83.

[0071] The above characterization demonstrates that Example 4 successfully carried out the proton exchange reaction of tetrahydroxypropylethylenediamine with sorbic acid and caffeic acid, and successfully synthesized an organic amine supramolecular ionic salt containing a diene bond structure.

[0072] Example 5 Maleic acid and ferulic acid An organic amine supramolecular ionic salt has the following structural formula:

[0073] The preparation method of organic amine supramolecular ionic salts is as follows: Maleic acid and tetrahydroxypropylethylenediamine were mixed and stirred at 65°C and 400 rpm for 3 h; then ferulic acid was added and stirred at 75°C and 400 rpm for 4 h. After washing with anhydrous ethanol and air drying, an organic amine supramolecular ionic salt was obtained; wherein the molar ratio of tetrahydroxypropylethylenediamine to maleic acid and ferulic acid was 1:1:1.

[0074] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 28 H 46 N2O 12 :C, 55.81; H, 7.64; N, 4.65; Measured elemental content (%): C, 55.66; H, 7.45; N, 4.63.

[0075] The above characterization demonstrates that Example 5 successfully carried out the proton exchange reaction of tetrahydroxypropylethylenediamine with maleic acid and ferulic acid, and successfully synthesized an organic amine supramolecular ionic salt containing a diene bond structure.

[0076] Example 6: Fumaric acid and caffeic acid An organic amine supramolecular ionic salt has the following structural formula:

[0077] The preparation method of organic amine supramolecular ionic salts is as follows: Fumaric acid and tetrahydroxypropylethylenediamine were mixed and stirred at 95°C and 600 rpm for 2 h; then caffeic acid was added and stirred at 85°C and 400 rpm for 5 h. After washing with anhydrous ethanol and air drying, an organic amine supramolecular ion salt was obtained; wherein the molar ratio of tetrahydroxypropylethylenediamine to fumaric acid and caffeic acid was 1:1:1.

[0078] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 27 H 44 N2O 12 :C, 55.10; H, 7.48; N, 4.76; Measured elemental content (%): C, 55.16; H, 7.50; N, 4.71.

[0079] The above characterization demonstrates that Example 6 successfully carried out the proton exchange reaction of tetrahydroxypropylethylenediamine with fumaric acid and caffeic acid, and successfully synthesized an organic amine supramolecular ionic salt containing a diene bond structure.

[0080] Example 7 Maleic acid and fumaric acid An organic amine supramolecular ionic salt has the following structural formula:

[0081] The preparation method of organic amine supramolecular ionic salts is as follows: Maleic acid and tetrahydroxypropylethylenediamine were mixed and stirred at 200 rpm for 20 min at room temperature; then fumaric acid was added and stirred at 400 rpm for 20 min at room temperature. The mixture was then washed with anhydrous ethanol and air-dried to obtain an organic amine supramolecular ionic salt; wherein the molar ratio of tetrahydroxypropylethylenediamine to maleic acid and fumaric acid was 1:1:1.

[0082] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 22 H 40 N2O 12 :C, 50.38; H, 7.63; N, 5.34; Measured elemental content (%): C, 50.26; H, 7.56; N, 5.31.

[0083] The above characterization demonstrates that Example 7 successfully carried out the proton exchange reaction of tetrahydroxypropylethylenediamine with maleic acid and fumaric acid, and successfully synthesized an organic amine supramolecular ionic salt containing a diene bond structure.

[0084] Example 8: Caffeic acid only An organic amine supramolecular ionic salt has the following structural formula:

[0085] Its preparation method is as follows: Tetrahydroxypropylethylenediamine and caffeic acid were mixed and stirred at 65°C and 400 rpm for 4 hours to obtain an organic amine supramolecular ionic salt. The molar ratio of tetrahydroxypropylethylenediamine to caffeic acid is 1:2.

[0086] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 32 H 48 N2O 12 :C, 58.90; H, 7.36; N, 4.29; Measured elemental content (%): C, 59.01; H, 7.17; N, 4.31.

[0087] Example 8 demonstrates that the organic amine supramolecular ionic salt with the structure shown was synthesized.

