Phosphorylcholine copolymer containing active groups, preparation method of phosphorylcholine copolymer and application of phosphorylcholine copolymer in modification of cosmetic raw materials

Abstract

The invention provides a phosphorylcholine copolymer containing active groups. The invention also provides a preparation method of the phosphorylcholine copolymer containing the active group. The invention further provides a method for modifying the functional raw material by using the phosphorylcholine copolymer containing the active group. The invention further provides application of the phosphorylcholine copolymer containing the active group or the functional raw material composition modified by the phosphorylcholine copolymer containing the active group in cosmetics. According to the phosphorylcholine copolymer containing the active groups, the preparation method of the phosphorylcholine copolymer and the application of the phosphorylcholine copolymer in modifying the cosmetic raw materials, the active groups are introduced into the phosphorylcholine polymer, so that the phosphorylcholine polymer has biological activity and is used for modifying the cosmetic functional raw materials, and the process is mild, simple, efficient and safe; the solubility, the activity stability, the color stability and the transdermal absorption efficiency of the functional raw materials can be obviously enhanced, so that the functional raw materials can be more easily applied to cosmetics.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional polymer materials, and relates to a phosphorylcholine copolymer containing active groups, a preparation method thereof, and an application in modifying cosmetic raw materials. Specifically, it relates to a phosphorylcholine copolymer containing active groups such as hydroxyl groups and carboxyl groups, a preparation method thereof, and its use as a polymer material for modifying efficacy cosmetic raw materials in daily chemicals. Background Art

[0002] Phosphorylcholine polymers are a type of polymer material similar to the phospholipid structure. They usually contain amphoteric end groups and alkane non-polar molecular chains. The amphoteric end groups are hydrophilic, and the alkane molecular chains are hydrophobic. This structure is very similar to that of biological membranes, so the blood compatibility of phosphorylcholine polymers is very close to that of biological membranes. In the field of biomaterials, the research on its properties and synthesis methods has attracted more and more attention. Research shows that phosphorylcholine polymers can modify the surface of biomaterials to mimic the outer structure of cells and are widely used in fields such as medicine and cosmetics.

[0003] Patent CN111467571A, "A multifunctional cardiovascular coating material with superhydrophilicity and its preparation method", polymerizes 2-methacryloyloxyethyl phosphorylcholine, vinyltrimethoxysilane, 2-acrylamido-2-methylpropanesulfonic acid, and maleimide-tris(ethylene glycol)-propionic acid, etc. under the action of an initiator to obtain an MPC multi-component copolymer with superhydrophilicity. Then, the obtained MPC copolymer is mixed evenly with chitosan quaternary salt to obtain a material with superhydrophilicity and good biocompatibility. However, the excessive hydrophilicity has great limitations in actual use.

[0004] Patent EP1095665A1, "Band-aid preparation, band-aid material and wound healing method", polymerizes 2-methacryloyloxyethyl phosphorylcholine, butyl methacrylate, etc. to obtain an MPC binary copolymer, and obtains a wound covering agent that is effective for cleaning wound sites and removing necrotic tissues, has excellent hydrophilicity and biocompatibility, and has the effect of promoting cell repair. However, this binary polymer needs to be waterproofed during use to avoid losing relevant properties.

[0005] At the same time, the current application scenarios of active ingredients often have certain application limitations due to their own properties. For example, sodium hyaluronate is a type of polysaccharide substance that has strong lubricity, film-forming properties and moisturizing properties. Its molecular form and physical and chemical properties are variable with different molecular weights. The molecular structure of sodium hyaluronate contains many hydrogen bonds and is a rigid spiral column in space. There are a large number of hydroxyl groups on the inside, which can bind a large number of water molecules. These water molecules are very firm in the column and have good water absorption and safety. The viscosity of the macromolecular sodium hyaluronate aqueous solution is very high. Patent CN202310540742.2 mentions that acids and alkalis can be used to change the viscosity of sodium hyaluronate, but acids and alkalis will affect the singleness of sodium hyaluronate and are challenging for cosmetic formulation applications.

[0006] Phytosphingosine is a precursor of ceramide and one of the lipid components of the skin. It has a natural barrier repair function. It also has a strong inhibitory effect on microbial activity and is effective in anti-inflammatory and redness removal. As one of the lipid components of the skin, phytosphingosine has multiple effects on the skin, adding points to high-end products such as anti-aging and repair. However, phytosphingosine is difficult to dissolve in water, making it difficult to use in cosmetic applications.

[0007] Patent CN105919824A "Oily cosmetics containing EGCG, preparation method and application thereof" discloses a method of first dissolving EGCG in an alcohol solution and further dispersing it in oil. Although this method improves the stability of EGCG, the alcohol used in the method is ethanol, which may irritate the skin; Patent CN117100629A achieves transdermal enhancement of active ingredients by preparing terpenoids of active ingredients such as resveratrol and glabridin, but terpenoids have high requirements for the operation process, and terpenoids often have poor stability. The patent does not examine the stability; Patent CN116725896A "A lactoferrin collagen anti-wrinkle supramolecular microcapsule and its preparation method" encapsulates collagen peptides in the form of supramolecular microcapsules, thereby improving the efficacy and transdermal penetration of collagen peptides, but the operation process uses high-pressure homogenization equipment, and the high temperature and high pressure generated in the process may affect the protein results, resulting in denaturation and inactivation of collagen. Summary of the invention

[0008] In view of the above-mentioned deficiencies in the prior art, the object of the present invention is to provide a phosphorylcholine copolymer containing an active group, a preparation method thereof, and an application of modifying cosmetic raw materials. The obtained copolymer polymer material can modify cosmetic functional raw materials to improve their application performance in cosmetics, so as to help the cosmetics industry better apply these active raw materials and maximize their efficacy.

[0009] To achieve the above and other related objectives, a first aspect of the present invention provides a phosphorylcholine copolymer containing active groups, and the chemical structure of the copolymer is shown in formula (I):

[0010]

[0011] In formula (I), x > 0; z > 0; y ≥ 0; 0 ≤ m ≤ 25; R is selected from H, (CH2) n OH, (CH2) n CHOCH2 or (CH2) n NH2, where 0 ≤ n ≤ 8.

