A silicone supramolecular ionic salt with hair care efficacy and a preparation method thereof

Abstract

The application discloses a silicone supramolecular ionic salt with hair care efficacy and a preparation method thereof, and belongs to the technical field of supramolecules. The silicone supramolecular ionic salt uses a siloxane chain as a central skeleton to connect a double bond structure, provides the product with the ability to repair hair, introduces a siloxane structure, fundamentally repairs hair, forms a siloxane protective film on the surface of hair, and makes the treated hair more supple and prevents further damage. The silicone supramolecular ionic salt belongs to a supramolecular ionic salt, is processed into water-soluble from completely hydrophobic siloxane chains, is more convenient for formula design, and can be directly used in formula design at the product end from the product end.

Description

Technical Field

[0001] The invention relates to an organosilicon supramolecular ion salt with hair care efficacy and a preparation method thereof, belonging to the technical field of supramolecular ions. Background Art

[0002] Nowadays, people have an increasing demand for hair care, and the frequency of hair washing, perming, dyeing and styling is higher. In addition, environmental stress can easily cause hair damage. These factors often lead to problems such as dry and frizzy hair, decreased softness, damaged hair quality, and easy breakage.

[0003] The damaging effects of perming hair are well known, involving the breakage and reformation of disulfide bonds within the hair. The typical perming process involves a two-step process. In the first step, reducing agents (such as thioglycolates and bisulfites) are used to cleave disulfide bonds into free sulfhydryl groups. Sometimes, to improve perming efficiency, strong oxidizing agents such as hydrogen peroxide are added during the second, oxidation step, which can further damage the hair surface and reduce hair fiber strength.

[0004] Studies have shown that prolonged exposure to reducing or oxidizing agents during the perming process reduces the content of α-helical proteins in hair. This phenomenon can be observed in the wide-angle X-ray diffraction (WAXD) pattern, that is, the signal intensity associated with accumulation is reduced at the level of individual keratin fibers.

[0005] The perming process converts the hydrophobic hair surface into a more hydrophilic one, which in turn increases the lipid loss in the hair cuticle during interaction with shampoo. Keratin, disulfide bonds, and lipid content are closely related to hair tensile properties, so perming can easily affect hair tensile properties.

[0006] Currently, polysiloxanes with a silicon-oxygen-silicon structure are also commonly used in hair care products. Although the silicon-oxygen-silicon structure cannot directly repair the hair structure, it can form a protective film on the hair surface, effectively reducing external damage and moisture loss from the hair. It can also fill the hair scales, improve frizziness, and reduce breakage and damage caused by combing. However, even with only two silicon atoms, the polysiloxane structure is highly hydrophobic. When used in formulas, it must be processed into an emulsion system, which increases the cost of use and makes it difficult for the hair to remain on the hair for a long time. In addition, the hair care principle of polysiloxane is to reduce the damage to the hair, and it cannot repair severely damaged hair.

[0007] Patent CN102525845B discloses the use of organopolysiloxane and maleic anhydride to prepare hair care cosmetics, wherein maleic anhydride is connected to the side chain of organopolysiloxane through a grafting reaction, and the prepared hair care cosmetics are covalent compounds bound by covalent bonds, and the hair care effect is specifically a softening effect. The above technology requires the use of organic solvents in the actual production process, which is not environmentally friendly. At the same time, there are problems with the reaction rate of the amidation reaction, and the product purification process is relatively complicated. The existing compound bisaminopropyl diglycol dimaleate discloses the function of repairing disulfide bonds in hair through a diene bond structure C=C, but the compound structure is a carbon chain polyether structure. It can improve the water solubility of the compound, but can only provide the ability to smooth the hair by repairing the hair. At the same time, the compound is in liquid form and is subject to certain limitations during storage and transportation.

[0008] Therefore, preparing a supramolecular compound that has good hair repairing effect, can soften hair, and is easy to store and transport has extremely high practical value and economic value. Summary of the Invention

[0009] To address the shortcomings of the prior art, the present invention uses maleic acid and amino-terminated siloxane to prepare an organosilicon supramolecular ion salt. The organosilicon supramolecular ion salt provided by the present invention has hair repair and softening functions, and can also fill damaged hair scales.

[0010] The first object of the present invention is to provide an organosilicon supramolecular ion salt having the following structural formula:

[0011]

[0012] Among them, the structural formula of A is as follows:

[0013]

[0014] n is an integer greater than or equal to 1.

[0015] Preferably, n is an integer of 1 to 5; more preferably, n is 1.

[0016] A second object of the present invention is to provide a method for preparing the above-mentioned organosilicon supramolecular ion salt, comprising the following steps:

[0017] Maleic acid and amino-terminated siloxane are mixed to prepare an organosilicon supramolecular ion salt.

[0018] In one embodiment, the method for preparing an organosilicon supramolecular ionic salt comprises:

[0019] Dissolving maleic acid in a solvent and mixing with amino-terminated siloxane to obtain an organosilicon supramolecular ion salt;

[0020] or,

[0021] The maleic acid is ground, mixed with the amino-terminated siloxane, and grinding is continued to obtain the silicone supramolecular ionic salt.

[0022] In one embodiment, the amino-terminated siloxane structure is as follows:

[0023]

[0024] n is an integer greater than or equal to 1.