[0088] Example 9: Ferulic acid only An organic amine supramolecular ionic salt has the following structural formula:

[0089] Its preparation method is as follows: Tetrahydroxypropylethylenediamine and ferulic acid were mixed and stirred at 85°C and 400 rpm for 3 hours to obtain an organic amine supramolecular ionic salt. The molar ratio of tetrahydroxypropylethylenediamine to ferulic acid is 1:2.

[0090] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 34 H 52 N2O 12 :C, 60.00; H, 7.65; N, 4.12; Measured elemental content (%): C, 59.97; H, 7.57; N, 4.09.

[0091] Example 9 demonstrates that the organic amine supramolecular ionic salt with the structure shown was synthesized.

[0092] Example 10 Fumaric acid only An organic amine supramolecular ionic salt has the following structural formula:

[0093] Its preparation method is as follows: Tetrahydroxypropylethylenediamine and fumaric acid were mixed and stirred at 75°C and 400 rpm for 7 h to obtain an organic amine supramolecular ionic salt. The molar ratio of tetrahydroxypropylethylenediamine to fumaric acid is 1:2.

[0094] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 22 H 40 N2O 12 :C, 50.38; H, 7.63; N, 5.34; Measured elemental content (%): C, 50.36; H, 7.66; N, 5.36.

[0095] Example 10 demonstrates that the organic amine supramolecular ionic salt with the structure shown was synthesized.

[0096] The obtained ionic salts were tested for their hair care properties, and the results are as follows: Table 1

[0097] Comparative Example 1: Glacial acetic acid and sorbic acid In Example 2, maleic acid was replaced with glacial acetic acid, while everything else remained the same as in Example 2.

[0098] Comparative Example 2: Increase the dosage of maleic acid The molar ratio of tetrahydroxypropylethylenediamine, maleic acid, and sorbic acid in Example 2 was adjusted to 1:1.4:1, while other aspects remained the same as in Example 2.

[0099] Comparative Example 3: Oleic acid and ferulic acid In Example 5, maleic acid was replaced with oleic acid, while everything else remained the same as in Example 5.

[0100] Comparative Example 4 Commercially available diaminopropyl diethylene glycol dimaleate is used.

[0101] Comparative Example 5 In Example 8, caffeic acid was replaced with oleic acid, while other aspects remained the same as in Example 8, resulting in an ionic salt.

[0102] Comparative Example 6 The molar ratio of tetrahydroxypropylethylenediamine and caffeic acid in Example 8 was adjusted to 1:1.5, while other aspects remained the same as in Example 8, to obtain an ionic salt.

[0103] Comparative Example 7 A method for preparing an organic amine supramolecular ionic salt includes the following steps: Maleic acid, sorbic acid, and tetrahydroxypropylethylenediamine were mixed and stirred at 400 rpm for 40 min at room temperature. The mixture was then washed with anhydrous ethanol and air-dried to obtain an organic amine supramolecular ionic salt. The molar ratio of tetrahydroxypropylethylenediamine to maleic acid and sorbic acid was 1:1:1.

[0104] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: The ionic salt and water were mixed at a mass ratio of 1:99, stirred at 20℃ and 500 rpm for 3 minutes until fully dissolved. The pH was then adjusted to 8 with 1M NaOH solution to obtain the repair solution. The repair effect was tested according to test method "2, Repair Effect Test". The test results are as follows: Figure 6 ; from Figure 6It can be seen that: after the repair solution corresponding to Example 1 was used to treat the damaged hair, the degree of damage was reduced, the number of damaged sites was reduced, the hair cuticles were smoother, and the tendency to lift was weakened; after the repair solution corresponding to Comparative Example 1 was used to treat the damaged hair, the hair was relatively rough, there were more damaged sites, and the hair cuticles tended to lift and peel off; after the repair solution corresponding to Comparative Example 2 was used to treat the damaged hair, the hair was relatively rough, there were more damaged sites, and the hair cuticles tended to lift and peel off; after the repair solution corresponding to Comparative Example 3 was used to treat the damaged hair, the hair was very rough, there were the most damaged sites, and the hair cuticles lifted and peeled off; after the repair solution corresponding to Comparative Example 4 was used to treat the damaged hair, the hair was slightly improved, but the degree of improvement was not significant.