[0012] A second aspect of the present invention provides a method for preparing a phosphorylcholine copolymer containing active groups, including: adding 2-methacryloyloxyethyl phosphorylcholine (MPC, III), fatty acid methacrylate (IV), and methacrylate containing active groups (V) to an initiator and a solvent for polymerization reaction, and then subjecting the obtained polymerization stock solution to post-treatment to obtain a phosphorylcholine copolymer (I) containing active groups;

[0013] The process route is as follows:

[0014]

[0015] In formula (IV), 0 ≤ m ≤ 25;

[0016] In formula (V), R is selected from H, hydroxyl (-OH), carboxyl (-COOH), amino (-NH2) or epoxy group;

[0017] In formula (I), x > 0; z > 0; y ≥ 0; 0 ≤ m ≤ 25; R is selected from H, (CH2) n OH, (CH2) n CHOCH2 or (CH2) n NH2, where 0 ≤ n ≤ 8.

[0018] A third aspect of the present invention provides the above-mentioned phosphorylcholine copolymer containing active groups, which is prepared by the above method.

[0019] A fourth aspect of the present invention provides a method for modifying an efficacy raw material with a phosphorylcholine copolymer containing active groups, including: mixing and reacting the efficacy raw material with the above-mentioned phosphorylcholine copolymer containing active groups and a solvent to provide a desired efficacy raw material composition modified with a phosphorylcholine copolymer containing active groups.

[0020] A fifth aspect of the present invention provides an efficacy raw material composition modified with a phosphorylcholine copolymer containing active groups, which is prepared by the above method.

[0021] The sixth aspect of the present invention provides the use of the above-mentioned phosphorylcholine copolymer containing active groups, or the efficacy raw material composition modified with the above-mentioned phosphorylcholine copolymer containing active groups in cosmetics.

[0022] As described above, a phosphorylcholine copolymer containing active groups provided by the present invention, its preparation method and the application of modifying cosmetic raw materials have the following beneficial effects compared with the prior art:

[0023] (1) A phosphorylcholine copolymer containing active groups provided by the present invention, its preparation method and the application of modifying cosmetic raw materials use 2-methacryloyloxyethyl phosphorylcholine (MPC) with biocompatibility, methacrylic acid fatty acid ester monomers and methacrylates containing active groups such as hydroxyl, carboxyl, amino, and epoxy groups as monomers, and prepare a binary or ternary copolymeric high molecular material by free radical solution copolymerization method as the phosphorylcholine copolymer containing active groups. This phosphorylcholine copolymer introduces active groups such as hydroxyl, carboxyl, amino, and epoxy groups into the phosphorylcholine polymer, making it have biological activity.

[0024] (2) A phosphorylcholine copolymer containing active groups provided by the present invention, its preparation method and the application of modifying cosmetic raw materials can modify the efficacy raw materials of cosmetics with the prepared phosphorylcholine copolymer containing active groups, and the process is mild, simple, efficient and safe.

[0025] (3) A phosphorylcholine copolymer containing active groups provided by the present invention, its preparation method and the application of modifying cosmetic raw materials. The prepared phosphorylcholine copolymer containing active groups can significantly enhance the solubility, activity stability, color stability, and transdermal absorption efficiency of the efficacy raw materials through supramolecular forces such as hydrogen bonds, intermolecular forces, and encapsulation between the phosphorylcholine copolymer and the efficacy raw material active molecules. At the same time, the efficacy of the active substance is equivalent or enhanced, making the active substance more stable, the discoloration and inactivation slower, the transdermal efficiency higher, and the efficacy enhanced.

[0026] (4) A phosphorylcholine copolymer containing active groups provided by the present invention, its preparation method and the application of modifying cosmetic raw materials enable the phosphorylcholine copolymer containing active groups to modify the cosmetic efficacy raw materials to improve their application performance in cosmetics, thereby solving the application difficulties of the corresponding efficacy raw materials and making them easier to be applied in cosmetics, which helps the cosmetics industry better apply these active raw materials and exert their maximum efficacy. Description of the Drawings

[0027] Figure 1 Shown is the nuclear magnetic resonance hydrogen spectrum of a phosphorylcholine ternary polymer containing carboxyl groups in Example 1 of the present invention.

[0028] Figure 2It shows the GPC chart of a carboxyl-containing phosphorylcholine ternary polymer in Example 1 of the present invention.

[0029] Figure 3 It shows the infrared spectrum of a carboxyl-containing phosphorylcholine ternary polymer in Example 1 of the present invention.

[0030] Figure 4 It shows the 1H NMR spectrum of a phosphorylcholine binary polymer containing epoxy groups in Example 2 of the present invention.

[0031] Figure 5 It shows the GPC chart of a phosphorylcholine binary polymer containing epoxy groups in Example 2 of the present invention.

[0032] Figure 6 It shows the infrared spectrum of a phosphorylcholine binary polymer containing epoxy groups in Example 2 of the present invention.

[0033] Figure 7 It shows the comparison chart of the fluidity of the samples of Example 6 and Comparative Example 1 of the present invention. Among them, the sample in the upper bottle is the sample of Example 6, and the sample in the lower bottle is the sample of Comparative Example 1.

[0034] Figure 8 It shows the infrared spectrum of sodium hyaluronate after being modified by a phosphorylcholine polymer in the present invention.

[0035] Figure 9 It shows the comparison chart of the appearance of the samples of Example 7 and Comparative Example 2 of the present invention. Among them, the sample in the left bottle is the sample of Example 7, and the sample in the right bottle is the sample of Comparative Example 2.

[0036] Figure 10 It shows the comparison chart of the difference in water content of the skin stratum corneum in the present invention.

[0037] Figure 11 It shows the comparison chart of cell viability in the present invention.

[0038] Figure 12 shows the comparison of the high-temperature color stability of the samples before and after modification in the present invention Figure 12a 、 12b 、12c, 12d, 12e; Among them, Figure 12a shows the investigation of the high-temperature color stability of the samples before and after modification at 0 days, Figure 12b shows the investigation of the high-temperature color stability of the samples before and after modification at 7 days, Figure 12c shows the investigation of the high-temperature color stability of the samples before and after modification at 15 days, Figure 12d shows the investigation of the high-temperature color stability of the samples before and after modification at 30 days, Figure 12e shows the investigation of the high-temperature color stability of the samples before and after modification at 60 days; Figure 12a 、 12b, in 12c, 12d, and 12e, the left bottle contains the sample before modification, and the right bottle contains the sample after modification.