[0025] In one embodiment, the amino-terminated siloxane includes one or both of 1,3-bis(3- aminopropyl)-1,1,3,3-tetramethyldisiloxane (CAS No. 2469-55-8, n = 1) or amodimethicone (CAS: 97917-34-5, n > 2) or an amino-silicone water-soluble emulsion system (product model Silsoft AM 1021N LV PMF emulsion).

[0026] In one embodiment, after the silicone supramolecular ionic salt is prepared, ethyl acetate can be used for washing and drying to obtain a high-purity silicone supramolecular ionic salt.

[0027] In one embodiment, the solvent includes, but is not limited to, water, methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, and other solvents that can dissolve maleic acid, but does not include solvents containing carboxyl groups or solvents with strong acidity.

[0028] Preferably, the solvent is selected from deionized water, methanol, ethanol, and other solvents with low boiling points.

[0029] In one embodiment, the molar ratio of maleic acid to amino groups in the amino-terminated siloxane is 1:0.8-1.3.

[0030] Preferably, the molar ratio of maleic acid to amino groups in the amino-terminated siloxane is 1:1-1.1.

[0031] In one embodiment, the mass ratio of maleic acid to solvent is 1-2:4.

[0032] In one embodiment, the temperature of the system during preparation is 25-40°C.

[0033] In one embodiment, the grinding is grinding at room temperature for 0.1-1 h until the system is a white uniform solid.

[0034] In one embodiment, the method of the silicone supramolecular ionic salt described above includes the following steps:

[0035] (1) maleic acid and deionized water are mixed in a mass ratio of 1-2:2-6, and stirred at room temperature for 5-30 minutes until the maleic acid is completely dissolved, thereby preparing a maleic acid aqueous solution;

[0036] (2) Weighing an amino double-capped end cap (the molar ratio of the amino double-capped end cap to maleic acid is 1:1-5), slowly dropping the amino double-capped end cap into the maleic acid aqueous solution under stirring, and continuing to stir the reaction for 1-3 hours after the addition is completed;

[0037] (3) After the reaction is completed, the solvent water in the system is volatilized, washed with ethyl acetate, filtered, and dried to obtain an organosilicon supramolecular ion salt (i.e., amino double-capped maleate).

[0038] In one embodiment, the method for preparing the organosilicon supramolecular ionic salt comprises the following steps:

[0039] Grind the maleic acid and add the amino double head (the molar ratio of the amino double head to maleic acid is 1:1-5); continue grinding until there is no obvious wet part, continue to drip the amino double head until the amino double head is completely added, continue grinding for 10-30 minutes until the system becomes fine and dry, add ethyl acetate for washing, filter, and dry to obtain an organosilicon supramolecular ion salt (i.e., amino double head maleate).

[0040] The third object of the present invention is to provide the use of the above-mentioned organosilicon supramolecular ion salt in the preparation of daily chemical products and medicines.

[0041] In one embodiment, the daily chemical products include: hair care cosmetics and detergents.

[0042] In one embodiment, the hair care cosmetics include: hair conditioner, hair oil, hair cream, hair wax, hair lotion, after-wash sunscreen lotion, steam-free hair cream, sunscreen shampoo, medicated hair cream, conditioning shampoo, shampoo, and aftershave.

[0043] The fourth object of the present invention is to provide a product containing an organosilicon supramolecular ion salt; the product is a daily chemical product or a medicine.

[0044] In one embodiment, the hair care cosmetics include: hair conditioner, hair oil, hair cream, hair wax, hair lotion, after-wash sunscreen lotion, steam-free hair cream, sunscreen shampoo, medicated hair cream, conditioning shampoo, shampoo, and aftershave.

[0045] A fifth object of the present invention is to provide a hair care product containing an organosilicon supramolecular ionic salt.

[0046] In one embodiment, the amount of the organosilicon supramolecular ion salt added is 0.01 to 20% w / w;

[0047] Preferably, the added amount of the organosilicon supramolecular ion salt is 0.01 to 15% w / w.

[0048] In one embodiment, the organosilicon supramolecular ionic salt can be added to commercially available hair care products without dispersibility issues.

[0049] In one embodiment, the above-mentioned organosilicon supramolecular ion salt is used as an effective ingredient to prepare a hair care product, the components of which include: sodium lauryl sulfate (SDS), cocamidopropyl betaine, an effective ingredient, citric acid and water;

[0050] The preparation method comprises: mixing SDS and water, adding cocamidopropyl betaine and functional ingredients, mixing well, and adjusting the pH to a value close to the natural pH value of the scalp using citric acid to obtain a hair care product.

[0051] In one embodiment, the content of sodium lauryl sulfate is 0.05-1% w / w, the content of cocamidopropyl betaine is 0.01-1% w / w, the content of the functional ingredient is 0.01-1% w / w, the content of citric acid is 0.1-0.5% w / w, and water is added to 100%.

[0052] Beneficial effects of the present invention

[0053] The present invention uses maleic acid and 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (amino double-capped) to prepare an organosilicon supramolecular ion salt. The organosilicon supramolecular ion salt provided by the present invention can structurally repair disulfide bonds in hair. At the same time, the siloxane structure can fill damaged hair scales in the hair to achieve the purpose of repairing hair and making hair smooth.

