Phosphorylcholine copolymer as well as preparation method and application thereof

Abstract

The invention provides a phosphorylcholine copolymer. The invention also provides a preparation method of the phosphorylcholine copolymer. The invention further provides application of the phosphorylcholine copolymer in the fields of cosmetics and biomedicine. According to the phosphorylcholine copolymer as well as the preparation method and the application thereof provided by the invention, the environmental and health problems caused by crystallization and recrystallization by using an organic solvent in the past can be solved, and the phosphorylcholine copolymer has excellent biocompatibility, safety and biological performance, has better moisturizing and repairing performance, softness and smoothness, and can be applied to the field of medical instruments. The carrier is a potential biocompatible active matter carrier and can be applied to the fields of cosmetics and biomedicine.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional polymer materials, and relates to a phosphorylcholine copolymer, a preparation method thereof and an application, in particular to a phosphorylcholine copolymer with a biomimetic structure, a preparation method thereof and an application as a raw material in cosmetics and the like. Background Art

[0002] Polymers containing phosphorylcholine can be used as humectants, skin protectants and skin conditioners in cosmetics due to their excellent moisturizing and repairing effects, and can also be applied in the fields of biomedicine and health such as contact lenses and medicine. At present, the more widely used phosphorylcholine polymer is the binary copolymer of 2-methacryloyloxyethyl phosphorylcholine and n-butyl methacrylate (the name in the catalog of raw materials already used in cosmetics is polyquaternium-51). Because of its excellent surface activity and wetting properties, it has been used in various cosmetic products; in view of the excellent surface activity and wetting properties of phosphorylcholine polymers, more compounds containing MPC groups can be developed to enrich their application fields and supplement the phosphorylcholine polymer series.

[0003] At present, there are many studies on the synthesis of phosphorylcholine copolymerization. Patent JP6590909B2 makes a copolymer composed of a phosphorylcholine structural unit and a hydrophobic structural unit by a polymerization method, and imparts biocompatibility to the substrate by phototreating the polymer on the substrate surface. However, the radical polymerization initiator for this polymerization reaction is an azo radical polymerization initiator, an organic oxide, a persulfate, etc., and acyl chloride and halogen solvents are used when manufacturing a monomer having a photoreactive azide group bonded to the substrate surface. Therefore, strict management is required during production to ensure safety during manufacturing; Patent CN100563716C prepared a kind of amphiphilic block MPC copolymer by a polymerization method, in which the hydrophobic chain segment is n-butyl methacrylate (BMA), and then a nano polymer micelle was prepared by the solvent evaporation method using the MPC copolymer to obtain a monodisperse nano polymer drug delivery system with good biocompatibility. The organic solvent is a mixed solvent of chloroform and ethanol, and after the reaction is completed, it needs to be added to water to form an oil-in-water emulsion. This method has a low drug loading amount and the organic solvent cannot be completely removed. CN116284548B provides a kind of phosphorylcholine quaternary copolymer with multiple self-inversions and a preparation method thereof. Four different types of hydrophilic and hydrophobic groups coexist on the side chain of this quaternary copolymer, namely a charged extremely hydrophilic group, an extremely hydrophobic group, a general hydrophilic group and a general hydrophobic group. In this method, the monomers are diluted by the solvent during the synthesis process, the polymerization rate is slow, and the molecular weight of the product is low; the consumption of the solvent is high and it is difficult to completely remove. Summary of the Invention

[0004] In view of the deficiencies of the prior art described above, the purpose of the present invention is to provide a phosphorylcholine copolymer, its preparation method and application. The obtained phosphorylcholine copolymer has a biomimetic structure, better moisture retention performance, softness and smoothness, and can also be used as the encapsulating wall material of cosmetic active additives, becoming a carrier for biologically active additives, making the product more comfortable to use and providing a better user experience.

[0005] To achieve the above and other related purposes, the first aspect of the present invention provides a phosphorylcholine copolymer, and the chemical structure of the copolymer is shown in formula (I):

[0006]

[0007] In formula (I), 2 ≤ l ≤ 20; 1 ≤ m ≤ 4; 2 ≤ n ≤ 20.

[0008] The second aspect of the present invention provides a preparation method of a phosphorylcholine copolymer, including: adding 2-methacryloyloxyethyl phosphorylcholine (MPC) shown in formula (II), fatty acid methyl acrylate shown in formula (III), 2-hydroxy fatty acid methyl acrylate shown in formula (IV), and fatty acid methyl acrylate shown in formula (V) into an initiator and a solvent for polymerization reaction, and then subjecting the obtained polymerization stock solution to post-treatment to obtain the phosphorylcholine copolymer shown in formula (I);

[0009] The process route is as follows:

[0010]

[0011] The third aspect of the present invention provides the above-mentioned phosphorylcholine copolymer, which is prepared by the above method.

[0012] The fourth aspect of the present invention provides the use of the above-mentioned phosphorylcholine copolymer in cosmetics.

[0013] The fifth aspect of the present invention provides the use of the above-mentioned phosphorylcholine copolymer in the biomedical field.

[0014] As described above, a phosphorylcholine copolymer, its preparation method and application provided by the present invention have the following beneficial effects compared with the prior art:

[0015] (1) A phosphorylcholine copolymer, its preparation method and application provided by the present invention introduce 2-hydroxy fatty acid methyl acrylate, optimize the reaction process, can avoid the use of toxic solvents, have no high-risk processes, precisely control the process, have high product stability, are conducive to post-stage purification, and obtain a product with a higher purity, solving the environmental and health problems caused by the use of organic solvents for crystallization and recrystallization in the past.

[0016] (2) The phosphorylcholine copolymer provided by the present invention, its preparation method and application have low residual amounts of reactant monomers. Moreover, 2-methacryloyloxyethyl phosphorylcholine is an amphoteric ionic compound designed and synthesized based on the cell membrane structure, so it has good biocompatibility and hydrophilicity. Methacrylic acid-2-hydroxy fatty acid ester is a kind of commonly used biological basic material with excellent biological properties. Introducing it into the polymer structure containing phosphorylcholine groups can further enhance the biocompatibility, safety and biological properties of the polymer.

[0017] (3) The phosphorylcholine copolymer provided by the present invention, its preparation method and application further expand the functionality of the prepared polymer. Compared with polyquaternium-51 (2-methacryloyloxyethyl phosphorylcholine and fatty acid methacrylate), it has more excellent moisturizing and repair effects.