[0039] Figure 13 It shows a comparison chart of the expression of skin repair-related groups in the present invention. Detailed implementation manners

[0040] The inventors of the present application developed a phosphorylcholine copolymer containing active groups, introduced active groups such as hydroxyl, carboxyl, amino, and epoxy groups into the phosphorylcholine polymer to endow it with biological activity. Additionally, a preparation method of a phosphorylcholine copolymer containing active groups was provided, using 2-methacryloyloxyethyl phosphorylcholine (MPC) monomer with biocompatibility, fatty acid methacrylate monomers, and methacrylate containing active groups such as hydroxyl, carboxyl, amino, and epoxy groups as monomers, and preparing binary or ternary copolymeric high molecular materials by free radical solution copolymerization method, with mild and simple process, high efficiency and safety. A method for modifying efficacy raw materials with a phosphorylcholine copolymer containing active groups was also provided, which can modify various efficacy raw materials. Moreover, an efficacy raw material composition modified with a phosphorylcholine copolymer containing active groups and its application in cosmetics were provided, significantly enhancing the solubility, activity stability, color stability, transdermal absorption efficiency, etc. of the efficacy raw materials, and at the same time, the efficacy of the active substances is equivalent or enhanced. Thus, the present invention was completed and is specifically described as follows.

[0041] Term definitions

[0042] Unless otherwise specified, the following words, phrases, and symbols used in this specification generally have the meanings described below.

[0043] Generally, the nomenclature used herein (e.g., IUPAC nomenclature) and the laboratory procedures described below (including those for cell culture, organic chemistry, analytical chemistry, pharmacology, etc.) are those well-known and commonly used in the art. Unless otherwise defined, all scientific and technical terms used herein in connection with the present disclosure described herein have the same meaning as commonly understood by those skilled in the art. Additionally, in the claims and / or the specification, when the term "a" or "an" is used in combination with the term "comprising" or a noun, its meaning may be "one", but it is also consistent with the meanings of "one or more", "at least one", and "one or more than one". Similarly, the term "another" or "other" may mean at least a second or more.

[0044] It should be understood that whenever an aspect is described herein using the terms "comprising" or "including", other similar aspects described by "consisting of" and / or "consisting essentially of" are also provided.

[0045] In the first aspect of the present invention, a phosphorylcholine copolymer containing active groups is provided, and the chemical structure of the copolymer is shown in formula (I):

[0046]

[0047] In formula (I), x > 0; z > 0; y ≥ 0; 0 ≤ m ≤ 25; R is selected from H, (CH2) n OH, (CH2) n CHOCH2 or (CH2) n NH2, where 0 ≤ n ≤ 8.

[0048] In reaction formula (I), x, y, and z respectively represent the number of repeating units. x is a positive integer greater than 0, z is a positive integer greater than 0, and y is an integer greater than or equal to 0.

[0049] For example, x can be 500 - 1000. In some specific embodiments, x can be 500 - 600, 500 - 700, 500 - 900, 900 - 1000.

[0050] For example, y can be 0 - 300. In some specific embodiments, y can be 0 - 100, 0 - 200, 0 - 300.

[0051] For example, z can be 50 - 500. In some specific embodiments, z can be 50 - 100, 100 - 200, 200 - 500.

[0052] In reaction formula (I), x:y:z is 5 - 10:0 - 3:0.5 - 5. In some specific embodiments, x:y:z can be 5 - 8:0 - 3:0.5 - 5, 8 - 10:0 - 3:0.5 - 5, 5 - 10:0 - 1:0.5 - 5, 5 - 10:2 - 3:0.5 - 5, 5 - 10:0 - 3:0.5 - 2, 5 - 10:0 - 3:2 - 5.

[0053] In reaction formula (I), m is a positive integer greater than or equal to 0 and less than or equal to 25. For example, 1 ≤ m ≤ 5, 5 ≤ m ≤ 10, 2 ≤ m ≤ 9, 3 ≤ m ≤ 8, 4 ≤ m ≤ 7, 15 ≤ m ≤ 25. In some specific embodiments, m can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25.

[0054] In Reaction Scheme (I), n is an integer greater than or equal to 0 and less than or equal to 8. For example, 0≤n≤4, 4≤n≤8, 1≤n≤7, 2≤n≤6, 3≤n≤5, 4≤n≤6, 3≤n≤7, 2≤n≤8. In some specific embodiments, n can be 0, 1, 2, 3, 4, 5, 6, 7, 8.

[0055] In Reaction Scheme (I), when y is not equal to 0, the chemical structure of the copolymer is a terpolymer as shown in Formula (I).

[0056] In Reaction Scheme (I), when y is equal to 0, the chemical structure of the copolymer is a binary copolymer as shown in Formula (II);

[0057]

[0058] In Reaction Scheme (II), x and y respectively represent the number of repeating units. x is a positive integer greater than 0, and y is a positive integer greater than 0.

[0059] For example, x can be 500 - 1000. In some specific embodiments, x can be 500 - 600, 500 - 700, 500 - 900, 900 - 1000.

[0060] For example, y can be 50 - 500. In some specific embodiments, y can be 50 - 100, 100 - 200, 200 - 500.

[0061] The second aspect of the present invention provides a method for preparing a phosphorylcholine copolymer containing active groups, comprising: adding 2-methacryloyloxyethyl phosphorylcholine (MPC, III), fatty acid methacrylate (IV), and methacrylate containing active groups (V) to an initiator and a solvent for polymerization reaction, and then subjecting the obtained polymerization stock solution to post-treatment to obtain a phosphorylcholine copolymer (I) containing active groups;

[0062] The process route is as follows:

[0063]

[0064] In Formula (IV), 0≤m≤25;

[0065] In Formula (V), R is selected from H, hydroxyl (-OH), carboxyl (-COOH), amino (-NH2), or epoxy group;

[0066] In Formula (I), x>0; z>0; y≥0; 0≤m≤25; R is selected from H, (CH2) n OH, (CH2) n CHOCH2 or (CH2) n NH2, where 0≤n≤8.

[0067] When m in formula (IV) is not equal to 0, the chemical structure of the copolymer prepared is a terpolymer as shown in formula (I).

[0068] When m in formula (IV) is equal to 0, the chemical structure of the copolymer prepared is a binary copolymer as shown in formula (II);

[0069]

[0070] In reaction formula (II), x and y respectively represent the number of repeating units. x is a positive integer greater than 0, and y is a positive integer greater than 0.

[0071] In the above preparation method, the molar ratio of 2-methacryloyloxyethyl phosphorylcholine, fatty acid methacrylate, and methacrylate containing an active group is 1 - 15: 0 - 4: 0.5 - 4. For example, the molar ratio of 2-methacryloyloxyethyl phosphorylcholine, fatty acid methacrylate, and methacrylate containing an active group can be 4 - 10: 0 - 3: 0.5 - 3. In some specific embodiments, it can be 6 - 8: 0 - 3: 0.5 - 3, 6 - 8: 1 - 2: 1 - 2, 4 - 10: 1 - 2: 1 - 2.

