Method for preparing amphiphilic BAB triblock polymer

Abstract

The present application discloses a method for preparing an amphiphilic BAB triblock polymer. The method comprises: subjecting a compound represented by formula (I) and a compound represented by formula (II) to an addition reaction by using Karstedt as a catalyst, to obtain the amphiphilic BAB triblock polymer, wherein the structure of the compound represented by formula (I) is: formula (I), and the structure of the compound represented by formula (II) is: formula (II). In the preparation method of the present application, on the basis of an Si-H addition reaction using Karstedt as a catalyst, by means of a basic strategy of respectively constructing a hydrophobic-end PDMS prepolymer B and hydrophilic-end prepolymers A such as PMOXA / PEG, and by applying the concept of green chemistry, the amphiphilic BAB triblock polymer is synthesized under mild conditions, thereby simplifying a post-treatment purification process, reducing production energy consumption and environmental pollution, improving the overall yield and polymer dispersity, and providing a convenient method for wider structural modification.

Description

Preparation method of amphiphilic BAB triblock polymer

[0001] Priority information

[0002] This application claims priority and benefit to patent application PCT / CN2025 / 075410 filed with the World Intellectual Property Organization on January 27, 2025, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of polymer materials technology, specifically to a method for preparing an amphiphilic BAB triblock polymer. Background Technology

[0004] Self-assembly at the nanoscale is a key property upon which the formation of biological membranes in nature depends. These membranes construct a functionalized molecular framework by embedding channels, receptors, and molecular pumps within a microenvironment and functional framework. Utilizing hydrophobic-hydrophilic interactions, these membranes self-assemble into other structures such as bilayers and vesicles. Self-assembled membranes are a crucial component if we wish to mimic the principles of natural nanostructures. In recent years, a range of polymer systems have been used for drug delivery, biopharmaceutical coatings, virus-assisted gene delivery, and nanoreactors through their self-assembly. These are amphiphilic diblock or triblock copolymers that self-assemble in suitable solvents into micelles, worm-like micelles, tubular structures, membranes, or vesicles.

[0005] Block copolymers exhibit a wide variety of structures, with amphiphilic ABA triblock copolymers receiving particular attention in recent years due to their inherent ability to self-assemble into vesicle structures, despite their high hydrophobicity and hydrophilicity. From a biomedical perspective, polyoxazoline provides a pseudopolypeptide structure, making it especially attractive and thus chosen as hydrophilic block A. Polymethylsiloxanes (PDMS), due to the ionic nature of the Si-CH3 bonds, exhibit a very low glass transition temperature and are mostly liquid at room temperature. Furthermore, poly(siloxanes) possess very low surface energy and extremely high hydrophobicity; therefore, they were chosen as hydrophobic block B. Extensive research has been conducted on these ABA triblock copolymer systems, demonstrating their interesting biomedical and self-assembly properties.

[0006] However, there is relatively little research on amphiphilic BAB-type triblock polymers. Summary of the Invention

[0007] This application aims to at least partially address one of the technical problems existing in the prior art. To this end, this application provides a method for preparing an amphiphilic BAB triblock polymer.

[0008] This application is based on the following discoveries of the inventors:

[0009] In 2012, Sepideh Khoee designed and synthesized amphiphilic ABA triblock copolymers (m-PEG-PCL-m-PEG) and amphiphilic BAB-type triblock polymers (PCL-PEG-PCL) using the two methods shown in Figure 1. These two types of triblock polymers exhibit significant differences in properties such as stability and critical micelle concentration. Among them, the amphiphilic BAB-type triblock polymer (PCL-PEG-PCL) demonstrates superior characteristics such as a higher critical micelle concentration and less tendency to aggregate.

[0010] In 2012, as shown in Figure 2, Alireza Foroumadi et al. also designed and synthesized amphiphilic ABA triblock copolymers (m-PEG-PBA-m-PEG) and amphiphilic BAB-type triblock polymers (PBA-PEG-PBA) with similar molecular weights but different block sequences. Based on the differences in the stacking morphology of the two types of polymers, they differ in drug loading capacity, encapsulation efficiency, controlled release, particle size, and size distribution.

[0011] However, the aforementioned amphiphilic BAB-type triblock polymers PCL-PEG-PCL and PBA-PEG-PBA have the following drawbacks: 1) The hydrophilic block is limited to PEG (polyethylene glycol), and no other hydrophilic blocks have been reported; 2) The hydrophobic blocks are PCL and PBA, respectively, resulting in excessively high glass transition temperatures; 3) There is no flexible linker between the hydrophilic and hydrophobic blocks, reducing the flexibility of the polymer stacking and hindering film formation; 4) The process is complex, and the polymer structure modification is limited. Furthermore, as shown in Figure 2, the synthesis of PBA-PEG-PBA requires a reduced pressure environment, which imposes stringent process requirements and is not environmentally friendly.