[0054] (1) Structurally, the organosilicon supramolecular ionic salt (amino dicapped maleate) of the present invention uses a siloxane chain as a central skeleton to connect the diene bond structure. While providing the product with the ability to repair hair, it also introduces a siloxane structure, enabling the product to fundamentally repair hair and simultaneously forming a siloxane protective film on the hair surface, making the treated hair more supple and preventing further damage.

[0055] Specifically, the organosilicon supramolecular ion salt of the present invention reduces the static friction coefficient and kinetic friction coefficient of hair by 25.49% and 29.20% respectively, and reduces the dry combing work by 11.7%; its repair and softening effects on damaged and lost hair are significantly better than those of the existing compound (bisaminopropyl diglycol dimaleate).

[0056] (2) In terms of properties, the organosilicon supramolecular ionic salt (amino double-capped maleate) of the present invention is a supramolecular ionic salt, which processes the completely hydrophobic siloxane chain into water-soluble, making it more convenient to design the formula; and the production process does not require the addition of additional solvents or directly uses water as a solvent, and the reaction rate and yield are both high, and can be directly applied from the product end to the product end formula design. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] Figure 1 This is the Fourier transform infrared spectrum of the organosilicon supramolecular ion salt prepared in Example 1.

[0058] Figure 2 This is the H-NMR spectrum of the organosilicon supramolecular ion salt prepared in Example 1.

[0059] Figure 3 This is the Fourier transform infrared spectrum of the organosilicon supramolecular ion salt prepared in Example 2.

[0060] Figure 4 This is the H-NMR spectrum of the organosilicon supramolecular ion salt prepared in Example 2.

[0061] Figure 5 These are photos of original hair (a), hair reduced with thioglycolic acid (b), and hair treated with repair solution A (c) in Example 3, taken under a fluorescence microscope.

[0062] Figure 6 SEM images of original hair (a), thioglycolic acid-reduced hair (b) in Example 3, hair treated with repair solution E (c) in Comparative Example 4, and hair treated with repair solution A (d) are shown.

[0063] Figure 7 The products obtained in Comparative Example 1, Comparative Example 2, and Comparative Example 4 were used to prepare repair solutions C, D, and E, and then the hair was treated with the repair solutions C, D, and E, respectively. The photos of the treated hair under a fluorescence microscope were obtained. DETAILED DESCRIPTION

[0064] 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. The technical solutions of the present invention are further described below by means of specific examples. It should be understood that the implementation of the present invention is not limited to the following examples, and any pro forma modifications and / or changes made to the present invention will fall within the scope of protection of the present invention. In the present invention, unless otherwise specified, all parts and percentages are weight units, and the equipment and raw materials used can be purchased from the market or are commonly used in this area. The methods in the following embodiments, unless otherwise specified, are conventional methods in this area.

[0065] The raw materials used in the embodiment are:

[0066] 1,3-Bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (referred to as amino double-capped in the subsequent examples; wherein n=1 in the siloxane chain) was purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd.; CAS number: 2469-55-8;

[0067] Aminopropyl-terminated polydimethylsiloxane was purchased from Huangshan Qiangli Chemical Co., Ltd.; CAS number: 99904-16-2;

[0068] Bisaminopropyl diglycol dimaleate was purchased from Jining Tangyi Chemical Co., Ltd., CAS No.: 1629579-82-3;

[0069] Silsoft AM 1021N LV PMF emulsion (hereinafter referred to as aminosilicone water-soluble emulsion system 1201) was purchased from Guangzhou Best Chemical Co., Ltd.

[0070] The original hair mentioned in the examples is: dyed damaged straight hair (22.5 cm x 5.5 cm x 7 g, free 19.5 cm), purchased from Shanghai Canyu Trading Co., Ltd.

[0071] The reduced hair mentioned in the examples is obtained by soaking purchased hair in an 8% by mass aqueous solution of thioglycolic acid with a pH of 8.5 and shaking the solution at 50° C. for 30 minutes.

[0072] The repaired hair mentioned in the examples was obtained by immersing restored hair in the repair solution prepared in the corresponding example and shaking at 50°C for 30 minutes. The human hair pieces mentioned in the examples were healthy human hair pieces (25 cm × 2.5 cm × 3 g, free 22.5 cm) purchased from Shanghai Canyu Trading Co., Ltd.

[0073] The aminopolysiloxane water-soluble systems mentioned in the examples are: various common aminopolysiloxane water-soluble systems on the market, such as aminosilicone water-soluble emulsion system 1201.

[0074] Test method:

[0075] 1. Infrared test:

[0076] Liquid sample testing: Take 20-30 mg of sample and dilute it with 3-5 mL of dichloromethane. Place approximately 0.2 mL of the diluted solution onto a potassium bromide window that has been previously cleaned and dried with anhydrous ethanol. Heat the sample using an infrared lamp until a thin film forms on the window. The window is then placed in a Nicolet iS5 Fourier transform infrared spectrometer for analysis.

[0077] Solid sample testing: A solid sample and potassium bromide crystals were mixed in a mass ratio of 2:98. The mixture was evenly mixed in a mortar and ground into a solid system with finer particles. The solid system was dried with an infrared lamp and pressed into tablets using a tablet press. The tablets were then placed in a Nicoleti S5 Fourier infrared spectrometer for testing to obtain the results.