[0072] The above preparation method is a free radical solution copolymerization method. Among them, 2-methacryloyloxyethyl phosphorylcholine, fatty acid methacrylate, and methacrylate containing an active group are used as monomers. 2-methacryloyloxyethyl phosphorylcholine is an amphoteric ionic compound designed and synthesized based on the cell membrane structure, so it has good biocompatibility and hydrophilicity.

[0073] In the above preparation method, the concentration of 2-methacryloyloxyethyl phosphorylcholine ≤ 2000 mg / kg.

[0074] In the above preparation method, the concentration of fatty acid methacrylate ≤ 1000 mg / kg.

[0075] In the above preparation method, the concentration of methacrylate containing an active group ≤ 1000 mg / kg.

[0076] In the above preparation method, the initiator is an additive reagent that initiates a radical polymerization reaction. Specifically, for example, the initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, or N,N-dimethylaniline.

[0077] In the above preparation method, the mass ratio of 2-methacryloyloxyethyl phosphorylcholine to the initiator is 100:0.5 - 2. For example, it can be 100:0.5 - 1, 100:0.5 - 1.5, 100:1 - 1.5. In some specific embodiments, it can be 100:0.5 - 1.5, 100:1 - 1.5, 100:1.5 - 2.

[0078] In the above preparation method, the solvent is selected from one or a mixture of two of water or alcohol. Specifically, the alcohol is selected from one or a mixture of more of anhydrous ethanol, n-propanol, isopropanol or butanol.

[0079] In the above preparation method, the total volume ratio of the solvent to the reactants is 2 - 5:1. For example, it can be 2 - 2.5:1. In some specific embodiments, it can be 2 - 3:1, 2 - 4:1, 2 - 4.5:1.

[0080] The reactants include 2-methacryloyloxyethyl phosphorylcholine, fatty acid methyl acrylate, and methacrylate containing active groups.

[0081] In the above preparation method, the polymerization reaction is carried out in a polymerization reactor.

[0082] In the above preparation method, the 2-methacryloyloxyethyl phosphorylcholine, fatty acid methyl acrylate, methacrylate containing active groups, initiator and solvent are fully mixed and homogenized.

[0083] In the above preparation method, high-purity nitrogen is bubbled before the polymerization reaction to remove oxygen, and the high-purity nitrogen is nitrogen with a concentration of greater than or equal to 99.999%.

[0084] In some specific embodiments, the high-purity nitrogen bubbling time is 15 - 20 min, preferably 20 min.

[0085] In the above preparation method, the heating temperature of the polymerization reaction is 20 - 100 °C, preferably 30 - 90 °C. In some specific embodiments, it can be 30 - 50 °C, 50 - 70 °C, 70 - 90 °C.

[0086] In the above preparation method, the reaction time of the polymerization reaction is 4 - 50 h, preferably 5 - 48 h. In some specific embodiments, it can be 5 - 20 h, 20 - 30 h, 30 - 48 h.

[0087] In the above preparation method, the polymerization reaction is stirred and mixed by a stirrer. In some specific embodiments, the stirrer is a magnetic stirrer.

[0088] In the above preparation method, the post-treatment includes: cooling the polymerization stock solution, adding a precipitant for sedimentation, standing still, and then taking the solid for washing and drying to provide the required phosphorylcholine terpolymer.

[0089] In the above post-treatment, it is cooled to room temperature. The room temperature is 20 - 30 °C.

[0090] In the above post-treatment, the precipitant is selected from at least one of petroleum ether, n-hexane, ethyl acetate, acetone, or anhydrous diethyl ether.

[0091] In the above post-treatment, the sedimentation time is 1 - 15 h, preferably 2 - 12 h. In some specific embodiments, it can be 2 - 4 h, 4 - 8 h, or 8 - 12 h.

[0092] In the above post-treatment, the volume ratio of the precipitant to 2-methacryloyloxyethyl phosphorylcholine is 2 - 20:1. For example, it can be 5 - 15:1. In some specific embodiments, it can be 5 - 6:1, 6 - 7:1, or 7 - 8:1.

[0093] In the above post-treatment, it is left standing overnight.

[0094] In the above post-treatment, the solvent used for washing is acetone or petroleum ether.

[0095] In the above post-treatment, the drying is vacuum drying, and the drying temperature is 20 - 100 °C, preferably 30 - 90 °C. In some specific embodiments, it can be 30 - 50 °C, 50 - 60 °C, 60 - 70 °C, or 70 - 90 °C.

[0096] In the above post-treatment, it needs to be pulverized after drying. The phosphorylcholine copolymer containing active groups is a white powdery solid.

[0097] The third aspect of the present invention provides the above phosphorylcholine copolymer containing active groups, which is obtained by the above method.

[0098] The fourth aspect of the present invention provides a method for modifying an efficacy raw material with a phosphorylcholine copolymer containing active groups, including: mixing and reacting the efficacy raw material with the above phosphorylcholine copolymer containing active groups and a solvent to provide the required composition of the efficacy raw material modified with the phosphorylcholine copolymer containing active groups.

[0099] In the above method, the efficacy raw material is selected from at least one of sodium hyaluronate, phytosphingosine, collagen, tea extract (EGCG), ergothioneine, glabridin, resveratrol, retinoic acid, dihydroxyacetone, or retinol and its derivatives.

[0100] The above-mentioned phosphorylcholine copolymer modified functional raw materials containing active groups work by using the supramolecular forces between the phosphorylcholine copolymer and the active molecules of the functional raw materials, such as hydrogen bonds, intermolecular forces, encapsulation, etc. The modification results can significantly enhance the solubility, activity stability, color stability, and transdermal absorption efficiency of the functional raw materials. At the same time, the efficacy of the active substances is equivalent or enhanced, making it easier to be applied in cosmetics.

[0101] The above-mentioned functional raw materials all contain active groups such as hydroxyl, amino, and carboxyl groups. And the above-mentioned functional raw materials have relatively strong cosmetic effects, such as moisturizing, repairing, whitening, tanning, anti-aging and antioxidant, etc. However, there are certain application difficulties, including poor solubility, easy decomposition and inactivation, easy color change, low transdermal efficiency, sticky and muddy skin feeling, etc.

[0102] In some specific embodiments, the molecular formulas and structural formulas of the functional raw materials are shown in Table 1 below.

[0103] Table 1

[0104]

[0105]

[0106] Among the above-mentioned functional raw materials, the derivatives of retinol are selected from at least one of retinol propionate, retinol acetate, hydroxypinacolone retinoate, or retinol retinoate.