[0105] This demonstrates that the organic amine supramolecular ionic salt obtained in Example 1 exhibits excellent hair repair properties. Comparative Examples 1, 2, and 4, while possessing some hair repair effects, showed only minor improvements; Comparative Example 3, however, did not demonstrate any hair repair properties.

[0106] Table 2

[0107] Example 11 The tetrahydroxypropylethylenediamine in Example 1 was changed to triethylene glycol diamine, while everything else remained the same as in Example 1, to obtain the ionic salt.

[0108] The structural formula of the ionic salt is as follows:

[0109] The obtained organic amine supramolecular ionic salt was subjected to performance testing, and the test results are as follows: Theoretical element content (%) C 18 H 32 N2O6: C, 58.06; H, 8.60; N, 7.53; Measured elemental content (%): C, 58.11; H, 8.69; N, 7.42.

[0110] Example 11 demonstrates the synthesis of the organic amine supramolecular ionic salt with the structure shown.

[0111] Example 12 In Example 1, tetrahydroxypropylethylenediamine was replaced with polyetheramine MA2203ED, while other aspects remained the same as in Example 1, resulting in an ionic salt.

[0112] The structural formula of the ionic salt is as follows:

[0113] Where x is 3; y is 39; z is 3.

[0114] Infrared spectrum of ionic salts as follows Figure 4 ,from Figure 4 It can be seen that: compared with the raw materials sorbic acid and polyetheramine MA2203ED, the supramolecular ionic salt has a thickness of 3443-2491 cm⁻¹. -1 The presence of a broad absorption peak is a hallmark of the protonation of the amino group (-NH2) in MA2203ED to form a salt (+NH3), indicating that the carboxyl hydroxyl group in sorbic acid has been successfully transferred to the amino group in MA2203ED. Furthermore, the carbonyl group in sorbic acid (1645 cm⁻¹) shows a significant absorption peak. -1 After forming an ionic salt, it shifts to 1697 cm⁻¹. -1 This also indicates that the carbonyl electron cloud density changes after salt formation, thereby altering infrared absorption; the above results prove that Example 12 successfully synthesized a supramolecular ionic salt.

[0115] Example 13 The tetrahydroxypropylethylenediamine in Example 1 was changed to polyetheramine MA-2200, while other aspects remained the same as in Example 1, to obtain an ionic salt.

[0116] The structural formula of the ionic salt is as follows:

[0117] Where x is 33.

[0118] Infrared spectrum of ionic salts as follows Figure 5 ,from Figure 5 It can be seen that: supramolecular ionic salts have a 2500-3324 cm⁻¹ -1 The presence of a broad absorption peak indicates that the amino group (-NH2) in MA-2200 has been protonated to form a salt (+NH3), signifying that the carboxyl hydroxyl group in sorbic acid has been successfully transferred to the amino group in MA-2200. The above results confirm that the supramolecular ionic salt was successfully synthesized in Example 13.

[0119] Example 14 In Example 5, tetrahydroxypropylethylenediamine was replaced with triethylene glycol diamine, while other aspects remained the same as in Example 5, resulting in an ionic salt.

[0120] The structural formula of the ionic salt is as follows:

[0121] Example 15 In Example 5, tetrahydroxypropylethylenediamine was replaced with polyetheramine MA-2200, while other aspects remained the same as in Example 5, resulting in an ionic salt.

[0122] The structural formula of the ionic salt is as follows:

[0123] Where x is 33.

[0124] Example 16 In Example 5, tetrahydroxypropylethylenediamine was replaced with polyetheramine MA2203ED, while other aspects remained the same as in Example 5, resulting in an ionic salt.

[0125] The structural formula of the ionic salt is as follows:

[0126] Where x is 3; y is 39; z is 3.

[0127] Example 17 In Example 8, tetrahydroxypropylethylenediamine was replaced with triethylene glycol diamine, while other aspects remained the same as in Example 8, resulting in an ionic salt.