[0012] However, the hydrophobic block of the amphiphilic BAB triblock polymer designed in this application is PDMS, which overcomes the shortcomings of complex structural modification and insufficient personalized design and synthesis for applicable scenarios. It is applied to biomembrane applications such as capsule rupture preparation. The preparation method is based on the Si-H addition reaction with Karstedt as catalyst (e.g., Karstedt Catalyst, in Xylene, Pt ~ 2%, this catalyst is a commercial reagent, the concentration is expressed as Pt ~ 2%, purchased from Anaiji Chemical). The basic strategy is to construct hydrophobic prepolymer B and hydrophilic prepolymer A respectively. Using the concept of green chemistry, the amphiphilic BAB triblock polymer was synthesized under mild conditions, which simplifies the post-processing purification process, reduces production energy consumption and environmental pollution, improves the overall yield and polymer dispersibility, and provides a convenient method for a wider range of structural modifications.

[0013] In a first aspect, this application proposes a method for preparing an amphiphilic BAB triblock polymer. According to embodiments of this application, the method includes:

[0014] Using Karstedt as a catalyst, the compound shown in formula (I) and the compound shown in formula (II) were subjected to an addition reaction to obtain the amphiphilic BAB triblock polymer; wherein:

[0015] The structure of the compound shown in formula (I) is as follows:

[0016] The structure of the compound shown in formula (II) is as follows:

[0017] Each R1 is independently selected from C 1～6 Alkyl groups, or 6- to 10-membered aromatic groups;

[0018] R2 is selected from C 1～6 Alkyl groups, or 6- to 10-membered aromatic groups;

[0019] R3 is selected from -R 3a - or -R 3a -LR 3b -, where each R 3a Each is independently selected from polyamide-imide (PAI) and polyoxyalkylene (POXA) groups. L is selected from -O-, Each R 3b Each is independently selected from H or C. 1～6 Alkyl groups, each x being independently selected from 3 to 15;

[0020] R4 is selected from

[0021] Each R6 is independently selected from C 1～6 Alkyl groups, or 6- to 10-membered aromatic groups;

[0022] Each R7 is independently selected from C 1～6 alkyl;

[0023] Each R8 is independently selected from C 1～6 Alkyl or acetyl groups;

[0024] Each R9 is independently selected from C 1～6 Alkylene;

[0025] n is any integer between 20 and 40;

[0026] m is selected from any integer between 3 and 12;

[0027] q is selected from integers between 0 and 10.

[0028] The method in this application is based on the Si-H addition reaction with Karstedt as catalyst. Using the concept of green chemistry, this amphiphilic BAB triblock polymer was synthesized under mild conditions. This simplifies the post-processing purification process, reduces production energy consumption and environmental pollution, improves the overall yield and polymer dispersibility, and provides a convenient method for a wider range of structural modifications.

[0029] According to the embodiments of this application, n is selected from 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40.

[0030] According to the embodiments of this application, m is selected from 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12.

[0031] According to an embodiment of this application, q is selected from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.

[0032] According to embodiments of this application, each x is independently selected from 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15. For example, each x is independently selected from 3 to 10.

[0033] According to embodiments of this application, the amphiphilic BAB triblock polymer has the structure shown in Formula III:

[0034] R5 is selected from C 2～10 Alkylene

[0035] Each R6 is independently selected from C 1～6 Alkyl groups, 6- to 10-membered aromatic groups;

[0036] Each R7 is independently selected from C 1～6 alkyl;

[0037] Each R8 is independently selected from C 1～6 Alkyl, acetyl;

[0038] Each R9 is independently selected from C 1～6 Alkylene.

[0039] In an optional embodiment of this application, R3 is selected from polyamide-imide (PAI), polyoxyalkylene (POXA),

[0040] In an optional embodiment of this application, R3 is selected from...

[0041] In one optional embodiment of this application, the amphiphilic BAB triblock polymer is selected from PDMS-PEG-PDMS, PDMS-PEG-PMOXA-PDMS, PDMS-PMOXA-PDMS, PDMS-PMOXA-Linker2-PMOXA-PDMS, where Linker2 is shown in R5.

[0042] According to an embodiment of this application, the molar ratio of the compound shown in formula (I) and the compound shown in formula (II) is (1.8 to 2.5):1, for example 1.8:1, 1.9:1, 2.0:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1 or any two of these ratios are used as a range between endpoint values.

[0043] According to an embodiment of this application, the temperature of the addition reaction is 60°C to 80°C, for example, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C, 71°C, 72°C, 73°C, 74°C, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, or any two of these values ​​as a range between endpoint values.

[0044] According to an embodiment of this application, the addition reaction time is 20h to 30h, for example 20h, 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, 30h, or any two of these values ​​as a range between endpoint values.

[0045] According to embodiments of this application, the solvent in the addition reaction is selected from at least one of toluene, tetrahydrofuran, and DMF.

[0046] According to embodiments of this application, the compound represented by formula (I) is obtained by the following manner:

[0047] S1. The compound shown in formula (Ia) is reacted with the compound shown in formula (Ib) to obtain the compound shown in formula (Ic);

[0048] S2. The compound shown in formula (Ic) is subjected to a halogenation reaction with the compound shown in formula (Id) to obtain the compound shown in formula (I);

[0049] According to an embodiment of this application, the first reaction is carried out under DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) conditions.