[0107] In the above method, the mass ratio of the functional raw material to the phosphorylcholine copolymer containing active groups is 0.1 - 1000:1. In some specific embodiments, it can be 0.1 - 1:1, 1 - 10:1, 10 - 100:1, 100 - 1000:1, 5 - 500:1.

[0108] In the above method, the solvent is selected from at least one of water, butylene glycol, propylene glycol, ethoxydiglycol, triglyceride caprylate / caprate, or glyceride caprylate / caprate.

[0109] In the above method, the mass ratio of the functional raw material to the solvent is 1:9 - 11. For example, it can be 1:9 - 10, 1:10 - 11. In some specific embodiments, it can be 1:10.

[0110] In the above method, the stirring rate of the mixing reaction is ≤500 rpm / min. For example, it can be ≤400 rpm / min. In some specific embodiments, it can be ≤300 rpm / min.

[0111] In the above method, the mixing reaction is carried out in a reaction kettle.

[0112] In the above method, the temperature of the mixing reaction is 10 to 80 °C, preferably 20 - 70 °C. In some specific embodiments, it can be 20 to 40 °C, 40 to 60 °C, or 60 to 70 °C.

[0113] In the above method, the reaction time of the mixing reaction is 0.5 to 5 h. In some specific embodiments, it can be 0.5 to 1 h, 1 to 3 h, or 3 to 5 h.

[0114] In the above method, the system of the efficacy raw material composition modified with the phosphorylcholine copolymer containing active groups is selected from one of an aqueous solution, an oil solution, an emulsion, or a liquid crystal system.

[0115] The fifth aspect of the present invention provides an efficacy raw material composition modified with a phosphorylcholine copolymer containing active groups, which is obtained by the above method.

[0116] The sixth aspect of the present invention provides the use of the above phosphorylcholine copolymer containing active groups or the above efficacy raw material composition modified with the phosphorylcholine copolymer containing active groups in cosmetics.

[0117] In the above use, the cosmetics include but are not limited to various dosage forms such as emulsions, essences, creams, essential oils, and color cosmetics. The efficacy raw material composition modified with the phosphorylcholine copolymer containing active groups is used as an efficacy raw material in cosmetics.

[0118] The efficacy raw material composition modified with the phosphorylcholine copolymer containing active groups can solve the application difficulties of the corresponding efficacy raw materials, significantly enhance the solubility, activity stability, color stability, and transdermal absorption efficiency of the efficacy raw materials, and at the same time, the efficacy of the active substances is equivalent or enhanced.

[0119] The following specific examples illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation manners. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention.

[0120] When the examples give a numerical range, it should be understood that unless otherwise specified in the present invention, any value at both ends of each numerical range and any value between the two ends can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meaning as commonly understood by those skilled in the art of this technology. Except for the specific methods, equipment, and materials used in the examples, according to the knowledge of those skilled in the art of this technology and the description of the present invention, any methods, equipment, and materials similar to or equivalent to those described in the examples of the present invention in the prior art can also be used to implement the present invention.

[0121] Example 1

[0122] Weigh 40.82 g of 2-methacryloyloxyethyl phosphorylcholine, 19.66 g of n-butyl methacrylate, 6.33 g of methacrylic acid and 0.57 g of azobisisobutyronitrile and transfer them to a 1000 mL round-bottom flask. Then add 300 ml of absolute ethanol, stir at room temperature until completely dissolved, bubble with high-purity nitrogen for 20 minutes and then seal. Start heating to 60 °C and carry out the polymerization reaction for 18 hours. Stir with a magnetic stirrer throughout the polymerization process. After the reaction is completed, carry out sedimentation in anhydrous ether for 8 h. The volume ratio of anhydrous ether to 2-methacryloyloxyethyl phosphorylcholine is 10:1. Then wash with acetone and dry to constant weight at 40 °C under vacuum to obtain 60.25 g of a whitish powder-like polymer, that is, the phosphorylcholine copolymer sample 1# containing active groups. After qualitative detection, the phosphorylcholine copolymer sample 1# containing active groups is a phosphorylcholine terpolymer containing carboxyl active groups. Its nuclear magnetic resonance hydrogen spectrum is shown in Figure 1 , the GPC spectrum is shown in Figure 2, and the infrared spectrum is shown in Figure 3 . Figure 2 Among them, the weight-average molecular weight M w of the phosphorylcholine copolymer sample 1# containing active groups = 114511 g / mol, and PDI = 3.42.

[0123] Example 2

[0124] Weigh 66.44 g of 2-methacryloyloxyethyl phosphorylcholine, 3.25 g of glycidyl methacrylate (the chemical structures shown in Reaction Formula IV and Reaction Formula V are the same), and 0.808 g of benzoyl peroxide, and transfer them to a 1000 mL round-bottom flask. Then add 180 mL of absolute ethanol and 90 mL of DMF to the round-bottom flask, stir at room temperature until the solid is completely dissolved, bubble with high-purity nitrogen for 30 minutes and then seal, and heat to 40 °C to carry out the polymerization reaction for 14 h. Stir with a magnetic stirrer throughout the polymerization process. After the reaction is completed, cool the polymerization solution to room temperature and carry out sedimentation in acetone for 10 h. The volume ratio of acetone to 2-methacryloyloxyethyl phosphorylcholine is 15:1. Then wash with acetone and dry to constant weight at 40 °C under vacuum to obtain 67.91 g of a whitish powder-like polymer, that is, the phosphorylcholine copolymer sample 2# containing active groups. After qualitative detection, the phosphorylcholine copolymer sample 2# containing active groups is a phosphorylcholine binary polymer containing epoxy active groups. Its nuclear magnetic resonance hydrogen spectrum is shown in Figure 4 , the GPC spectrum is shown in Figure 5, and the infrared spectrum is shown in Figure 6 .

[0125] Example 3

[0126] Weigh 48.06 g (162.75 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 23.14 g (162.75 mmol) of n-butyl methacrylate, 55.10 g (162.75 mmol) of octadecyl methacrylate, and 1.14 g (7 mmol) of azobisisobutyronitrile and transfer them to a 2000 mL round-bottom flask. Then add 600 mL of absolute ethanol, stir at room temperature until completely dissolved, bubble with high-purity nitrogen for 20 minutes and then seal. Start heating to 60 °C and carry out the polymerization reaction for 10 hours. Stir with a magnetic stirrer throughout the polymerization process. After the reaction is completed, carry out sedimentation in anhydrous ether for 1 h. The volume ratio of anhydrous ether to 2-methacryloyloxyethyl phosphorylcholine is 5:1. Then wash with acetone and dry to constant weight at 40 °C under vacuum to obtain 110 g of a white powdery polymer, namely the phosphorylcholine copolymer sample 3# containing active groups. After qualitative detection, the phosphorylcholine copolymer sample 3# containing active groups is a phosphorylcholine terpolymer containing octadecyl long-chain active groups.