[0018] (4) The phosphorylcholine copolymer provided by the present invention, its preparation method and application have a hydrophilic-lipophilic amphiphilic molecular structure, which can form bilayer vesicles with a cell-like structure. As an artificial cell membrane material, when it is used as a transport carrier, the hydrophobic core material is embedded in the middle of the bilayer lipid membrane, and the hydrophilic core material is wrapped in the hydrophilic cavity. It can also be used as the encapsulating wall material of cosmetic active additives. It is a potential biocompatible active substance carrier, which can exert biological activities such as encapsulation, slow release, and promoting transdermal penetration, and has better moisturizing and repair properties, softness and smoothness. It can be used as a moisturizer, skin protectant, skin conditioner, etc. in cosmetics, making the product more comfortable to use and providing a better user experience.

[0019] (5) The phosphorylcholine copolymer provided by the present invention, its preparation method and application can also be applied to biological and health fields such as contact lens care solutions and medicine. Description of the Drawings

[0020] Figure 1 It shows the NMR data diagram of the phosphorylcholine terpolymer in the present invention.

[0021] Figure 2 It shows the GPC diagram of the phosphorylcholine terpolymer in the present invention.

[0022] Figure 3 It shows the infrared spectrum diagram of the phosphorylcholine terpolymer in the present invention.

[0023] Figure 4 It shows the particle size diagram of the ceramide liposome encapsulated with the phosphorylcholine terpolymer as the wall material in the present invention.

[0024] Figure 5 It shows the infrared spectrum diagram of ceramide NP in the present invention.

[0025] Figure 6 It shows the infrared spectrum of ceramide NP liposomes in the present invention.

[0026] Figure 7 It shows the comparison chart of skin moisturizing property in Test Comparative Example 1 of the present invention.

[0027] Figure 8 It shows the comparison chart of repair performance in Test Comparative Example 1 of the present invention.

[0028] Figure 9 shows the ceramide NP liposome stock solution encapsulated in the liposome structure in the present invention Figure 9a , 9b , 9c, where Figure 9a is the figure of the ceramide NP liposome stock solution encapsulated in the liposome structure, Figure 9b is the figure of the ceramide NP liposome encapsulated in a 10% water dilution, Figure 9c is the figure of the ceramide NP liposome encapsulated in a 5% essence formula.

[0029] Figure 10 shows the comparison between the glabridin alcohol solution and the glabridin aqueous solution modified with phosphorylcholine terpolymer in the present invention Figure 10a , 10b , 10c, 10d, 10e, 10f, 10g, 10h, 10i, 10A, 10B, 10C, 10D, 10E, 10F, 10G, 10H, 10I, where Figure 10a is the initial state of the glabridin alcohol solution, Figure 10b is the state of the glabridin alcohol solution after 7 days at room temperature, Figure 10c is the state of the glabridin alcohol solution after 7 days at 50 °C, Figure 10d is the state of the glabridin alcohol solution after 14 days at room temperature, Figure 10e is the state of the glabridin alcohol solution after 14 days at 50 °C, Figure 10f is the state of the glabridin alcohol solution after 21 days at room temperature, Figure 10g is the state of the glabridin alcohol solution after 21 days at 50 °C, Figure 10h is the state of the glabridin alcohol solution after 28 days at room temperature, Figure 10i is the state of the glabridin alcohol solution after 28 days at 50 °C, Figure 10A is the initial state of the glabridin aqueous solution modified with phosphorylcholine terpolymer, Figure 10B is the state of the glabridin aqueous solution modified with phosphorylcholine terpolymer after 7 days at room temperature, Figure 10C is the state of the glabridin aqueous solution modified with phosphorylcholine terpolymer after 7 days at 50 °C, Figure 10D is the state of the glabridin aqueous solution modified with phosphorylcholine terpolymer after 14 days at room temperature, Figure 10EThe state of the liquiritin aqueous solution modified by phosphorylcholine terpolymer after 14 days at 50°C, Figure 10F The state of the liquiritin aqueous solution modified by phosphorylcholine terpolymer after 21 days at room temperature, Figure 10G The state of the liquiritin aqueous solution modified by phosphorylcholine terpolymer after 21 days at 50°C, Figure 10H The state of the liquiritin aqueous solution modified by phosphorylcholine terpolymer after 28 days at room temperature, Figure 10I The state of the liquiritin aqueous solution modified by phosphorylcholine terpolymer after 28 days at 50°C.

[0030] Figure 11 Shown is a comparative graph of the color change curves of the liquiritin alcohol solution and the phosphorylcholine terpolymer modification in the present invention.

[0031] Figure 12 Shown is a comparative graph of skin moisturizing properties in Test Comparative Example 2# and Comparative Example 3# of the present invention.

[0032] Figure 13 Shown is a comparative graph of repair performance in Test Comparative Example 2# and Comparative Example 3# of the present invention. Detailed Description of the Invention

[0033] The inventors of the present application have developed a phosphorylcholine copolymer with a biomimetic structure, having better moisturizing properties, softness and smoothness; additionally, a preparation method of the phosphorylcholine copolymer is provided, introducing 2-hydroxy fatty acid methacrylate, optimizing the reaction process, without high-risk processes, with precise process control, high product stability, facilitating post-stage purification, and solving the environmental and health problems caused by using organic solvents for crystallization and recrystallization in the past; also provided is the application of the phosphorylcholine copolymer in cosmetics, contact lens care solutions, and biomedicine, as a carrier of bioactive additives, exerting biological activities such as encapsulation, slow release, and transdermal promotion; thus completing the present invention, which is specifically described as follows.

[0034] Term Definitions

[0035] Unless otherwise specified, the following words, phrases, and symbols used in this specification generally have the meanings described below.

[0036] 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 have the same meaning as commonly understood by one of ordinary skill in the art. Additionally, in the claims and / or the specification, when the term "a" or "an" is used in conjunction with the term "comprising" or a noun, it may mean "one", but is also consistent with the meaning 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.

[0037] It should be understood that whenever an aspect is described herein using the term "comprising" or "including", other similar aspects described by "consisting of" and / or "consisting essentially of" are also provided.

[0038] The first aspect of the present invention provides a phosphorylcholine copolymer, and the chemical structure of the copolymer is shown in formula (I):

[0039]

[0040] In formula (I), 2 ≤ l ≤ 20; 1 ≤ m ≤ 4; 2 ≤ n ≤ 20.