[0050] According to embodiments of this application, the molar ratio of the compound shown in formula (Ia) to the compound shown in formula (Ib) is (5-10):1, for example 5.0:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, 6.0:1, 6.1:1, 6.2:1, 6.3:1, 6.4:1, 6.5:1, 6.6:1, 6.7:1, 6.8:1, 6.9:1, 7.0:1, 7.1:1, 7.2:1, 7... 3:1, 7.4:1, 7.5:1, 7.6:1, 7.7:1, 7.8:1, 7.9:1, 8.0:1, 8.1:1, 8.2:1, 8.3:1, 8.4:1, 8.5:1, 8.6:1, 8.7:1, 8.8:1, 8.9:1, 9.0:1, 9.1:1, 9.2:1, 9.3:1, 9.4:1, 9.5:1, 9.6:1, 9.7:1, 9.8:1, 9.9:1, 10.0:1, or any two of these ratios are used as the range values ​​between the endpoint values.

[0051] According to an embodiment of this application, the temperature of the first reaction is 25°C to 35°C, for example, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, or any two of these values ​​as a range between endpoint values.

[0052] According to an embodiment of this application, the time of the first reaction is 60h to 80h, for example, 60h, 61h, 62h, 63h, 64h, 65h, 66h, 67h, 68h, 69h, 70h, 71h, 72h, 73h, 74h, 75h, 76h, 77h, 78h, 79h, 80h, or any two of these values ​​as a range between endpoint values.

[0053] According to an embodiment of this application, the solvent in the first reaction is selected from tetrahydrofuran.

[0054] According to embodiments of this application, the acid-binding agent for the halogenation reaction is selected from pyridine.

[0055] According to embodiments of this application, the molar ratio of the compound represented by formula (Ic) to the compound represented by formula (Id) is 1:(3-8), for example 1:3.0, 1:3.1, 1:3.2, 1:3.3, 1:3.4, 1:3.5, 1:3.6, 1:3.7, 1:3.8, 1:3.9, 1:4.0, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9, 1:5.0, 1:5.1, 1:5.2, 1 5.3, 1:5.4, 1:5.5, 1:5.6, 1:5.7, 1:5.8, 1:5.9, 1:6.0, 1:6.1, 1:6.2, 1:6.3, 1:6.4, 1:6.5, 1:6.6, 1:6.7, 1:6.8, 1:6.9, 1:7.0, 1:7.1, 1:7.2, 1:7.3, 1:7.4, 1:7.5, 1:7.6, 1:7.7, 1:7.8, 1:7.9, 1:8.0, or any two of these ratios, are used as the range values ​​between the endpoint values.

[0056] According to embodiments of this application, the compound represented by formula (II) is obtained by the following manner:

[0057] Under inert gas conditions, compound 1 and compound 2 were subjected to a capping reaction to obtain the compound shown in formula (II).

[0058] According to embodiments of this application, compound 1 is selected from polyethylene glycol (PEG), polyoxazoline (POXA), polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylamide (PAM), polymethyl methacrylate (PMMA), poly(N,N-dimethylacrylamide) (PDMA), polyacrylamide (PAI), and polyhydroxyalkyl acrylate (PHPMA).

[0059] According to embodiments of this application, compound 2 is selected from compounds containing alkenyl or ynyl structures. Thus, the compound shown in formula (II) can be formed by Si-H addition.

[0060] According to embodiments of this application, compound 2 is selected from...

[0061] Among them, R6 is selected from C 1～6 Alkyl groups, 6- to 10-membered aromatic groups;

[0062] R7 is selected from C 1～6 alkyl;

[0063] R8 is selected from C 1～6 Alkyl, acetyl;

[0064] R9 is selected from C 1～6 Alkylene;

[0065] q is selected from integers between 0 and 10.

[0066] According to an embodiment of this application, the molar ratio of compound 1 to compound 2 is 1:(1.5 to 2.5), for example 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, or any two of these ratios as a range between endpoint values.

[0067] According to an embodiment of this application, the capping reaction is carried out under strong alkaline solution conditions.

[0068] According to embodiments of this application, the solvent for the capping reaction is selected from at least one of tetrahydrofuran and diethyl ether.

[0069] According to an embodiment of this application, the strong alkali solution is selected from NaH.

[0070] In a second aspect of this application, an amphiphilic BAB triblock polymer is provided. According to an embodiment of this application, the amphiphilic BAB triblock polymer is prepared by the method described in the first aspect.

[0071] In a third aspect of this application, the application proposes the use of an amphiphilic BAB triblock polymer prepared according to the method described in the first aspect or the amphiphilic BAB triblock polymer described in the second aspect in the preparation of vesicles or biomimetic membranes.

[0072] In a fourth aspect, this application provides a vesicle. According to embodiments of this application, the vesicle comprises an amphiphilic BAB triblock polymer prepared according to the method described in the first aspect or the amphiphilic BAB triblock polymer described in the second aspect.