[0127] Example 4

[0128] Weigh 48.06 g (162.75 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 23.14 g (162.75 mmol) of n-butyl methacrylate, 30.15 g (162.75 mmol) of diethylaminoethyl methacrylate, and 1.14 g (7 mmol) of azobisisobutyronitrile and transfer them to a 2000 mL round-bottom flask. Then add 600 mL of absolute ethanol, stir at room temperature until completely dissolved, bubble with high-purity nitrogen for 20 minutes and then seal. Start heating to 60 °C and carry out the polymerization reaction for 10 hours. Stir with a magnetic stirrer throughout the polymerization process. After the reaction is completed, carry out sedimentation in anhydrous ether for 1 h. The volume ratio of anhydrous ether to 2-methacryloyloxyethyl phosphorylcholine is 20:1. Then wash with acetone and dry to constant weight at 40 °C under vacuum to obtain 100 g of a white powdery polymer, namely the phosphorylcholine copolymer sample 4# containing active groups. After qualitative detection, the phosphorylcholine copolymer sample 4# containing active groups is a phosphorylcholine terpolymer containing amino active groups.

[0129] Example 5

[0130] Weigh 48.06 g (162.75 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 23.14 g (162.75 mmol) of n-butyl methacrylate, 21.18 g (162.75 mmol) of 2-hydroxyethyl methacrylate, and 1.14 g (7 mmol) of azobisisobutyronitrile and transfer them to a 1000 mL round-bottom flask. Then add 300 mL of absolute ethanol, stir at room temperature until completely dissolved, bubble with high-purity nitrogen for 20 minutes and then seal it. Start heating to 50 °C and carry out the polymerization reaction for 15 hours. Stir with a magnetic stirrer throughout the polymerization process. After the reaction is completed, sediment in anhydrous ether for 2 h. The volume ratio of anhydrous ether to 2-methacryloyloxyethyl phosphorylcholine is 12:1. Then wash with acetone and dry to a constant weight at 30 °C under vacuum to obtain a white powder-like polymer, that is, 5.85 g of the phosphorylcholine copolymer sample containing active groups. After qualitative detection, the phosphorylcholine copolymer sample 5# containing active groups is a phosphorylcholine copolymer containing hydroxyl groups.

[0131] Example 6

[0132] Weigh 6.0 g of sodium hyaluronate with an average molecular weight of 1.2 million Daltons, and add 1.2 g of the phosphorylcholine copolymer sample 1# containing active groups obtained in Example 1 to a 500 mL round-bottom flask. Then add 182.8 g of deionized water, heat to 50 °C, stir at 500 rpm / min for 3 h until completely dissolved, and then cool to room temperature. After stirring evenly, a modified sodium hyaluronate aqueous solution is obtained as the efficacy raw material composition sample 1*.

[0133] Example 7

[0134] Weigh 2.0 g of phytosphingosine powder, and add 8.0 g of the phosphorylcholine copolymer containing amino groups obtained in Example 4 to a 500 mL round-bottom flask. Then add 180.0 g of deionized water, heat to 40 °C, stir at 400 rpm / min for 4 h until completely dissolved and then cool to room temperature to obtain a modified phytosphingosine aqueous solution as the efficacy raw material composition sample 2*.

[0135] Example 8

[0136] Weigh 1.0 g of tea extract EGCG, and add 0.4 g of the phosphorylcholine copolymer containing hydroxyl groups obtained in Example 5, 30.0 g of caprylic / capric triglyceride, 35.0 g of isononyl isononanoate, and 33.6 g of propylene glycol to a 300 mL beaker. Heat to 30 °C, stir at 300 rpm / min for two hours and then cool to room temperature to obtain a modified EGCG oil solution as the efficacy raw material composition sample 3*.

[0137] Example 9

[0138] Weigh 2.0 g of collagen, add 1.0 g of the hydroxyl-containing phosphorylcholine copolymer obtained in Example 5 and 97.0 g of deionized water into a 300 mL beaker, heat up to 35 °C, stir at 300 rpm / min for 1 h, and then cool to room temperature to obtain a modified collagen aqueous solution as the efficacy raw material composition sample 4*.

[0139] Comparative Example 1

[0140] Weigh 6.0 g of sodium hyaluronate with an average molecular weight of 1.2 million Daltons, add it to a 500 mL round-bottom flask, then add 184 g of deionized water, heat up to 50 °C, stir for 3 h until completely dissolved, and then cool to room temperature. After stirring evenly, obtain a sodium hyaluronate hydrogel as Comparative Sample 1.

[0141] Comparative Example 2

[0142] Weigh 2.0 g of phytosphingosine, then add 188 g of deionized water, heat up to 40 °C, stir for 4 h, and then cool to room temperature to obtain a suspension of phytosphingosine as Comparative Sample 2.

[0143] Comparative Example 3

[0144] Weigh 1.0 g of tea extract EGCG, then add 99 g of deionized water, add it to a 300 mL beaker, heat up to 30 °C, stir at 300 rpm / min for 2 h until completely dissolved, and then cool to room temperature. After stirring evenly, obtain a modified EGCG oil solution as Comparative Sample 3.

[0145] Comparative Example 4

[0146] Weigh 2.0 g of collagen, then add 98 g of deionized water, add it to a 300 mL beaker, heat up to 35 °C, stir at 300 rpm / min for 1 h, and then cool to room temperature to obtain a modified collagen aqueous solution as Comparative Sample 4.

[0147] Comparative Example 5

[0148] Weigh 48.06 g (162.75 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 23.14 g (162.75 mmol) of n-butyl methacrylate, 21.18 g (162.75 mmol) of methacrylate containing reactive groups, and 1.14 g (7 mmol) of azobisisobutyronitrile and transfer them to a 3000 mL round-bottom flask. Then add 1000 mL of absolute ethanol, stir at room temperature until completely dissolved, bubble with high-purity nitrogen for 20 minutes, then seal, start heating to 85 °C, and carry out the polymerization reaction for 3 hours. Stir with a magnetic stirrer throughout the polymerization process. After the reaction is completed, carry out sedimentation in anhydrous ether for 1 h. The volume ratio of anhydrous ether to 2-methacryloyloxyethyl phosphorylcholine is 1:1. Then wash with acetone and dry to constant weight at 80 °C under vacuum to obtain a white powdery polymer, which is Comparative Sample 5.