[0041] In reaction formula (I), w, x, y, and z respectively represent the number of repeating units, and w, x, y, and z are positive integers greater than or equal to 1.

[0042] If l = n, the copolymer shown in formula (I) is a phosphorylcholine terpolymer; if l ≠ n, the copolymer shown in formula (I) is a phosphorylcholine quaternary copolymer.

[0043] For example, w can be 50 - 1000. In some specific embodiments, w can be 50 - 200, 50 - 500, 50 - 1000.

[0044] For example, x can be 50 - 1000. In some specific embodiments, x can be 50 - 200, 50 - 500, 50 - 1000.

[0045] For example, y can be 10 - 500, and y can be 10 - 100, 10 - 200, 10 - 500.

[0046] For example, z can be 10 - 500. z can be 10 - 100, 10 - 200, 10 - 500.

[0047] In Reactive Formula (I), l is the degree of branching, and l is a positive integer greater than or equal to 2 and less than or equal to 20. For example, 2 ≤ l ≤ 10, 10 ≤ l ≤ 20, 5 ≤ l ≤ 15, 2 ≤ l ≤ 5, 15 ≤ l ≤ 20, 8 ≤ l ≤ 12, 2 ≤ l ≤ 4, 16 ≤ l ≤ 20. In some specific embodiments, l can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0048] In Reactive Formula (I), m is the degree of branching, and m is a positive integer greater than or equal to 1 and less than or equal to 4. For example, 1 ≤ m ≤ 2, 2 ≤ m ≤ 3, 3 ≤ m ≤ 4, 1 ≤ m ≤ 3, 2 ≤ m ≤ 4. In some specific embodiments, m can be 1, 2, 3, 4.

[0049] In Reactive Formula (I), n is the degree of branching, and n is a positive integer greater than or equal to 2 and less than or equal to 20. For example, 2 ≤ n ≤ 10, 10 ≤ n ≤ 20, 5 ≤ n ≤ 15, 2 ≤ n ≤ 5, 15 ≤ n ≤ 20, 8 ≤ n ≤ 12, 2 ≤ n ≤ 4, 16 ≤ n ≤ 20. In some specific embodiments, n can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0050] In the above copolymer, the relative molecular mass of the copolymer is 1 - 1,000,000 g / mol. For example, the relative molecular mass of the copolymer is 1 - 50,000 g / mol, 50,000 - 500,000 g / mol, 500,000 - 1,000,000 g / mol, 100,000 - 400,000 g / mol, 200,000 - 300,000 g / mol.

[0051] In the above copolymer, the relative average molecular mass of the copolymer is 1 - 150,000 g / mol. For example, the relative average molecular mass of the copolymer is 1 - 40,000 g / mol, 40,000 - 100,000 g / mol, 100,000 - 150,000 g / mol, 50,000 - 90,000 g / mol, 60,000 - 80,000 g / mol, 50,000 - 70,000 g / mol.

[0052] In the above copolymer, the degree of polymerization of the copolymer is 100 - 1500. For example, the degree of polymerization of the copolymer is 100 - 500, 1000 - 1500, 500 - 1000, 600 - 900, 700 - 800.

[0053] In some specific embodiments, the phosphorylcholine copolymer is a compound represented by the following formula (I-1):

[0054]

[0055] In formula (I-1), x, y, and z respectively represent the number of repeating units, and x, y, and z are positive integers greater than or equal to 1.

[0056] For example, x can be 50 - 1000. In some specific embodiments, x can be 50 - 200, 50 - 500, 50 - 1000.

[0057] For example, y can be 10 - 500, and y can be 10 - 100, 10 - 200, 10 - 500.

[0058] For example, z can be 10 - 500. The z can be 10 - 100, 10 - 200, 10 - 500.

[0059] The second aspect of the present invention provides a method for preparing a phosphorylcholine copolymer, including: adding 2-methacryloyloxyethyl phosphorylcholine (MPC) shown in formula (II), fatty acid methyl acrylate shown in formula (III), 2-hydroxy fatty acid methyl acrylate shown in formula (IV), and fatty acid methyl acrylate shown in formula (V) into an initiator and a solvent for a polymerization reaction, and then subjecting the obtained polymerization stock solution to post-treatment to obtain the phosphorylcholine copolymer shown in formula (I);

[0060] The process route is as follows:

[0061]

[0062] In the above preparation method, in formula (III), 2 ≤ l ≤ 20. l is the degree of branching, and l is a positive integer greater than or equal to 2 and less than or equal to 20. For example, 2 ≤ l ≤ 10, 10 ≤ l ≤ 20, 5 ≤ l ≤ 15, 2 ≤ l ≤ 5, 15 ≤ l ≤ 20, 8 ≤ l ≤ 12, 2 ≤ l ≤ 4, 16 ≤ l ≤ 20. In some specific embodiments, l can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0063] In the above preparation method, in formula (IV), 1 ≤ m ≤ 4. m is the degree of branching, and m is a positive integer greater than or equal to 1 and less than or equal to 4. For example, 1 ≤ m ≤ 2, 2 ≤ m ≤ 3, 3 ≤ m ≤ 4, 1 ≤ m ≤ 3, 2 ≤ m ≤ 4. In some specific embodiments, m can be 1, 2, 3, 4.

[0064] In the above preparation method, in formula (V), 2 ≤ n ≤ 20. n is the degree of branching, and n is a positive integer greater than or equal to 2 and less than or equal to 20. For example, 2 ≤ n ≤ 10, 10 ≤ n ≤ 20, 5 ≤ n ≤ 15, 2 ≤ n ≤ 5, 15 ≤ n ≤ 20, 8 ≤ n ≤ 12, 2 ≤ n ≤ 4, 16 ≤ n ≤ 20. In some specific embodiments, n can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.

[0065] In the above preparation method, the molar ratio of 2-methacryloyloxyethyl phosphorylcholine (MPC) shown in formula (II), fatty acid methyl acrylate shown in formula (III), 2-hydroxy fatty acid methyl acrylate shown in formula (IV), and fatty acid methyl acrylate shown in formula (V) is 1-15: 0.5-4: 0.5-4: 0.5-4. For example, the molar ratio of 2-methacryloyloxyethyl phosphorylcholine (MPC) shown in formula (II), fatty acid methyl acrylate shown in formula (III), 2-hydroxy fatty acid methyl acrylate shown in formula (IV), and fatty acid methyl acrylate shown in formula (V) can be 4-10: 0.5-3: 0.5-3: 0.5-3. In some specific embodiments, it can be 6-8: 0.5-3: 0.5-3: 0.5-3, 4-10: 1-2: 1-2: 1-2, 6-8: 1-2: 1-2.