[0073] In a fifth aspect of this application, a biomimetic membrane is proposed. According to embodiments of this application, the biomimetic membrane comprises an amphiphilic BAB triblock polymer prepared according to the method described in the first aspect or the amphiphilic BAB triblock polymer described in the second aspect.

[0074] Additional aspects and advantages of this application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of this application. Attached Figure Description

[0075] The above and / or additional aspects and advantages of this application will become apparent and readily understood from the description of the embodiments taken in conjunction with the following drawings, in which:

[0076] Figure 1 shows the synthesis of amphiphilic ABA triblock copolymer (m-PEG-PCL-m-PEG) (Figure 1a) and amphiphilic BAB-type triblock polymer (PCL-PEG-PCL) (Figure 1b);

[0077] Figure 2 shows the synthesis of amphiphilic ABA triblock copolymer (m-PEG-PBA-m-PEG) (Figure 2a) and amphiphilic BAB-type triblock polymer (PBA-PEG-PBA) (Figure 2b);

[0078] Figure 3 shows the hydrogen NMR spectrum of S3-1 in Example 1 of this application;

[0079] Figure 4 shows the hydrogen NMR spectrum of S5-1 in Example 1 of this application;

[0080] Figure 5 shows S5-1GPC in Embodiment 1 of this application;

[0081] Figure 6 shows the hydrogen NMR spectrum of S8-1 in Example 1 of this application;

[0082] Figure 7 shows the 1H NMR spectrum of PDMS-PEG-PDMS(P1) in Example 1 of this application;

[0083] Figure 8 shows the PDMS-PEG-PDMS(P1)GPC in Example 1 of this application;

[0084] Figure 9 shows the hydrogen NMR spectrum of S5-2 in Example 2 of this application;

[0085] Figure 10 shows S5-2GPC in Embodiment 2 of this application;

[0086] Figure 11 shows the hydrogen NMR spectrum of SB-2 in Example 2 of this application;

[0087] Figure 12 shows the hydrogen NMR spectrum of SB-3-X in Example 2 of this application;

[0088] Figure 13 shows the hydrogen NMR spectrum of SB-4-X in Example 2 of this application;

[0089] Figure 14 shows the hydrogen NMR spectrum of SB-5-X in Example 2 of this application;

[0090] Figure 15 shows the 1H NMR spectrum of SB-6-XY in Example 2 of this application;

[0091] Figure 16 shows the 1H NMR spectrum of PDMS-PMOXA-Piperazine-PMOXA-PDMS(P2) in Example 2 of this application;

[0092] Figure 17 shows the PDMS-PMOXA-Piperazine-PMOXA-PDMS(P2)GPC in Embodiment 2 of this application;

[0093] Figure 18 shows the 1H NMR spectrum of SC-3 in Example 3 of this application;

[0094] Figure 19 shows the 1H NMR spectrum of PDMS-PEG-PMOXA-PDMS(P3) in Example 3 of this application;

[0095] Figure 20 shows the PDMS-PEG-PMOXA-PDMS(P3)GPC in Example 3 of this application;

[0096] Figure 21 shows the 1H NMR spectrum of SD-2 in Example 4 of this application;

[0097] Figure 22 shows the 1H NMR spectrum of PDMS-PMOXA-PDMS(P4) in Example 4 of this application;

[0098] Figure 23 shows the PDMS-PMOXA-PDMS(P4)GPC in Embodiment 4 of this application. Detailed Implementation

[0099] The embodiments of this application are described in detail below. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application.

[0100] It should be noted that the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Therefore, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. Furthermore, in the description of this application, unless otherwise stated, "multiple" means two or more.

[0101] Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of that feature. In the description of this disclosure, "a plurality of" means at least two, such as two, three, etc., unless otherwise explicitly specified.

[0102] In this document, the terms “comprising” or “including” are open-ended expressions, meaning that they include the contents specified in this invention, but do not exclude other aspects.

[0103] The term "C1-C" 10"Alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1-10 carbon atoms. Such alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc. "C1-C6 alkyl" should be understood to refer to a straight-chain or branched saturated monovalent hydrocarbon group having 1-6 carbon atoms. Other related terms follow the same principle.

[0104] The term "alkylene" refers to a form of "alkyl" that lacks an H atom.

[0105] The term "6-10 aryl" should be understood to preferably refer to a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6-10 carbon atoms. In particular, it refers to a ring with 6 carbon atoms ("C6 aryl"), such as phenyl; or a ring with 9 carbon atoms ("C9 aryl"), such as indenyl or indenyl; or a ring with 10 carbon atoms ("C9 aryl"). 10 Aryl), such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl. The term "C6-C" is used. 10 "Aryl" should preferably be understood to refer to a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6-10 carbon atoms and possessing monovalent aromaticity or partial aromaticity. Other related terms follow the same principle.