[0078] 2. MRI test:

[0079] Deuterated chloroform was used as a deuterated reagent for double-capped amino groups, and deuterated DMSO was used as a deuterated reagent for maleic acid. 5 to 10 mg of each sample was dissolved in a nuclear magnetic resonance tube and tested using an AVANCE III HD 400 MHz nuclear magnetic resonance spectrometer to obtain the results.

[0080] 3. Repair effect test:

[0081] When hair is damaged, the disulfide bonds in the hair's keratin are cut, causing it to lose elasticity and luster, become dry and brittle, etc. The cleavage of the disulfide bonds will produce two free sulfhydryl groups, so measuring the sulfhydryl content in damaged hair can more intuitively determine the extent of hair damage.

[0082] Rhodamine B (RB) is one of the most commonly used fluorescent dyes. 3- ) can react with RB to quench its fluorescence and weaken its fluorescence intensity, while the thiol group can 3- Restore to I - , thereby enhancing the fluorescence intensity. Through the fluorescence interaction between iodine solution and rhodamine B, the residual thiol groups in the hair can be reduced to I 3- , and then observe the fluorescence intensity of the hair under a fluorescence microscope. If the repair goes smoothly, the fluorescence intensity of the repaired hair should be much lower than that of the damaged hair, thereby visualizing the repair effect of the thiol group.

[0083] Pre-configuration 10 -3 mol / L iodine standard solution, 10 -4 mol / L rhodamine B solution and acetic acid-sodium acetate buffer were prepared for use.

[0084] In this experiment, hair was placed in the reducing agent, thioglycolic acid, and shaken in a constant-temperature shaking incubator for 3 hours. The hair was then removed, dried, and stored in nitrogen to obtain the restored hair. Appropriate amounts of the restored hair were then cut and incubated with various repair solutions (prepared in the Examples or Comparative Examples) for 20 minutes. The hair was then removed and dried in a nitrogen atmosphere to obtain the repaired hair.

[0085] Several repaired hairs from each group were placed in 2 mL of iodine-labeled solution and vortexed for 5 minutes. Then, 3 mL of rhodamine B solution and 5 mL of acetic acid-sodium acetate buffer were added. The hairs were allowed to stand for 10 minutes, then removed and soaked in deionized water. After vortexing for 5 minutes, the hairs were removed and rinsed several times with deionized water to remove any residual rhodamine B. After drying, the hairs were observed under a 360 nm fluorescence microscope.

[0086] 4. Friction coefficient test

[0087] The experiments were conducted at a temperature of (25±2)°C and a humidity of (50±5)%. Each group of hair strands was immersed in a different repair solution (prepared in the Examples or Comparative Examples) for 30 seconds and then allowed to air dry in a constant temperature and humidity environment for 4 hours. The friction coefficient of each hair strand was measured using a fiber friction coefficient tester, comparing the dynamic and static friction coefficients before and after application of the repair solution. Fifteen sets of data were measured for each group, and the average was calculated.

[0088] 5. Dry combing work test

[0089] The experiment was conducted at a temperature of (25 ± 2)°C and a relative humidity of (50 ± 5)%. A 40 cm long, 25 g human hair piece was thoroughly moistened with 40°C warm water. Using a dropper, 5 mL of a 10% SDS aqueous solution was evenly applied to both sides of the piece and rubbed to create a lather. Avoid folding or twisting the hair to prevent tangles. Rinse the foam off with warm water. Repeat this process twice before allowing the piece to air dry in a constant temperature and humidity environment.

[0090] 10g of a 1% mass fraction of various repair solutions (prepared in the Examples or Comparative Examples) was evenly sprayed onto each hair tress. A simple combing process was then performed using a comb. After the hair tresses were air-dried at a constant temperature, the dry combing work of each tress was measured using a combing instrument. Each group of hair tresses was tested using two tresses of the same specifications, and the test was repeated seven times. Data processing yielded a combing curve, which was then integrated to determine the dry combing work.

[0091] 6. Scanning electron microscope (SEM) test

[0092] The treated and dried hair was cut into small segments of about 0.3 cm, fixed on an electron microscope stage with conductive glue, and the hair morphology was observed using a Hitachi S-4800 field emission scanning electron microscope.

[0093] The room temperature mentioned in the present invention is 15-30° C.; the stirring is 300-500 rpm for 5-10 minutes; within the above range, parameter changes will not affect product synthesis.

[0094] Example 1: Preparation of organosilicon supramolecular ion salt by solvent method

[0095] An organosilicon supramolecular ion salt, the structure of which is as follows:

[0096]

[0097] in,

[0098] n=1.

[0099] The preparation method of the above-mentioned organosilicon supramolecular ion salt is as follows:

[0100] 18.7 g of maleic acid and 40 g of deionized water were mixed in a reaction flask equipped with a stirring device, and stirred at room temperature for 10 min until the maleic acid was completely dissolved to prepare a maleic acid aqueous solution;

[0101] Accurately weigh 20 g of amino double head (the molar ratio of amino double head to maleic acid is 1:2), and slowly drop the amino double head into the maleic acid aqueous solution (approximately one drop of liquid per second) under stirring conditions, so that the system temperature is maintained at room temperature. After the addition is completed, stirring is continued for 2 hours; after the reaction is completed, the solvent water in the system is evaporated, washed with ethyl acetate, filtered, and dried to obtain 38.7 g of organosilicon supramolecular ion salt (i.e., amino double head maleate).