[0066] In the above preparation method, it is free radical solution copolymerization. Among them, 2-methacryloyloxyethyl phosphorylcholine (MPC) shown in formula (II), fatty acid methyl acrylate shown in formula (III), 2-hydroxy fatty acid methyl acrylate shown in formula (IV), and fatty acid methyl acrylate shown in formula (V) are used as monomers. 2-methacryloyloxyethyl phosphorylcholine shown in formula (II) is a zwitterionic compound designed and synthesized based on the cell membrane structure, so it has good biocompatibility and hydrophilicity. 2-hydroxy fatty acid methyl acrylate shown in formula (IV) is a kind of commonly used biological basic material with excellent biological properties. Introducing it into the polymer structure containing phosphorylcholine groups can further enhance the biocompatibility, safety and biological properties of the polymer.

[0067] In the above preparation method, the concentration of 2-methacryloyloxyethyl phosphorylcholine shown in formula (II) ≤ 4000 mg / kg. In some specific embodiments, the concentration of 2-methacryloyloxyethyl phosphorylcholine shown in formula (II) ≤ 3000 mg / kg.

[0068] In the above preparation method, the concentration of the fatty acid methacrylate shown in formula (III) ≤ 2000 mg / kg. In some specific embodiments, the concentration of the fatty acid methacrylate shown in formula (III) ≤ 1500 mg / kg.

[0069] In the above preparation method, the concentration of 2-hydroxy fatty acid methacrylate shown in formula (IV) ≤ 2000 mg / kg. In some specific embodiments, the concentration of 2-hydroxy fatty acid methacrylate shown in formula (IV) ≤ 1500 mg / kg.

[0070] In the above preparation method, the concentration of the fatty acid methacrylate shown in formula (V) ≤ 2000 mg / kg. In some specific embodiments, the concentration of the fatty acid methacrylate shown in formula (V) ≤ 1500 mg / kg.

[0071] In the above preparation method, the initiator is an additive reagent that initiates a free radical polymerization reaction. Specifically, for example, the initiator is azobisisobutyronitrile.

[0072] In the above preparation method, the mass ratio of the initiator to 2-methacryloyloxyethyl phosphorylcholine shown in formula (II) is 1:50 - 600. For example, it can be 1:50 - 100, 1:100 - 500, 1:500 - 600. In some specific embodiments, it can be 1:100 - 300, 1:300 - 500, 1:200 - 400.

[0073] 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 anhydrous ethanol, n-propanol, isopropanol or butanol.

[0074] In the above preparation method, the total volume ratio of the solvent to the reactants is 1 - 7:1. For example, it can be 2 - 6:1. In some specific embodiments, it can be 2 - 3:1, 3 - 4:1, 5 - 6:1.

[0075] The reactants include 2-methacryloyloxyethyl phosphorylcholine (MPC) shown in formula (II), fatty acid methacrylate shown in formula (III), 2-hydroxy fatty acid methacrylate shown in formula (IV), and fatty acid methacrylate shown in formula (V).

[0076] In the above preparation method, the polymerization reaction is carried out in a polymerization reactor.

[0077] In the above preparation method, 2-methacryloyloxyethyl phosphorylcholine (MPC) represented by formula (II), fatty acid methyl acrylate represented by formula (III), 2-hydroxy fatty acid methyl acrylate represented by formula (IV), fatty acid methyl acrylate represented by formula (V), an initiator, and a solvent are fully and uniformly mixed.

[0078] In the above preparation method, high-purity nitrogen is bubbled before the polymerization reaction to remove oxygen. The high-purity nitrogen is nitrogen with a concentration of greater than or equal to 99.999%.

[0079] In some specific embodiments, the high-purity nitrogen bubbling time is 15 - 25 min, preferably 20 min.

[0080] In the above preparation method, the heating temperature of the polymerization reaction is 40 - 90 °C, preferably 50 - 80 °C. In some specific embodiments, it can be 50 - 60 °C, 60 - 70 °C, or 70 - 80 °C.

[0081] In the above preparation method, the stirring rate of the polymerization reaction is 100 - 700 rpm / min, preferably 150 - 600 rpm / min. In some specific embodiments, it can be 150 - 200 rpm / min, 200 - 300 rpm / min, 300 - 400 rpm / min, 400 - 500 rpm / min, or 500 - 600 rpm / min.

[0082] In the above preparation method, the reaction time of the polymerization reaction is 5 - 30 h, preferably 6 - 24 h. In some specific embodiments, it can be 6 - 10 h, 10 - 20 h, or 20 - 24 h.

[0083] In the above preparation method, the post-treatment includes: cooling the polymerization stock solution and then adding a precipitant for sedimentation, followed by standing and then taking the solid for washing and drying to provide the desired phosphorylcholine copolymer.

[0084] In the above post-treatment, it is cooled to room temperature. The room temperature is 20 - 30 °C.

[0085] In the above post-treatment, the precipitant is selected from at least one of petroleum ether, n-hexane, ethyl acetate, acetone, or anhydrous ether.

[0086] In the above post-treatment, the sedimentation time is 1 - 15 h, preferably 2 - 10 h. In some specific embodiments, it can be 2 - 4 h, 4 - 8 h, or 8 - 10 h.

[0087] In the above post-treatment, the volume ratio of the precipitating agent to 2-methacryloyloxyethyl phosphorylcholine shown in formula (II) is 1-10:1. For example, it can be 2-8:1. In some specific embodiments, it can be 2-4:1, 4-6:1, 6-8:1.

[0088] In the above post-treatment, it is left standing overnight.

[0089] In the above post-treatment, the solvent used for washing is acetone or petroleum ether.

[0090] In the above post-treatment, the drying is vacuum drying, and the drying temperature is 30-90°C, preferably 40-80°C. In some specific embodiments, it can be 40-50°C, 50-60°C, 60-70°C, 70-80°C.

[0091] In the above post-treatment, it needs to be pulverized after drying. The phosphorylcholine copolymer is a white powdery solid.

[0092] The third aspect of the present invention provides the above-mentioned phosphorylcholine copolymer, which is obtained by the above method.