[0106] This application discloses a method for preparing an amphiphilic BAB triblock polymer. The amphiphilic BAB triblock polymer has the structure shown in formula (IIIa):

[0107] The preparation method is as follows:

[0108] Step 1: Under argon protection, add compound S2 to a Schlenk flask using a pipette, seal the top with a rubber stopper, then add tert-butylsiloxane S1 using a syringe, along with DBU as a catalyst, wherein the molar ratio of compound S1 to S2 is 8:1. Next, add DBU using a microsyringe, and then add dry tetrahydrofuran to dissolve and stir. React at 30°C for 72 hours.

[0109] Step 2: Dissolve dry compound S3 in dry tetrahydrofuran under an argon atmosphere. Add dimethylchlorosilane and pyridine, and react at room temperature for 12 h. The molar ratio of compound S3, dimethylchlorosilane, and pyridine is 1:(4-6):(4-6).

[0110] Step 3: Under argon protection, add dry NaH and tetrahydrofuran, and cool and stir in an ice bath for 15 minutes. Add polyethylene glycol S7 dropwise, and stir thoroughly in an ice bath for 30 minutes. Add allyl bromide S6 dropwise, and slowly heat to room temperature. After reacting for 30 minutes, heat to reflux and stir overnight. The molar ratio of compound S6 to compound S7 is (1.5–2.5):1.

[0111] Step 4: Dissolve compound S5 and dried compound S8 in 30 mL of dry toluene under argon atmosphere. After complete dissolution, add 120 μL of Karstedt Catalyst (Karstedt Catalyst, in Xylene, Pt ~2%, this catalyst is a commercial reagent, concentration expressed as Pt ~2%, purchased from Anaiji Chemicals), then heat to 70 °C and stir at 70 °C for 24 h. The molar ratio of compound S5 to compound S8 is (1.5 ~ 3.0): 1.

[0112] In an optional embodiment of this application, the structure of the amphiphilic BAB triblock polymer is as follows:

[0113]

[0114] The preparation method is described in Example 1 of this application.

[0115] This application discloses a method for preparing an amphiphilic BAB triblock polymer. The amphiphilic BAB triblock polymer has the structure shown in formula (IIIb):

[0116] The preparation method is as follows:

[0117] Step 1, Preparation of compound S5-2: Compound S2 was added under argon protection, followed by methylsiloxane S1-2, with DBU added as a catalyst. The molar ratio of compounds S1-2 to S2 was 8:1. DBU was then added using a microsyringe, and dry tetrahydrofuran was added to dissolve and stir. The reaction was carried out at 30°C for 72 h. Dimethylchlorosilane and pyridine were then added, and the reaction was carried out at room temperature for 12 h. The molar ratio of compounds S3, dimethylchlorosilane, and pyridine was 1:(4-6):(4-6).

[0118] Step 2: Under argon protection, p-toluenesulfonic acid and silver oxide were added to dry acetonitrile and stirred thoroughly for 30 mins. The salt was quickly removed by filtration, and the filtrate was collected in a reaction flask. Allyl bromide was added, and the mixture was stirred at 70 °C for 16 h. After removing the solvent by vacuum distillation, the product was purified by silica gel chromatography to obtain the intermediate product SB-2.

[0119] Step 3: Under argon protection, SB-2 was dissolved in 100 mL of dry acetonitrile, and 2-methyloxazoline was added at 80 °C. The mixture was refluxed at 80 °C for 12 h. After removing the solvent by vacuum distillation, intermediate product SB-3-X or SB-3-Y was obtained. The molar ratio (1:X / Y) of compound SB-2 and compound 2-methyloxazoline was 1:(3.0~10.0).

[0120] Step 4: Under argon protection, SB-3 was dissolved in 100 mL of dry acetonitrile, B℃-piperazine and potassium carbonate were added, and the mixture was stirred at room temperature for 12 h. The salt was quickly removed by filtration, and the filtrate was collected in a reaction flask. The solvent was removed by vacuum distillation, and the residue of B℃-piperazine was removed by washing with diethyl ether three times to obtain the intermediate product SB-4-X.

[0121] Step 5: Dissolve SB-4-X in 40 mL of dilute hydrochloric acid (1 M) and stir at room temperature for 24 h. Add potassium carbonate until the solution is neutral. After removing the solvent by vacuum distillation, add 100 mL of dichloromethane to dissolve it completely. Filter to remove the salt, collect the filtrate, and remove the solvent by vacuum distillation to obtain the intermediate product SB-5-X.

[0122] Step 6: Under argon protection, SB-5-X and SB-3-Y were dissolved in 100 mL of dry acetonitrile, potassium carbonate was added, and the mixture was stirred at room temperature for 12 h. The salt was quickly removed by filtration, and the filtrate was collected in a reaction flask. The solvent was removed by vacuum distillation, and the product was washed three times with diethyl ether to obtain the intermediate product SB-6-XY.

[0123] Step 7: Dissolve compound S5 and dried compound SB-6-XY in 30 mL of dry toluene under argon atmosphere. After complete dissolution, add 120 μL of Karstedt Catalyst (Karstedt Catalyst, in Xylene, Pt ~2%, this catalyst is a commercial reagent, concentration expressed as Pt ~2%, purchased from Anaiji Chemicals), then heat to 70 °C and stir at 80 °C for 72 h. The molar ratio of compound S5 to compound SB-6-XY is 3.0:1.