[0102] The amino double-capped maleate prepared in Example 1 was subjected to structural analysis, and the test results are as follows:

[0103] Infrared spectrum such as Figure 1 As shown. Figure 1 It can be seen that the amino double-capped maleate and maleic acid prepared in Example 1 have a -1 The characteristic peaks of silicon-oxygen-silicon appeared at , which proved that the siloxane structure was successfully introduced into the product.

[0104] Comparison of the amino double-end maleate and amino double-end prepared in Example 1 shows that 3350cm -1 The double peaks attributable to the amino group disappear and become a strong and broad peak. This is because the carboxyl peak in the introduced maleic acid structure covers the original amino peak position. At the same time, the product peak at 2100 cm -1 A broad peak appeared at , which indicated the presence of protonated amino groups, so the reaction process achieved the process of proton transfer.

[0105] NMR spectra such as Figure 2 As shown, specifically:

[0106] NMR data of amino double-capped maleate: 1H NMR (400MHz, d-DMSO) δ7.65(s,6H),6.03(m,4H),2.77(t,4H),1.534(m,4H),0.52(m,4H),0.067(s,12H).

[0107] Amino double head NMR data: 1 H NMR (400MHz, CDCl3) δ2.653(t,4H),1.395~1.482(m,8H),0.493(m,4H),0.041(s,12H).

[0108] In the amino double-capped maleate 1 In the H-NMR spectrum, a characteristic peak of protonated amino groups appears at position e (δ = 7.8 ppm), with an integrated area of ​​6. Comparing the 1H-NMR spectra of the amino dicapped maleate and amino dicapped maleates, the integrated area at position c (δ = 1.5 ppm) decreases by 4 compared to that at position g (δ = 1.5 ppm), indicating that the two terminal amino groups of the amino dicapped maleate successfully underwent proton transfer and became protonated amino groups. The peaks at position a (δ = 0.1 ppm) are characteristic of Si-CH3, while the peaks at positions b (δ = 0.5 ppm), c (δ = 1.5 ppm), and d (δ = 2.75 ppm) are characteristic of the methylene groups in the amino dicapped maleate. The integrated areas of these four characteristic peaks remain unchanged before and after the reaction, indicating that the amino dicapped maleate structure is retained. The peak at position f (δ = 6 ppm) is characteristic of -CH=CH-, with an integrated area of ​​4, indicating the presence of two maleic acid structures in the product structure. It can be seen that the amino double-headed group and maleic acid undergo proton transfer to form amino double-headed maleate, and at the same time, the amino groups at both ends of the amino double-headed group exchange protons with one maleic acid each to form a molecule with a diene bond structure.

[0109] The above structural analysis shows that Example 1 successfully carried out a proton exchange reaction between the amino double-capped group and maleic acid, and successfully synthesized an organosilicon supramolecular ion salt containing a diene bond structure.

[0110] Example 2: Preparation of organosilicon supramolecular ion salt by grinding method

[0111] An organosilicon supramolecular ion salt, the structure of which is as follows:

[0112]

[0113] in,

[0114] n=1.

[0115] The preparation method of organosilicon supramolecular ion salt is as follows:

[0116] Put 18.7g of maleic acid into a mortar and grind it with a mortar; accurately weigh 20g of amino double head, slowly drip it into the mortar at room temperature (about one drop of liquid per second), and continue grinding. When there is no obvious wet part in the system, continue to drip the amino double head until the amino double head is completely added, continue grinding for 10 minutes, until the system becomes fine and dry, add ethyl acetate for washing, filter, and dry to obtain 38.7g of organosilicon supramolecular ion salt (i.e., amino double head maleate).

[0117] The structure of the organosilicon supramolecular ion salt obtained in Example 2 was analyzed, and the results were as follows:

[0118] Infrared spectrum such as Figure 3 As shown. Figure 3 It can be seen that the amino double-capped maleate and maleic acid prepared in Example 2 have a -1 The characteristic peak of silicon-oxygen-silicon appeared at 3350cm, which proved that the siloxane structure was successfully introduced into the product. -1 The double peaks attributable to the amino group disappear and become a strong and broad peak. This is because the carboxyl peak in the introduced maleic acid structure covers the original amino peak position. At the same time, the product peak at 2100 cm -1 A broad peak appeared at , which indicated the presence of protonated amino groups, so the reaction process achieved the process of proton transfer.

[0119] NMR spectra such as Figure 4 As shown, specifically:

[0120] NMR data of amino double-capped maleate:

[0121] 1 H NMR (400MHz, d-DMSO) δ7.65(s,6H),6.03(m,4H),2.77(t,4H),1.534(m,4H),0.52(m,4H),0.067(s,12H).

[0122] Amino double head NMR data

[0123] 1 H NMR (400MHz, CDCl3) δ2.653(t,4H),1.395~1.482(m,8H),0.493(m,4H),0.041(s,12H).