[0093] The fourth aspect of the present invention provides the use of the above-mentioned phosphorylcholine copolymer in cosmetics.

[0094] In the above use, the phosphorylcholine copolymer can be an active additive of cosmetics. In some specific embodiments, the phosphorylcholine copolymer can be a moisturizer, skin protectant, skin conditioner, skin film-forming agent or skin barrier repair agent of cosmetics. Specifically, the phosphorylcholine copolymer can be a carrier of the above-mentioned reagents of cosmetics, that is, a coating wall material.

[0095] The above-mentioned phosphorylcholine copolymer can form bilayer vesicles with a cell membrane-like structure due to its amphiphilic molecular structure of hydrophilic and lipophilic. When it is used as a transport carrier, the hydrophobic core material is embedded in the middle of the bilayer lipid membrane, and the hydrophilic core material is encapsulated in the hydrophilic cavity. It is a potential biocompatible active substance carrier, and exerts biological activities such as encapsulation, slow release, and transdermal promotion.

[0096] The fifth aspect of the present invention provides the use of the above-mentioned phosphorylcholine copolymer in the biomedical field.

[0097] In the above use, the biomedical field includes but is not limited to organ transplantation, ophthalmic care, wound repair, etc. Specifically, for example, the phosphorylcholine copolymer is used as a moisturizer in contact lens care solution in ophthalmic care.

[0098] The following specific examples illustrate the implementation modes 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 modes. All 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.

[0099] When the embodiments give a numerical range, it should be understood that unless otherwise specified in the present invention, both endpoints of each numerical range and any value between the two endpoints 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 technical field of the present invention. In addition to the specific methods, devices, and materials used in the embodiments, according to the knowledge of those skilled in the technical field of the present invention and the description of the present invention, any methods, devices, and materials of the prior art similar to or equivalent to those described in the embodiments of the present invention can also be used to implement the present invention.

[0100] Example 1

[0101] Weigh 23.62 g (80 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 1.3 g (10.0 mmol) of 2-hydroxyethyl methacrylate, 1.42 g (10.0 mmol) of n-butyl methacrylate, and 0.16 g (1.0 mmol) of azobisisobutyronitrile and transfer them to a 250 mL round-bottom flask. Then add 100 mL of absolute ethanol to the round-bottom flask and stir at room temperature until the solids are completely dissolved. After bubbling with high-purity nitrogen for 20 min, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 60 °C to start the polymerization reaction. The entire polymerization process is carried out with a magnetic stirrer at 400 rpm / min. After the polymerization proceeds for 16 h, stop the reaction, remove the rubber stopper from the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 1 L of acetone for 6 h. After standing overnight, pour out the liquid. The obtained solid is washed with acetone and dried in vacuo at 40 °C to constant weight. After being pulverized by a pulverizer, a powdery polymer is obtained, which is the required phosphorylcholine terpolymer sample 1#. The NMR spectrum of phosphorylcholine terpolymer sample 1# is shown in Figure 1 , and the GPC spectrum of phosphorylcholine terpolymer sample 1# is shown in Figure 2 , and the IR spectrum of phosphorylcholine terpolymer sample 1# is shown in Figure 5 .

[0102] Example 2

[0103] The specific experimental steps are as follows: Weigh 79.72 g (270 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 4.3 g (30 mmol) of 2-hydroxypropyl methacrylate, 1.7 g (10.0 mmol) of n-hexyl methacrylate, and 0.49 g (3.0 mmol) of azobisisobutyronitrile and transfer them to a 1000 mL round-bottom flask. Then add 300 mL of anhydrous ethanol to the round-bottom flask, stir at room temperature and add it to the round-bottom flask. Stir at room temperature until the solids are completely dissolved. After bubbling with high-purity nitrogen for 20 minutes, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 70 °C to start the polymerization reaction. The entire polymerization process is carried out with a magnetic stirrer. After the polymerization proceeds for 12 hours, stop the reaction, pull out the rubber stopper of the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 2 L of petroleum ether for 5 h. After standing overnight, pour out the liquid. The obtained solid is washed with petroleum ether and dried in vacuo at 60 °C to constant weight. After passing through a pulverizer, a powdery polymer is obtained, which is the required phosphorylcholine terpolymer sample 2#.

[0104] Example 3

[0105] Weigh 23.62 g (80 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 1.43 g (11 mmol) of 2-hydroxyethyl methacrylate, 2.13 g (15.0 mmol) of n-butyl methacrylate, and 0.16 g (1.0 mmol) of azobisisobutyronitrile and transfer them to a 250 mL round-bottom flask. Then add 80 mL of anhydrous ethanol to the round-bottom flask, stir at room temperature and add it to the round-bottom flask. Stir at room temperature until the solids are completely dissolved. After bubbling with high-purity nitrogen for 22 min, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 50 °C to start the polymerization reaction. The entire polymerization process is carried out with a magnetic stirrer at 500 rpm / min. After the polymerization proceeds for 14 h, stop the reaction, pull out the rubber stopper of the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 0.8 L of acetone for 4 h. After standing overnight, pour out the liquid. The obtained solid is washed with acetone and dried in vacuo at 60 °C to constant weight. After passing through a pulverizer, a powdery polymer is obtained, which is the required phosphorylcholine terpolymer sample 3#.

[0106] Example 4

[0107] Weigh 23.62 g (80 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 2.6 g (20 mmol) of 2-hydroxyethyl methacrylate, 2.84 g (20 mmol) of n-butyl methacrylate, and 0.16 g (1.0 mmol) of azobisisobutyronitrile and transfer them to a 250 mL round-bottom flask. Then add 120 mL of absolute ethanol to the round-bottom flask, stir at room temperature and add it to the round-bottom flask. Stir at room temperature until the solid is completely dissolved. After bubbling with high-purity nitrogen for 18 min, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 70 °C to start the polymerization reaction. The entire polymerization process is carried out with a magnetic stirrer at 300 rpm / min. After the polymerization proceeds for 12 h, stop the reaction. Pull out the rubber stopper of the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 1.0 L of acetone for 8 h. After standing overnight, pour out the liquid. The obtained solid is washed with acetone and dried in vacuo at 80 °C to constant weight. After being pulverized by a pulverizer, a powdery polymer is obtained, which is the required phosphorylcholine terpolymer sample 4#.