[0124] In an optional embodiment of this application, the structure of the amphiphilic BAB triblock polymer is as follows:

[0125] The preparation method is described in Example 2 of this application.

[0126] This application discloses a method for preparing an amphiphilic BAB triblock polymer. The amphiphilic BAB triblock polymer has the structure shown in formula (IIIc):

[0127] The preparation method is as follows:

[0128] Step 1, Preparation of compound S5-2: Under argon protection, compound S2 was added to a Schlenk flask using a pipette, followed by the addition of methylsiloxane S1-2 and DBU as a catalyst, with a molar ratio of S1-2 to S2 of 8:1. DBU was then added via a microsyringe, followed by the addition of dry tetrahydrofuran for dissolution and stirring. The reaction was carried out at 30°C for 72 h. Dimethylchlorosilane and pyridine were then added, and the reaction was carried out at room temperature for 12 h. The molar ratio of compound S3, dimethylchlorosilane, and pyridine was 1:(4–6):(4–6).

[0129] Step 2, Preparation of compound SC-3: Under argon protection, compound SC-1 was dissolved in dry acetonitrile, and 2-methyloxazoline was added at 80°C. The mixture was refluxed at 80°C for 12 h. After cooling to room temperature, potassium carbonate and SC-2 were added, wherein the molar ratio of compound SC-1 to compound 2-methyloxazoline was (3-20):1. The mixture was stirred at room temperature for another 12 h.

[0130] Step 3: Dissolve compound S5-2 and dried compound SC-3 in dry toluene under argon atmosphere. After complete dissolution, add 120 μL of Karstedt Catalyst, then heat to 80 °C and stir at 80 °C for 72 h. The molar ratio of compound S5-2 to compound SC-3 (m = 12) is 3:1.

[0131] In an optional embodiment of this application, the structure of the amphiphilic BAB triblock polymer is PDMS-PEG-PMOXA-PDMS:

[0132] The preparation method is described in Example 3 of this application.

[0133] This application discloses a method for preparing an amphiphilic BAB triblock polymer. The amphiphilic BAB triblock polymer has the structure shown in formula (IIId):

[0134] The preparation method is as follows:

[0135] Step 1, Preparation of compound S5-2: Under argon protection, compound S2 was added to a Schlenk flask using a pipette, followed by the addition of methylsiloxane S1-2 and DBU as a catalyst, with a molar ratio of S1-2 to S2 of 8:1. DBU was then added via a microsyringe, followed by the addition of dry tetrahydrofuran for dissolution and stirring. The reaction was carried out at 30°C for 72 h. Dimethylchlorosilane and pyridine were then added, and the reaction was carried out at room temperature for 12 h. The molar ratio of compound S3, dimethylchlorosilane, and pyridine was 1:(4–6):(4–6).

[0136] Step 2, preparation of compound SD-2: under argon protection, compound SD-1 was dissolved in 100 mL of dry acetonitrile, 2-methyloxazoline was added at 80 °C, and the mixture was refluxed at 80 °C for 12 h. The molar ratio of compound SD-1 to compound 2-methyloxazoline was (3-20):1.

[0137] Step 3: Dissolve compound S5-2 and dried compound SD-2 in dry toluene under argon atmosphere. After complete dissolution, add 120 μL of Karstedt Catalyst, then heat to 80 °C and stir at 80 °C for 72 h. The molar ratio of compound S5-2 to compound SD-2 (m = 12) is 3:1.

[0138] In an optional embodiment of this application, the structure of the amphiphilic BAB triblock polymer is PDMS-PEG-PMOXA-PDMS:

[0139] The preparation method is described in Example 4 of this application, where M = 9 and y = 13.

[0140] The following will explain the solution of this application with reference to embodiments. Those skilled in the art will understand that the following embodiments are for illustrative purposes only and should not be considered as limiting the scope of this application. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0141] Example 1: Synthesis of the triblock polymer PDMS-PEG-PDMS(P1)

[0142] Step 1, Synthesis of PDMS-H prepolymer S3-1:

[0143] Under argon protection, 21 mL of compound S2 (0.956 g / mL, 296.62 g / mol, 67.68 mmol) was added to a Schlenk flask using a pipette, and the flask was sealed with a rubber stopper. Then, 1.5 mL of tert-butylsiloxane S1 (0.76 g / mL, 134.33 g / mol, 8.49 mmol) was added using a syringe, followed by 120 μL of DBU as a catalyst. The molar ratio of compound S1 to compound S2 was 8:1, and the mixture was deoxygenated three times. Next, 76.5 μL of DBU (1.696 g / mL, 150.08 g / mol, 0.86 mmol) was added using a microsyringe, and 100 mL of dry tetrahydrofuran was added to dissolve and stir. The reaction was carried out at 30 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, and methanol (30 mL, 3 times) was added. The methanol phase was removed, and the residual organic phase was collected and removed by rotary evaporation. After vacuum drying at 120℃ for about 8 hours, silanol-terminated PDMS prepolymer S3 was obtained. Its structure and degree of polymerization were determined by integral of the 1H NMR spectrum (see Figure 3).