[0124] In the 1H-NMR spectrum of the amino double-capped maleate salt, a characteristic peak of the protonated amino group appears at e (δ = 7.8 ppm) with an integral area of 6. Meanwhile, compared with the 1H-NMR spectra of the amino double-capped maleate salt and the amino double-capped, the integral area at c (δ = 1.5 ppm) is reduced by 4 compared with that at g (δ = 1.5 ppm), which indicates that the two terminal amino groups of the amino double-capped are successfully converted into protonated amino groups through the proton transfer process. The characteristic peak of Si-CH3 is at a (δ = 0.1 ppm), and the three peaks at b (δ = 0.5 ppm), c (δ = 1.5 ppm), and d (δ = 2.75 ppm) are the characteristic peaks of the methylene groups in the amino double-capped, respectively. The integral areas of these four characteristic peaks remain unchanged before and after the reaction, which indicates that the structure of the amino double-capped is retained. The peak at f (δ = 6 ppm) is the characteristic peak of -CH=CH-, and the integral area is 4, which indicates that two maleic acid structures exist in the product structure. Therefore, it can be seen that the amino double-capped and the maleic acid undergo proton transfer to form the amino double-capped maleate salt, and the amino groups at both ends of the amino double-capped are exchanged with one maleic acid, respectively, to form a molecule with a double-bond structure.

[0125] The above structural analysis shows that the proton exchange reaction of the amino double-capped and the maleic acid is successfully carried out, and an organic silicon supramolecular ionic salt containing a double-bond structure is successfully synthesized. From the nuclear magnetic resonance data, the organic silicon supramolecular ionic salt prepared in Example 2 and Example 1 is the same substance, and the two only differ in preparation methods.

[0126] Example 3: Performance detection of the organic silicon supramolecular ionic salt

[0127] The repair effect of the organic silicon supramolecular ionic salt (amino double-capped maleate salt) prepared in Example 1 (the organic silicon supramolecular ionic salt prepared in Example 2 and Example 1 is the same substance, and Example 1 is taken as an example for performance detection) on damaged hair and the friction coefficient.

[0128] 1. Hair repair

[0129] The organic silicon supramolecular ionic salt (amino double-capped maleate salt) prepared in Example 1 and water are stirred at 20°C and 500 rpm for 3 min at a mass ratio of 1:99, and after being fully dissolved, the pH is adjusted to 8 with a 1M NaOH solution to obtain a repair solution A (used for repairing the reduced hair later).

[0130] Mercaptoacetic acid and deionized water are configured into a mercaptoacetic acid solution with a mass fraction of 8%, and the pH is adjusted to 8.5 with a 1M NaOH solution to obtain a reducing agent A (used for cutting the disulfide bond in the original hair to form free thiol groups, simulating damaged hair).

[0131] Cut an appropriate amount of original hair (untreated damaged hair), soak it in reducing agent A, reduce it at 50°C for 30 minutes, take it out and dry it to obtain the reduced hair.

[0132] Cut about 20 restored hairs of about 2 cm in length and soak them in repair solution A. Treat them at 50°C for 20 minutes, take them out and dry them to obtain repaired hair, and test the repair effect.

[0133] The fluorescence detection results of hair are as follows Figure 5 As shown, the results show that the untreated damaged hair (a) has strong fluorescence under a fluorescence microscope, and the gaps in the hair scales can be clearly seen, which indicates that the hair scales of the damaged hair will open, exposing the keratin structure containing thiol groups inside the hair.

[0134] The fluorescence of the reduced hair treated with thioglycolic acid (b) is also strong. At the same time, the gaps between the hair scales are widened, and large fluorescent spots appear on the hair surface due to the peeling of hair scales. This indicates that treating the hair with thioglycolic acid will break the disulfide bonds in the hair, causing the hair scales to open or even break, and increase the content of free sulfhydryl groups.

[0135] However, the fluorescence of hair (c) treated with organosilicon supramolecular ionic salt (amino dicapped maleate) was significantly reduced, and the gaps in the surface hair scales were basically unobservable. This indicates that after the hair is treated with the product, the free thiol groups on the hair surface are reduced, and the damaged or open hair scales are filled, making the hair surface smoother.

[0136] Scanning electron microscopy results of hair Figure 6 As shown in the figure, the results show that the surface of untreated damaged hair (a) is relatively rough, with more damaged sites, and the hair scales tend to lift and flake. The surface of reduced hair (b) treated with thioglycolic acid is even rougher, with more damaged sites, and a more pronounced tendency for the hair scales to lift and flake, with some scales already damaged and flake. On the other hand, the surface of reduced hair (d) treated with the product shows a clear reduction in damage, with fewer damaged sites, smoother hair scales, and a reduced tendency to lift. This indicates that, macroscopically, the degree of hair damage is reduced after product treatment.

[0137] 2. Dynamic and static friction coefficients

[0138] The organosilicon supramolecular ion salt obtained in Example 1 and water were mixed in a mass ratio of 1:99, stirred at 20°C and 500 rpm for 3 minutes, and after being fully dissolved, the pH was adjusted to 8 with 1M NaOH solution to obtain repair solution A;

[0139] Thioglycolic acid and deionized water were prepared into a thioglycolic acid solution with a mass fraction of 8%, and the pH was adjusted to 8.5 with 1 M NaOH solution to obtain reducing agent A (which was subsequently used to treat hair as it was to obtain reduced hair).

[0140] 90 hairs of 5 cm to 7 cm in length were cut and divided into three groups.