[0108] Example 5

[0109] Weigh 23.62 g (80 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 1.42 g (10.0 mmol) of n-butyl methacrylate, 1.3 g (10 mmol) of 2-hydroxyethyl methacrylate, 1.7 g (10.0 mmol) of n-hexyl methacrylate, and 0.16 g (1.0 mmol) of azobisisobutyronitrile and transfer them to a 250 mL round-bottom flask. Then add 100 mL of absolute ethanol to the round-bottom flask, stir at room temperature and add it to the round-bottom flask. Stir at room temperature until the solid is completely dissolved. After bubbling with high-purity nitrogen for 20 min, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 60 °C to start the polymerization reaction. The entire polymerization process is carried out with a magnetic stirrer at 400 rpm / min. After the polymerization proceeds for 16 h, stop the reaction. Pull out the rubber stopper of the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 1 L of acetone for 6 h. After standing overnight, pour out the liquid. The obtained solid is washed with acetone and dried in vacuo at 40 °C to constant weight. After being pulverized by a pulverizer, a powdery polymer is obtained, which is the required phosphorylcholine quaternary copolymer sample 1*.

[0110] Comparative Example 1

[0111] Weigh 79.72 g (270 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 4.26 g (30.0 mmol) of n-butyl methacrylate, and 0.49 g (3.0 mmol) of azobisisobutyronitrile and transfer them to a 1000 mL round-bottom flask. Then add 300 mL of absolute ethanol to the round-bottom flask, stir at room temperature and add it to the round-bottom flask. Stir at room temperature until the solids are completely dissolved. After bubbling with high-purity nitrogen for 20 min, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 60 °C to start the polymerization reaction. The entire polymerization process is carried out with a magnetic stirrer at 400 rpm / min. After the polymerization proceeds for 16 h, stop the reaction, remove the rubber stopper of the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 3 L of acetone. After standing overnight, pour out the liquid. The obtained solid is washed with acetone and dried in vacuo at 40 °C to constant weight, and then pulverized to obtain a powdery polyquaternium-51 polymer, which is used as Comparative Sample 1.

[0112] Comparative Example 2

[0113] Weigh 23.62 g (80 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 2.6 g (20 mmol) of 2-hydroxyethyl methacrylate, and 0.20 g (1.25 mmol) of azobisisobutyronitrile and transfer them to a 250 mL round-bottom flask. Then add 100 mL of absolute ethanol to the round-bottom flask, stir at room temperature and add it to the round-bottom flask. Stir at room temperature until the solids are completely dissolved. After bubbling with high-purity nitrogen for 10 min, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 30 °C to start the polymerization reaction. The entire polymerization process is carried out with a magnetic stirrer at 800 rpm / min. After the polymerization proceeds for 5 h, stop the reaction, remove the rubber stopper of the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 0.6 L of acetone for 0.5 h. After standing overnight, pour out the liquid. The obtained solid is washed with acetone and dried in vacuo at 20 °C to constant weight, and then pulverized to obtain a powdery polymer, which is used as Comparative Sample 2.

[0114] Comparative Example 3

[0115] Weigh 23.62 g (80 mmol) of 2-methacryloyloxyethyl phosphorylcholine, 2.84 g (20 mmol) of n-butyl methacrylate, and 0.16 g (1.0 mmol) of azobisisobutyronitrile and transfer them to a 250 mL round-bottom flask. Then add 80 mL of absolute ethanol to the round-bottom flask. Stir at room temperature until the solids are completely dissolved. After bubbling with high-purity nitrogen for 30 min, stopper the round-bottom flask with a rubber stopper and place it in an oil bath at 100 °C to start the polymerization reaction. Stir the whole polymerization process with a magnetic stirrer at 100 rpm / min. Stop the reaction after 5 h of polymerization. Pull out the rubber stopper of the round-bottom flask, cool the polymerization solution to room temperature, and precipitate it in 0.8 L of acetone for 16 h. After standing overnight, pour out the liquid. The obtained solid is washed with acetone and dried in vacuo at 100 °C to constant weight. After being pulverized by a pulverizer, a powdery polymer is obtained as Comparative Sample 3.

[0116] Test Comparative Example 1

[0117] Compare the performance of the phosphorylcholine terpolymer sample 1# obtained in Example 1 with the comparative sample 1 (phosphorylcholine binary copolymer polyquaternium-51) obtained in Comparative Example 1.

[0118] 1. Test of skin stratum corneum water content

[0119] The skin water content value can directly reflect the dryness of the skin and further reflect the moisturizing effect of the product. Healthy male or female subjects aged 25-40 are selected. Random, single-blind, and controlled tests are carried out. Moisturizing water is used on the left and right forearms of the subjects according to the random principle, and applied to the test sites at a dose of (2.0 ± 0.1) mg / cm 2 .

[0120] Before using the sample, 1 h, 2 h, and 4 h after using the product, the tester uses the CM 825 skin water content tester to measure the skin water content of the experimental sites. Each site is measured 5 times and the average value is taken. The skin water content data is as Figure 7 .

[0121] The experimental results show that adding 0.1% hyaluronic acid (abbreviation: HA, molecular weight: 150w), 0.1% binary copolymer, and 0.1% terpolymer all have moisturizing effects. Among them, from Figure 7 the water content data at 4 h above, it can be seen that the moisturizing effect of the terpolymer is 19.2% and 23.6% higher than that of HA and the binary copolymer. Therefore, the phosphorylcholine terpolymer has a moisturizing effect, and its moisturizing ability is better than that of the phosphorylcholine binary copolymer.

[0122] 2. Test of HaCaT cells to investigate the repair performance

[0123] Human keratinocytes HaCaT were cultured and subjected to light (ultraviolet) damage. Then, the effects of different concentrations of phosphorylcholine terpolymers on filaggrin (FLG) in the cells were studied, and the repair effect of phosphorylcholine terpolymers after (ultraviolet) damage was evaluated. See Figure 8 , Table 1.

[0124] Table 1 Comparison of test data of HaCaT cells

[0125]

[0126] The experimental results show that: under the action of low concentrations of phosphorylcholine terpolymers, there is a significant promoting effect on filaggrin expression, and it has a strong skin barrier repair effect. From the data in Table 1, it can be seen that when the concentration of phosphorylcholine terpolymer is 0.025%, the FLG promotion rate is 39.73%, and the promotion rate is 3.5 times that of the binary copolymer.