[0149] Comparative Example 6

[0150] Weigh 10 g of sodium hyaluronate and 2 g of Comparative Sample 5 obtained in Comparative Example 5, add them to a 500 mL round-bottom flask, then add 130 g of deionized water, heat to 35 °C, stir at 600 rpm / min for 0.5 h until completely dissolved, then cool to room temperature, and stir evenly to obtain a modified sodium hyaluronate aqueous solution as Comparative Sample 6.

[0151] Test Comparative Example 1

[0152] Compare the efficacy raw material composition sample 1* obtained in Example 6 with Comparative Sample 1 obtained in Comparative Example 1. For the specific appearance situation of the two, see Figure 7 , and for the specific substance situation, see Figure 8 . From Figure 7 it can be seen that the stickiness of the modified sodium hyaluronate aqueous solution of the efficacy raw material composition sample 1* is significantly reduced and the fluidity is significantly improved; it shows that through the supramolecular technology, under certain conditions, the phosphorylcholine copolymer and sodium hyaluronate interact in a non-covalent bond form, forming a new stable structure through intermolecular forces or hydrogen bond interactions, greatly weakening the hydration of sodium hyaluronate and water molecules, thereby reducing the viscosity of its aqueous solution; while Comparative Sample 1 has no fluidity. At the same time, from Figure 8 it can be seen that there is no characteristic peak at the characteristic frequency region of the ester at 1735 - 1750 cm -1 for the efficacy raw material composition sample 1*, thus proving that no new substance is formed.

[0153] Test Comparative Example 2

[0154] Carry out a 25-person moisturizing clinical efficacy test on the efficacy raw material composition sample 1* obtained in Example 6. The test results are shown in Figure 10 . From Figure 10It can be seen that after modification with the phosphorylcholine polymer containing active groups, not only the sticky skin feel of sodium hyaluronate is greatly improved, but also the overall moisturizing ability of the raw materials is enhanced. After 25-person clinical moisturizing efficacy tests, the results show that the modified sodium hyaluronate has better moisturizing effects, which are superior to those of sodium hyaluronate used alone, the polymer, and their combination, compared with before use.

[0155] Test Comparative Example 3

[0156] The sample 2* of the efficacy raw material composition obtained in Example 7 was compared with the comparative sample 2 obtained in Comparative Example 2. For the specific appearance of the two, see Figure 9 . From Figure 9 it can be seen that the sample 2* of the efficacy raw material composition is a clear solution, while there are a large number of insoluble substances in the comparative sample 2 and it has no fluidity. It can be seen that the phosphorylcholine copolymer and phytosphingosine improve the water solubility of phytosphingosine through supramolecular interactions, which is beneficial for high-content addition in cosmetics and can be used in clear aqueous formulations or essence formulations, expanding the formulation possibilities.

[0157] Test Comparative Example 4

[0158] The sample 2* of the efficacy raw material composition obtained in Example 7 was used with rabbit corneal epithelial cells (SIRC) cultured in vitro, briefly exposed to cosmetic raw materials, and the acute corneal irritation effect was simulated. The eye damage caused by cosmetic chemical raw materials was predicted by calculating the relative cell survival rate. The test results are shown in Figure 11 . From Figure 11 it can be seen that the safety of phytosphingosine is improved. After modification with the phosphorylcholine copolymer containing active groups, its safety is superior to that of unmodified phytosphingosine itself.

[0159] Test Comparative Example 5

[0160] The sample 3* of the efficacy raw material composition obtained in Example 8 and the comparative sample 3 obtained in Comparative Example 3 were placed in an oven at 45 °C to investigate the color stability. The results are shown in Figure 12, and at the same time, the retention rate of the active substance was monitored by HPLC. The results are shown in Table 2.

[0161] Table 2

[0162]

[0163] From Figure 12 and Table 2, it can be seen that after modification with the phosphorylcholine copolymer, the discoloration and active substance loss of EGCG under high-temperature accelerated test conditions are significantly improved, indicating that modification can improve the stability of the active substance.

[0164] Test Comparative Example 6

[0165] The efficacy raw material composition sample 4* obtained in Example 9 and the comparative sample 4 obtained in Comparative Example 4 were tested for the expression of genes related to skin barrier repair before and after modification. The results are shown in Figure 13 .

[0166] It can be seen from Figure 13 that the collagen modified with phosphorylcholine copolymer shows a significant improvement in the effects of repairing the stratum corneum, promoting keratinocyte differentiation, moisturizing, and maintaining normal skin functions, indicating that modification can promote the efficacy of active substances.

[0167] Test Comparative Example 7

[0168] The efficacy raw material composition sample 1* obtained in Example 6 was compared with the comparative sample 6 obtained in Comparative Example 6, and a 25-person clinical moisturizing efficacy test was conducted. Specifically, it was a test on the reduction of skin water loss: It is an important indicator to evaluate the strength of skin barrier function by the level of transepidermal water loss (TEWL value).

[0169] Test instrument: Skin transepidermal water loss tester.

[0170] Test samples: Efficacy raw material composition sample 1* obtained in Example 6 VS Comparative sample 6 obtained in Comparative Example 6

[0171] Twenty-five skin-dry subjects aged 20 - 40 were selected. On the inner sides of the forearms of the subjects' hands, test areas of 3×3 cm2 were marked. Multiple areas could be marked on the same arm, with an interval of 1 cm between areas. The test samples and the blank control were randomly distributed on the left and right arms. A capacitance method skin measuring instrument was used to measure the test areas and the control areas. Each area was measured 15 times in parallel. First, the blank values of each test area were measured, and then according to the dosage of 0.5 g test sample / 9 cm 2 , it was evenly coated on the test area. After application, the skin water content of the test areas and the blank control areas was measured at 1, 2, 4, and 8 hours respectively (measured at this time during verification). No products (cosmetics or topical medications) could be used on the test sites 2 - 3 days before the test. The test environment temperature was controlled at 25 ± 1 °C, and the relative humidity was 40 ± 5%. Before the test, the subjects' arms were wiped with pure water at about 36 °C, and the subjects were allowed to sit quietly in the test environment for 30 min before the test. The TEWL values at each time period were measured according to the experimental design, and the reduction of skin water loss at each time point was calculated. The greater the reduction of skin water loss, the better the effect of skin barrier repair. The results are shown in Table 3 below.