[0141] Group 1: No treatment was performed, the hair was left as is.

[0142] Group 2: Soaked in reducing agent A, reduced at 50°C for 30 minutes, taken out and dried to obtain reduced hair.

[0143] Group 3: Soaked in reducing agent A, reduced at 50℃ for 30 minutes, taken out and dried, then soaked in repairing liquid A, treated at 50℃ for 20 minutes, taken out and dried to obtain repaired hair.

[0144] The friction coefficient results are shown in Table 1. After restoration, the static friction coefficient of the original hair increased by 4.24% and the dynamic friction coefficient increased by 5.29%. Compared to the restored hair, the static and dynamic friction coefficients of the repaired hair treated with Repair Fluid A decreased by 25.49% and 29.20%, respectively. Compared to the original hair, the static and dynamic friction coefficients decreased by 22.15% and 25.25%, respectively. These results indicate that the smoothness of hair treated with the organosilicon supramolecular ion salt is significantly improved compared to both the restored and original hair.

[0145] Table 1 Friction coefficient test

[0146]

[0147] 3. Combing test

[0148] The organosilicon supramolecular ion salt obtained in Example 1 and water were mixed in a mass ratio of 1:99, stirred at 20°C and 500 rpm for 3 minutes, and after being fully dissolved, the pH was adjusted to 8 with 1M NaOH solution to obtain repair solution A;

[0149] The human hair pieces were treated with a 10% mass fraction SDS solution to obtain SDS-treated hair pieces, and the dry combing work was measured after natural drying; the hair pieces were then treated with repair solution A, and the dry combing work after treatment was measured again after natural drying. The test results are shown in Table 2.

[0150] As can be seen from Table 2, the dry combing work of the hair after being treated with Repair Fluid A was reduced by 11.7% compared to that before treatment, which indicates that the hair becomes more supple and combable after treatment with the product.

[0151] Table 2 Dry combing work

[0152]

[0153]

[0154] Example 4: Preparation of supramolecular ionic salt using long-chain aminopolysiloxane

[0155] Because long-chain aminopolysiloxanes have poor water solubility, direct reaction with maleic acid will form a gel, making them difficult to use in aqueous shampoo and hair care products. Therefore, before the reaction, the aminopolysiloxane must be prepared into a water-soluble system or a commercially available water-soluble system. Using aminosilicone water-soluble emulsion system 1201 as an example, we prepared an organosilicon supramolecular ionic salt.

[0156] The preparation of organosilicon supramolecular ionic salt using aminosilicone water-soluble emulsion system 1201 includes the following steps:

[0157] 9 g of maleic acid was mixed with 30 g of aminosilicone water-soluble emulsion system 1201, and the mixture was stirred at room temperature for 30 min to obtain 39 g of aminosilicone maleate water-soluble emulsion system.

[0158] Repairing liquid B was prepared in the same manner as in Example 3. The dry combing work of the hair was tested for the original hair, the hair treated only with the 1201 water-soluble system (aminosilicone water-soluble emulsion system 1201), and the hair treated with repairing liquid B. The results are shown in Table 3.

[0159] Table 3 Dry combing work

[0160]

[0161] The results showed that the repair solution prepared using the aminosilicone water-soluble emulsion system and maleate also had good hair smoothing ability, which was better than the hair treated with SDS and the hair treated with only the aminosilicone water-soluble emulsion system 1201.

[0162] Example 5: Preparation of hair care products using organosilicon supramolecular ionic salts.

[0163] The organosilicon supramolecular ion salt prepared in Example 1 was used to prepare shampoo, and the formula is shown in Table 4:

[0164] Table 4

[0165]

[0166] The preparation method is as follows:

[0167] In a beaker, the main surfactant sodium dodecyl sulfate (SDS) is mixed with an appropriate amount of water, cocamidopropyl betaine and the functional ingredients are added to the above mixture, and the mixture is stirred evenly. The pH value of the mixture is adjusted to close to the natural pH value of the scalp (about 5.5) with citric acid, and water is added to the designed system mass to prepare a shampoo.

[0168] The organosilicon supramolecular ion salt prepared in Example 1 was added to the shampoo prepared above as an active ingredient for a comparative sample, and a blank sample was prepared without the active ingredient. The dry combing performance of the comparative and blank samples after treating human hair was tested according to the method of Example 3. The results are shown in Table 5.

[0169] Table 5 Dry combing work

[0170]

[0171] The results show that the shampoo prepared using the organosilicon supramolecular ion salt of Example 1 has the effect of smoothing hair. Comparative Example 1: Preparation of organosilicon supramolecular ion salt using glacial acetic acid

[0172] On the basis of Example 1, deionized water was replaced with glacial acetic acid, and the remaining steps were consistent with Example 1 to prepare 29.67 g of liquid product.

[0173] Comparative Example 2: Preparation of organosilicon supramolecular ion salt by changing the amount of maleic acid

[0174] On the basis of Example 1, the amount of maleic acid was changed to 13.09 g, the molar ratio of amino double-capped maleate to maleic acid was 1:1.4, and the remaining steps were consistent with Example 1 to prepare 29.45 g of amino double-capped maleate.