[0144] 1 H NMR (500MHz, CDCl3) δ3.48 (s, 1H), 0.86 (s, 6.18H), 0.19-0.07 (m, 124.90H), 1 / 124.90=1 / 6nn=21.

[0145] Step 2, Synthesize prepolymer S5-1:

[0146] Dry compound S3 (8 mmol) was dissolved in dry tetrahydrofuran under an argon atmosphere. Dimethylchlorosilane (40 mmol) and pyridine (40 mmol) were added, and the reaction was carried out at room temperature for 12 h. The reaction was confirmed to be complete by 1H NMR spectroscopy. After the reaction was complete, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and methanol (30 mL, 3 times) was added. The methanol phase was removed, the residual organic phase was collected, and the residual methanol was removed by rotary evaporation. The mixture was dried under vacuum at 120 °C for about 8 h to obtain the silane-terminated PDMS prepolymer S5. Its structure and degree of polymerization were determined by 1H NMR integration (see Figure 4), and its GPC chromatogram is shown in Figure 5.

[0147] 1 ¹H NMR (500MHz, CDCl₃) δ 4.72–4.69 (m, 1H), 0.87 (s, 6.95H), 0.18–0.07 (m, 123.01H). The degree of polymerization n was calculated based on the Si-H characteristic peak c: 1 / 123.01 = 1 / 6n, n = 21

[0148] GPC (THF): Mw=1424g / mol, PDI 1.197.

[0149] Step 3, Synthesize prepolymer S8-1:

[0150] Dry NaH (105 mmol) was added under argon protection, followed by 100 mL of tetrahydrofuran. The mixture was cooled and stirred in an ice bath for 15 min. Polyethylene glycol S7-1 (50 mmol) was added dropwise, and the mixture was stirred thoroughly in an ice bath for 30 min. Allyl bromide S6-1 (105 mmol) was added dropwise, and the mixture was slowly heated to room temperature. After reacting for 30 min, the mixture was heated to reflux and stirred overnight. After the reaction was complete, the mixture was cooled to an ice bath, quenched dropwise with deionized water, and the solvent was removed under reduced pressure. The resulting polymer was dried under vacuum to obtain allyl-terminated polyethylene glycol S8-1, the structure of which and its degree of polymerization were determined by integral of 1H NMR spectroscopy (see Figure 6).

[0151] 1 ¹H NMR (500MHz, CDCl₃) δ 5.92–5.83 (m, 2H), 5.26–5.13 (m, 4H), 4.00–3.98 (m, 4H), 3.63–3.57 (m, 38H). Based on characteristic peak b, the values ​​are calculated as follows: 1.97 / 38 = 2 / 4 m, m = 10.

[0152] Step 4, Synthesis of triblock PDMS-PEG-PDMS S9-1:

[0153] Compound S5-1 (2.1 mmol) and dried compound S8-1 (1 mmol) were dissolved in 30 mL of dry toluene under argon atmosphere. After complete dissolution, 120 μL of Karstedt Catalyst (Karstedt Catalyst in Xylene, Pt ~2%, this catalyst is a commercial reagent, concentration expressed as Pt ~2%, purchased from Anaiji Chemical) was added. The temperature was then raised to 70 °C and stirred at 70 °C for 24 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed three times with diethyl ether (10 mL). The product was dissolved in 100 mL of ethanol and purified by percolation through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 1 kDa) with more than 600 mL of ethanol. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain triblock PDMS-PEG-PDMS polymer P. Its structure and degree of polymerization were determined by integral of 1H NMR (see Figure 7), with a yield of 43%. The GPC chromatogram is shown in Figure 8.

[0154] 1¹H NMR (500MHz, CDCl₃) δ 3.80-3.55 (m, 52.66H), 3.43-3.39 (m, 4.42H), 1.65-1.55 (m, 5.30H), 0.90-0.85 (m, 19.39H), 0.53-0.49 (m, 4.00H), 0.18-0.07 (m, 200.63H). Based on the characteristic peak c of Si-CH₂, the degree of polymerization of hydrophobic block PDMS is calculated as follows: n: 4 / 200.63 = 4 / 12n, n = 16.7; the degree of polymerization of hydrophilic block PEG is calculated as follows: m: 4 / 52.66 = 4 / 4m, m = 13.2. Therefore, the polymer Dp is PDMS-PEG-PDMS 17-13-17HLB = 3.7.

[0155] GPC (THF): Mw=2571g / mol, PDI=1.267.