[0127] In summary, compared with phosphorylcholine binary copolymers, phosphorylcholine terpolymers have stronger moisturizing and repair properties.

[0128] Test Comparative Example 2

[0129] The phosphorylcholine terpolymer sample 1# obtained in Example 1 was used as a lipid inclusion body. It is a carrier based on innovative amphiphilic cosmetic active ingredients. Currently, the formulation system often simply adds the active ingredients directly to the formulation system, and the transdermal absorption problem of active ingredients has always been a difficult problem. The phosphorylcholine terpolymer encapsulation technology adopted in the present invention is based on the fact that amphiphilic substances can form bilayer vesicles with cell-like structures. When used as a transport carrier, the hydrophobic core material is embedded in the middle of the bilayer lipid membrane, and the hydrophilic core material is wrapped in the hydrophilic cavity, and a stable liposome can be formed simply by mixing with water. The active ingredient ceramide was encapsulated, and the liquid was broken, mixed, and homogenized to form an inclusion with a particle size of about 90 nm, PDI: 0.2 - 1, Zeta: -70 - -30, and uniform particle size. The pH range of the liposome is 5.0 - 7.0, thus greatly enhancing the effect of the active ingredient on the skin. The particle size diagram of the encapsulated liposome is shown in Figure 4 . By comparing the characteristic peak distributions of the infrared spectra before and after encapsulating ceramide NP (as shown in Figure 5 , Figure 6 ), multiple characteristic peaks of ceramide NP disappeared after liposome encapsulation (especially in the 1200 - 1600 cm -1 section), indicating that the characteristic groups corresponding to ceramide NP in this region were successfully encapsulated, proving that ceramide was encapsulated in the liposome structure. The original solution of ceramide NP liposome after encapsulation is shown in Figure 9a , the 10% water dilution is shown in Figure 9b , 5 % essence formula is shown in Figure 9c .

[0130] Test Comparative Example 3

[0131] Similar to Test Comparative Example 2, the active ingredient glycyrrhizin flavonoids, liposome structure analogs, and emulsifiers were encapsulated, and they were mixed into an aqueous phase mixture in a certain proportion. Compared with the liquiritigenin alcohol solution (the alcohols used were butylene glycol, propylene glycol, 1,3 - propylene glycol, ethanol, ethoxydiglycol, etc.), the transdermal performance of the liquiritigenin aqueous solution modified with phosphorylcholine terpolymer was better, and the transdermal efficiency was 2 - 3 times that of the liquiritigenin alcohol solution, as shown in Table 2.

[0132] Table 2 Difference in Transdermal Ability

[0133]

[0134]

[0135] After the modification of liquiritigenin with phosphorylcholine, its photothermal stability was better, and the test results were expressed in terms of platinum - cobalt color degrees in the range of 0 to 500 (platinum - cobalt APHA - American Public Health Association standard). The test results were reported according to Table 3 below, and the gradient curve is shown in Figure 11 .

[0136] Table 3

[0137]

[0138] Test Comparative Example 4 Moisturizing Effect Test

[0139] Commercially available contact lens care solution was purchased as a blank sample, and commercially available contact lens care solution plus 0.5% of the phosphorylcholine terpolymer sample 1# prepared in Example 1 (the recommended addition amount is 0.1 - 1%) was used as a comparative sample. Six groups of silicone hydrogel contact lenses of the same model were prepared, with 3 replicates in each group. The dry weight of each contact lens was measured using a precision electronic balance. The six groups of contact lenses were immersed in the two groups of contact lens care solutions for 24 h. The immersed contact lenses were taken out, the surface liquid was wiped off, and the wet weight of the contact lenses was measured using a precision electronic balance. Subsequently, they were placed in a drying environment with a temperature of 35°C and a relative humidity of 40%. The wet weight of the contact lenses was measured every 1 h using a precision electronic balance, and the water content of the contact lenses was calculated according to the following formula: Water content = (wet weight - dry weight) / wet weight × 100%, and the results are shown in Table 4.

[0140] Table 4

[0141] Comparison 1 Comparison 2 Comparison 3 Blank 1 Blank 2 Blank 3 Water content at 1 h 88％ 85％ 87％ 87％ 85％ 86％ Water content at 2 h 86％ 83％ 85％ 85％ 83％ 84％ Water content at 3 h 84％ 81％ 83％ 83％ 80％ 81％ Water content at 4 h 82％ 79％ 81％ 81％ 78％ 79％ Water content at 6 h 79％ 76％ 79％ 76％ 73％ 76％ Water content at 8 h 77％ 73％ 75％ 71％ 68％ 69％ Water content at 10 h 73％ 69％ 72％ 67％ 63％ 64％ Water content at 12 h 70％ 65％ 69％ 61％ 59％ 59％ Water content at 14 h 67％ 62％ 66％ 56％ 53％ 54％ Water content at 16 h 64％ 59％ 63％ 51％ 48％ 49％

[0142] From the test results of the moisturizing effects of the comparative sample and the blank sample in Table 4, it can be seen that starting from the 8th hour, the water content of the sample 1# with phosphorylcholine terpolymer is significantly higher than that of the blank sample, indicating that the phosphorylcholine terpolymer can significantly improve and extend the moisturizing effect of the eyewash.

[0143] Test Comparative Example 5

[0144] The performance of the phosphorylcholine terpolymer sample 1# obtained in Example 1 was compared with the comparative sample 2 obtained in Comparative Example 2 and the comparative sample 3 obtained in Comparative Example 3.

[0145] 1. Test of the water content of the skin stratum corneum

[0146] The skin water content value can directly reflect the dryness of the skin and thus reflect the moisturizing efficacy of the product. Healthy male or female subjects aged 25 to 40 were selected. Using a random, single-blind, controlled test, moisturizing water was used on the left and right forearms of the subjects according to the random principle, and applied to the test site at a dose of (2.0 ± 0.1) mg / cm 2 of the dose.

[0147] Before using the sample, 1 hour, 2 hours, and 4 hours after using the product, the tester used the CM 825 skin water content tester to measure the skin water content of the experimental site. Each site was measured 5 times, and the average value was taken.

[0148] The experimental results showed that adding 0.1% phosphorylcholine terpolymer sample 1#, 0.1% comparative sample 2, and 0.1% comparative sample 3 all had moisturizing effects. The effect data are shown in Figure 12 , from Figure 12 the water content data shown, it can be seen that the moisturizing effect of the phosphorylcholine terpolymer sample 1# was 13.40% and 7.72% higher than that of the comparative sample 2 and the comparative sample 3 respectively 4 hours after use. Therefore, the moisturizing ability of the phosphorylcholine terpolymer sample 1# is better than that of the comparative sample 2 and the comparative sample 3.