[0175] Comparative Example 3: Preparation of organosilicon supramolecular ion salt using aminopropyl-terminated polydimethylsiloxane

[0176] The main structure of aminopropyl-terminated polydimethylsiloxane is a compound with aminopropyl groups at the end and a polydimethylsiloxane main chain structure. Here, aminopropyl-terminated polydimethylsiloxane with CAS number 99904-16-2 is used to prepare organosilicon supramolecular ion salt, which includes the following steps:

[0177] 0.15 g of maleic acid and 10.78 g of amino-terminated polydimethylsiloxane were mixed (the molar ratio of maleic acid to amino group was 1:1), and the mixture was stirred at room temperature. As the reaction proceeded, the viscosity of the system gradually increased, while the amount of maleic acid gradually decreased. After stirring for half an hour, the system was basically solidified, and a white solid still remained.

[0178] It can be seen that because the amino groups in the overly long-chain aminopropyl-terminated siloxane are far apart, they provide an environment for cross-linking between the dicarboxyl groups in maleic acid and different aminosiloxanes, causing the system to solidify and unable to continue reacting. At the same time, because aminopropyl-terminated polydimethylsiloxane has extremely poor water solubility, even if it is modified to be water-soluble through a salt-forming reaction, the viscosity after the reaction is still high, resulting in the entire system being unable to form a homogeneous phase in water.

[0179] Comparative Example 4: Comparison of repair effects of similar raw materials

[0180] On the basis of Example 3, the organosilicon supramolecular ion salt (amino bis-capped maleate) was replaced by the existing compound bisaminopropyl diglycol dimaleate, and the remaining steps were consistent with Example 3.

[0181] The products prepared in Comparative Example 1, Comparative Example 2, and Comparative Example 4 were respectively mixed with water in a mass ratio of 1:99, stirred at 20°C and 500 rpm for 3 min, and after being fully dissolved, the pH was adjusted to 8 with 1M NaOH solution to obtain repair liquid C (Comparative Example 1), repair liquid D (Comparative Example 2), and repair liquid E (Comparative Example 4), respectively.

[0182] Part of the restored hair was taken and soaked in repair liquid C, repair liquid D, and repair liquid E respectively, treated at 50°C for 20 minutes, taken out and dried to obtain repaired hair C, D, and E respectively.

[0183] The obtained hair samples were observed under a fluorescence microscope, and the results were as follows: Figure 7 The results show that Repair Solution C, corresponding to Comparative Example 1, has almost no repairing effect. This is because the acidic protonating agent used competes with maleic acid for reaction sites, resulting in a reaction product between acetic acid and a double capping agent. Acetic acid lacks unsaturated bonds in its structure, so the product is ineffective in repairing damaged hair.

[0184] In Example 1, one amino double head is combined with two maleic acid molecules, while in Comparative Example 2, due to the failure to strictly follow the reactant ratio, an excess of amino double heads occurs, resulting in part of the product being one amino double head combined with one maleic acid, thereby affecting the hair repair effect of repair liquid D.

[0185] Comparative Example 4 has a repairing effect on the hair, but the gaps in the hair scales with fluorescence can still be seen, which means that it has no silicone structure and its ability to repair the hair scales is weak. The electron microscopy results of hair E repaired in Comparative Example 4 are as follows Figure 6 As shown in Figure c, the results show that Comparative Example 4 has a certain degree of repair on the hair surface, but the hair scales are still lifted, which is consistent with the results of fluorescence microscopy.

[0186] The above results show that the organosilicon supramolecular ion salt prepared in Example 1 has excellent hair repair function, and its effect is significantly better than that of existing products.

[0187] Although the present invention has been disclosed above in terms of preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this technology can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be based on the definition of the claims.

Claims

1. A method for preparing an organosilicon supramolecular ion salt, characterized in that: The steps include: (1) Maleic acid and deionized water were mixed in a mass ratio of 1-2:2-6, and stirred at room temperature for 5-30 min until the maleic acid was completely dissolved, thereby preparing a maleic acid aqueous solution; (2) Weigh the amino double-capped end cap and slowly drip it into the maleic acid aqueous solution under stirring. After the addition is completed, continue stirring and reacting for 1 to 3 hours; (3) After the reaction is completed, the solvent water in the system is volatilized, washed with ethyl acetate, filtered, and dried to obtain an organosilicon supramolecular ion salt; The molar ratio of the amino double end cap to maleic acid is 1:2-5; the slow dripping is one drop of liquid per second; The structural formula of organosilicon supramolecular ion salt is as follows: The structure of amino double head is as follows: n is an integer from 1 to 5.

2. The method according to claim 1, characterized in that The method for preparing organosilicon supramolecular ion salt comprises the following steps: 18.7 g of maleic acid and 40 g of deionized water were mixed in a reaction flask equipped with a stirring device, and stirred at room temperature for 10 min until the maleic acid was completely dissolved to prepare a maleic acid aqueous solution; Accurately weigh 20 g of an amino double-capped end cap and slowly dropwise add it to the maleic acid aqueous solution while stirring. Keep the system at room temperature and continue stirring for 2 h after the addition is complete. After the reaction is complete, evaporate the solvent water in the system, wash with ethyl acetate, filter, and dry to obtain 38.7 g of organosilicon supramolecular ion salt. Among them, slow dripping means one drop of liquid per second; The structure of amino double head is as follows: n is 1.

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