[0172] Table 3

[0173] Group / Time 1h 2h 4h 8h Example 6 26.3 25.9 25.3 24.6 Comparative Example 6 22.1 21.4 20.2 18.5

[0174] As shown in the results of Table 3, the water reduction amount of the efficacy raw material composition sample 1* of Example 6 is small during the long-term moisturizing process, indicating that the phosphorylcholine copolymer sample 1# containing active groups obtained in Example 1 included in the efficacy raw material composition sample 1* can form long-term moisturization and provide water-locking ability for the skin.

[0175] The above embodiments are intended to illustrate the embodiments disclosed in the present invention and should not be construed as limitations on the present invention. In addition, various modifications listed herein and changes in the methods of the invention are obvious to those skilled in the art without departing from the scope and spirit of the present invention. Although the present invention has been specifically described in conjunction with various specific preferred embodiments of the present invention, it should be understood that the present invention should not be limited to these specific embodiments. In fact, all obvious modifications to those skilled in the art as described above to obtain the invention should be included within the scope of the present invention.

Claims

1. A phosphorylcholine copolymer containing reactive groups, and the chemical structure of the copolymer is shown in formula (I): In formula (I), x > 0; z > 0; y ≥ 0; 0 ≤ m ≤ 25; R is selected from H, (CH2) n OH, (CH2) n CHOCH2 or (CH2) n NH2, where 0≤n≤8。 2. The phosphorylcholine copolymer containing active groups according to claim 1, characterized in that, including any one or more of the following conditions: A1) x, y, and z respectively represent the number of repeating units, x is a positive integer greater than 0, z is a positive integer greater than 0, and y is an integer greater than or equal to 0; A2) m is a positive integer greater than or equal to 0 and less than or equal to 25; A3) n is an integer greater than or equal to 0 and less than or equal to 8; A4) When y is equal to 0, the chemical structure of the copolymer is shown in formula (II) and is a binary copolymer; In reaction formula (II), x and y respectively represent the number of repeating units, x is a positive integer greater than 0, and y is a positive integer greater than 0.

3. A preparation method of a phosphorylcholine copolymer containing active groups, comprising: 2-methacryloyloxyethyl phosphorylcholine (MPC, Ⅲ), fatty acid methacrylate (Ⅳ), and methacrylate containing reactive groups (Ⅴ) are added with an initiator and a solvent for polymerization reaction, and the obtained polymerization stock solution is post-treated to obtain a phosphorylcholine copolymer (I) containing reactive groups; The process route is as follows: In formula (Ⅳ), 0 ≤ m ≤ 25; In formula (Ⅴ), R is selected from H, hydroxyl group (-OH), carboxyl group (-COOH), amino group (-NH2), or epoxy group; In formula (I), x > 0; z > 0; y ≥ 0; 0 ≤ m ≤ 25; R is selected from H, (CH2) n OH, (CH2) n CHOCH2 or (CH2) n NH2, where 0 ≤ n ≤ 8.

4. The preparation method of the phosphorylcholine copolymer containing active groups according to claim 3, characterized in that, including any one or more of the following conditions: B1) When m in formula (Ⅳ) is equal to 0, the chemical structure of the prepared copolymer is shown in formula (II) and is a binary copolymer; B2) The molar ratio of 2-methacryloyloxyethyl phosphorylcholine, fatty acid methacrylate, and methacrylate containing reactive groups is 1 - 15:0 - 4:0.5 - 4; B3) The initiator is selected from at least one of azobisisobutyronitrile, benzoyl peroxide, or N,N-dimethylaniline; B4) The mass ratio of 2-methacryloyloxyethyl phosphorylcholine to the initiator is 100:0.5 - 2; B5) The solvent is selected from one or a mixture of two of water or alcohol; B6) The total volume ratio of the solvent to the reactants is 2 - 5:1; B7) High-purity nitrogen is bubbled before the polymerization reaction to remove oxygen; preferably, the high-purity nitrogen bubbling time is 15 - 20 min; B8) The heating temperature of the polymerization reaction is 20 - 100 °C; B9) The reaction time of the polymerization reaction is 4 - 50 h; B10) The post-treatment includes: cooling the polymerization stock solution and adding a precipitant for sedimentation, then standing and taking the solid for washing and drying to provide the required phosphorylcholine terpolymer.

5. The preparation method of the phosphorylcholine copolymer containing active groups according to claim 4, characterized in that, In item B10), including any one or more of the following conditions: B101) Cooling to room temperature; B102) The precipitant is selected from at least one of petroleum ether, n-hexane, ethyl acetate, acetone, or anhydrous ether; B103) The sedimentation time is 1 - 15 h; B104) The volume ratio of the precipitant to 2-methacryloyloxyethyl phosphorylcholine is 2 - 20:1; B105) Standing overnight; B106) The solvent used for washing is acetone or petroleum ether; B107) The drying is vacuum drying, and the drying temperature is 20 - 100 °C; B108) Crushing is required after drying.

6. A phosphorylcholine copolymer containing reactive groups, which is obtained by the method according to any one of claims 3-5.

7. A method for modifying an active ingredient with a phosphorylcholine copolymer containing active groups, comprising: Mix and react an active ingredient with the phosphorylcholine copolymer containing reactive groups according to any one of claims 1-2 and a solvent to provide a composition of an active ingredient modified with the phosphorylcholine copolymer containing reactive groups as required.

8. The method for modifying an active ingredient with a phosphorylcholine copolymer containing an active group according to claim 7, wherein Including any one or more of the following conditions: C1) The active ingredient is selected from at least one of sodium hyaluronate, phytosphingosine, collagen, tea extract (EGCG), ergothioneine, glabridin, resveratrol, tretinoin, dihydroxyacetone, or retinol and its derivatives; C2) The mass ratio of the active ingredient to the phosphorylcholine copolymer containing reactive groups is 0.1-1000:1; C3) The solvent is selected from at least one of water, butylene glycol, propylene glycol, ethoxydiglycol, triglyceride caprylate / caprate, or caprylate / caprate glyceride; C4) The mass ratio of the active ingredient to the solvent is 1:9-11; C5) The stirring rate of the mixing reaction is ≤500 rpm / min; C6) The temperature of the mixing reaction is 10-80 °C; C7) The reaction time of the mixing reaction is 0.5-5 h.

9. A composition of an active ingredient modified with a phosphorylcholine copolymer containing reactive groups, which is obtained by the method according to any one of claims 7-8.

10. Use of the phosphorylcholine copolymer according to any one of claims 1-2, the phosphorylcholine copolymer according to claim 6, or the composition of an active ingredient modified with the phosphorylcholine copolymer containing reactive groups according to claim 9 in cosmetics.

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