[0128] The structural formula of the ionic salt is as follows:

[0129] Example 18 In Example 8, tetrahydroxypropylethylenediamine was replaced with polyetheramine MA-2200, while other aspects remained the same as in Example 8, resulting in an ionic salt.

[0130] The structural formula of the ionic salt is as follows:

[0131] Where x is 33.

[0132] Example 19 In Example 8, tetrahydroxypropylethylenediamine was replaced with polyetheramine MA2203ED, while other aspects remained the same as in Example 8, resulting in an ionic salt.

[0133] The structural formula of the ionic salt is as follows:

[0134] Where x is 3; y is 39; z is 3.

[0135] The obtained ionic salts were tested for their hair care properties, and the results are as follows: Table 3

[0136] Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make various modifications and alterations without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be determined by the claims.

Claims

1. An organic amine supramolecular ionic salt, characterized in that, The structure is as follows: Formula I Formula II Formula III Formula IV R1 and R2 can be the same or different, and the specific structural formula can be any of the following: or or or or or In Equation III, x is 6-50; In Equation IV, x is 1-50, y is 1-80, and z is 1-50.

2. A method for preparing organic amine supramolecular ionic salts, characterized in that, Includes the following steps: Organic amines and organic acids are mixed to obtain organic amine supramolecular ionic salts; Among them, the organic acid is any one or two of maleic acid, sorbic acid, ferulic acid, caffeic acid, cinnamic acid, and fumaric acid; The organic amine is one of tetrahydroxypropylethylenediamine, triethylene glycol diamine, or polyetheramine; the polyetheramine includes one or two of MA-2200 and MA2203ED.

3. The method according to claim 2, characterized in that, When the organic acid is only one type, the method for preparing the supramolecular ionic salt of an organic amine includes the following steps: Organic amines and organic acids were stirred at 55-95℃ and 200-800 rpm for 3-10 h to obtain organic amine supramolecular ionic salts. The molar ratio of organic amines to organic acids is 1:

2.

4. The method according to claim 2, characterized in that, When there are two organic acids, the methods for preparing organic amine supramolecular ionic salts include the following two: Method 1: The first and second acids are ground at 15-35℃ for 20-60 min to form an organic acid mixture powder with a particle size controlled at 5-100 μm. Then, the organic acid mixture powder and organic amine are stirred at 55-95℃ and 350-800 rpm for 2-8 h to obtain an organic amine supramolecular ionic salt. The molar ratio of organic amine to the first and second acids is 1:1:

1. Method 2: The first organic acid and the organic amine are mixed and stirred at 55-95℃ and 200-800 rpm for 2-4 h; then the second organic acid is added and stirred at 55-95℃ and 200-800 rpm for 1-6 h to obtain the organic amine supramolecular ionic salt; wherein the molar ratio of the organic amine to the first acid and the second acid is 1:1:

1.

5. The method according to claim 2, characterized in that, After the reaction is complete, purification can be performed by washing with anhydrous ethanol and drying.

6. The use of the organic amine supramolecular ionic salt according to claim 1 in the preparation of daily chemical products or pharmaceuticals.

7. A hair care product, characterized in that, It contains the organic amine supramolecular ionic salt as described in claim 1.

8. The hair care product according to claim 7, characterized in that, The mass concentration of organic amine supramolecular ionic salts in hair care products is 0.01-20%.

9. The hair care product according to claim 7, characterized in that, The ingredients in hair care products include: Phase A: Disodium EDTA, Cetearyl Alcohol, Cetyl Alcohol, Fentacare 1831 70, Fentacare 2231 EF; Phase B: Water, hydroxyethyl cellulose; C phase: C13-15 alkyl, polydimethylsiloxane, bis-aminopropyl polydimethylsiloxane; Phase D: PE 9010, hair oil TC-2115, organic amine supramolecular ion salt, fragrance; Phase E: Citric acid.

10. A method for improving hair care products to repair damaged hair and improve hair smoothness, characterized in that, The organic amine supramolecular ionic salt described in claim 1 was used.

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