[0149] 2. Investigation of the repair performance by HaCaT cell test

[0150] Human keratinocytes HaCaT were cultured. After photo (ultraviolet) damage, the effects of the phosphorylcholine terpolymer sample 1#, the comparative sample 2, and the comparative sample 3 on the filaggrin FLG of the cells were studied, and the repair effect of the phosphorylcholine terpolymer after (ultraviolet) damage was evaluated. The test results are shown in Figure 13 , Table 5.

[0151] Table 5 Comparison of HaCaT cell test data

[0152]

[0153] The experimental results show that: under the action of the phosphorylcholine terpolymer sample 1#, it has a significant effect on promoting the expression of filaggrin and has a strong skin barrier repair effect. It can be seen from the data in Table 5 that when the concentration is 0.05%, the FLG promotion rate of the phosphorylcholine terpolymer sample 1# is 38.55%, and the promotion rate is better than that of Comparative Sample 2 and Comparative Sample 3.

[0154] In summary, compared with Comparative Sample 2 and Comparative Sample 3, the phosphorylcholine terpolymer sample 1# prepared under specific process conditions has stronger moisturizing and repair properties.

[0155] The above embodiments are intended to illustrate the embodiments disclosed in the present invention and should not be construed as limiting 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 connection 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, the chemical structure of the copolymer is shown in formula (I): In formula (I), 2 ≤ l ≤ 20; 1 ≤ m ≤ 4; 2 ≤ n ≤ 20.

2. The phosphorylcholine copolymer according to claim 1, wherein The reaction formula (I) includes any one or more of the following conditions: A1) w, x, y, z respectively represent the number of repeating units, and w, x, y, z are positive integers greater than or equal to 1; preferably, w is 50 - 1000, x is 50 - 1000, y is 10 - 500, and z is 10 - 500; A2) l is the degree of branching, and l is a positive integer greater than or equal to 2 and less than or equal to 20; A3) m is the degree of branching, and m is a positive integer greater than or equal to 1 and less than or equal to 4; A4) n is the degree of branching, and n is a positive integer greater than or equal to 2 and less than or equal to 20; A5) The relative molecular mass of the copolymer is 1 - 1,000,000 g / mol; A6) The relative average molecular mass of the copolymer is 1 - 150,000 g / mol; A7) The degree of polymerization of the copolymer is 100 - 1500.

3. A method for preparing a phosphocholine copolymer, comprising: 2-methacryloyloxyethyl phosphorylcholine shown in formula (II), fatty acid methyl acrylate shown in formula (III), 2-hydroxy fatty acid methyl acrylate shown in formula (IV), and fatty acid methyl acrylate shown in formula (V) are added with an initiator and a solvent for polymerization reaction, and the obtained polymerization stock solution is then post-treated to obtain the phosphorylcholine copolymer shown in formula (I); The process route is as follows:

4. The preparation method of the phosphorylcholine copolymer according to claim 3, characterized in that It includes any one or more of the following conditions: B1) In formula (III), 2 ≤ l ≤ 20. l is the degree of branching, and l is a positive integer greater than or equal to 2 and less than or equal to 20; B2) In formula (IV), 1 ≤ m ≤ 4. m is the degree of branching, and m is a positive integer greater than or equal to 1 and less than or equal to 4; B3) In formula (V), 2 ≤ n ≤ 20. n is the degree of branching, and n is a positive integer greater than or equal to 2 and less than or equal to 20; B4) The molar ratio of 2-methacryloyloxyethyl phosphorylcholine shown in formula (II), fatty acid methyl acrylate shown in formula (III), 2-hydroxy fatty acid methyl acrylate shown in formula (IV), and fatty acid methyl acrylate shown in formula (V) is 1 - 15: 0.5 - 4: 0.5 - 4: 0.5 - 4; B5) The initiator is an additive for initiating a radical polymerization reaction; preferably, the initiator is azobisisobutyronitrile; B6) The mass ratio of the initiator to 2-methacryloyloxyethyl phosphorylcholine shown in formula (II) is 1: 50 - 600; B7) The solvent is selected from one or a mixture of two of water or alcohol; B8) The total volume ratio of the solvent to the reactants is 1 - 7:

1.

5. The preparation method of the phosphorylcholine copolymer according to claim 3, characterized in that, It also includes any one or more of the following conditions: C1) High-purity nitrogen is bubbled before the polymerization reaction to remove oxygen; C2) The heating temperature of the polymerization reaction is 40 - 90 °C; C3) The stirring rate of the polymerization reaction is 100 - 700 rpm / min; C4) The reaction time of the polymerization reaction is 5 - 30 h; C5) The post-treatment includes: cooling the polymerization stock solution and then adding a precipitant for sedimentation, followed by standing and then taking the solid for washing and drying to provide the desired phosphorylcholine copolymer.

6. The preparation method of the phosphorylcholine copolymer according to claim 5, characterized in that, including any one or more of the following conditions: C11) The high-purity nitrogen bubbling time is 15 - 25 min; C51) Cooling to room temperature; C52) The precipitant is selected from at least one of petroleum ether, n-hexane, ethyl acetate, acetone or anhydrous ether; C53) The sedimentation time is 1 - 15 h; C54) The volume ratio of the precipitant to 2-methacryloyloxyethyl phosphorylcholine shown in formula (II) is 1 - 10:1; C55) Standing overnight; C56) The solvent used for washing is acetone or petroleum ether; C57) The drying is vacuum drying, and the drying temperature is 30 - 90 °C; C58) Crushing is to be carried out after drying.

7. A phosphorylcholine copolymer obtained by the method according to any one of claims 3 - 6.

8. Use of the phosphorylcholine copolymer according to any one of claims 1 - 2 or the phosphorylcholine copolymer according to claim 7 in cosmetics.

9. Use of the phosphorylcholine copolymer according to any one of claims 1 - 2 or the phosphorylcholine copolymer according to claim 7 in the biomedical field.

10. The use according to claim 9, wherein, The biomedical field includes organ transplantation, ophthalmic care, wound repair; preferably, the phosphorylcholine copolymer is used as a humectant in contact lens care solution for ophthalmic care.

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