[0156] Example 2: Synthesis of the triblock polymer PDMS-PMOXA-Piperazine-PMOXA-PDMS(P2)

[0157] Step 1, Synthesis of PDMS-H prepolymer S5-2:

[0158] Under argon protection, 21 mL of compound S2 (0.956 g / mL, 296.62 g / mol, 67.68 mmol) was added to a Schlenk flask using a pipette, and the flask was sealed with a rubber stopper. Then, 1.5 mL of methylsiloxane S1-2 (0.76 g / mL, 134.33 g / mol, 8.49 mmol) was added using a syringe, followed by 120 μL of DBU as a catalyst. The molar ratio of compound S1 to compound S2 was 8:1, and the mixture was deoxygenated three times. Next, 76.5 μL of DBU (1.696 g / mL, 150.08 g / mol, 0.86 mmol) was added using a microsyringe, and 100 mL of dry tetrahydrofuran was added and stirred. The reaction was carried out at 30 °C for 72 h. Then, dimethylchlorosilane (40 mmol) and pyridine (40 mmol) were added, and the reaction was carried out at room temperature for 12 h. The reaction was confirmed to be complete by 1H NMR spectroscopy. After the reaction was complete, the mixture was cooled to room temperature, the solvent was removed under reduced pressure, and methanol (30 mL, 3 times) was added. The methanol phase was removed, the residual organic phase was collected, and the residual methanol was removed by rotary evaporation. The mixture was dried under vacuum at 120 °C for about 8 h to obtain the silane-terminated PDMS prepolymer S5, a colorless and transparent liquid with a yield of 95%. Its structure and degree of polymerization were determined by integral of 1H NMR spectroscopy (see Figure 9). The GPC chromatogram is shown in Figure 10.

[0159] 1H NMR (500MHz, CDCl3) δ4.80-4.60 (m, 1H), 0.25-0.00 (m, 84.28H), 1 / 84.28=1 / 6n n=14.

[0160] GPC(DMF): 1.101.

[0161] Step 2, Synthesis of prepolymer SB-2:

[0162] Under argon protection, p-toluenesulfonic acid and silver oxide were added to dry acetonitrile and stirred thoroughly for 30 mins. The salt was quickly removed by filtration, and the filtrate was collected in a reaction flask. Allyl bromide SB-1 was added, and the mixture was stirred at 70 °C for 16 h. After removing the solvent by vacuum distillation, the product was purified by silica gel chromatography to obtain the intermediate product SB-2, a pale yellow liquid with a yield of 65%. Its structure was determined by 1H NMR spectroscopy (see Figure 11).

[0163] 1 H NMR (500MHz, CDCl3) δ7.88-7.70(m,2H),7.45-7.30(m,2H),5.90-5.70(m,1H),5.45-5.10(m,2H),4.62-4.40(m,2H),2.45(s,3H).

[0164] Step 3: Synthesize prepolymer SB-3-6

[0165] Under argon protection, SB-2 (10 mmol) was dissolved in 100 mL of dry acetonitrile, and 2-methyloxazoline (6 eq. 60 mmol) was added at 80 °C. The mixture was refluxed at 80 °C for 12 h. After removing the solvent by vacuum distillation, the intermediate product SB-3-6 was obtained. Its structure and degree of polymerization were determined by integrating the 1H NMR spectrum (see Figure 12).

[0166] 1 H NMR (500MHz, CDCl3) δ7.80-7.66(m,2H),7.31-7.21(m,2H),6.00-5.75(m,1H ),4.10-3.40(m,23.17H),2.39(s,3H),2.25-2.00(m,18.40H).x=18.40 / 3=6.

[0167] Step 4: Synthesize prepolymer SB-4-6

[0168] Under argon protection, SB-3-6 was dissolved in 100 mL of dry acetonitrile, and B℃-piperazine and potassium carbonate were added. The mixture was stirred at room temperature for 12 h. The salt was quickly removed by filtration, and the filtrate was collected in a reaction flask. The solvent was removed by vacuum distillation, and the residue was washed three times with diethyl ether to remove the residual piperazine, yielding the intermediate product SB-4-6. Its structure and degree of polymerization were determined by integrating the 1H NMR spectrum (see Figure 13).

[0169] 1 H NMR(500MHz, CDCl3)δ6.00-5.75(m,1H),5.40-5.10(m,2H),3.75-3.40(m,30.25H), 3.38-3.24(m,14.62H),2.90-2.45(m,8.88H),2.25-2.00(m,18.83H).x=18.83 / 3=6.

[0170] Step 5: Synthesize prepolymer SB-5-6

[0171] SB-4-X was dissolved in 40 mL of dilute hydrochloric acid (1 M) and stirred at room temperature for 24 h. Potassium carbonate was added until the solution was neutral. After removing the solvent by vacuum distillation, 100 mL of dichloromethane was added to dissolve the solvent completely. The salt was removed by filtration, and the filtrate was collected and the solvent was removed by vacuum distillation to obtain the intermediate product SB-5-X. Its structure and degree of polymerization were determined by integrating the 1H NMR spectrum, as shown in Figure 14.

[0172] 1 H NMR (500MHz, CDCl3) δ6.00-5.75(m,1H),5.40-5.10(m,2H),3.80-3.40(m,32.52H),2.90-2.45(m,7.05H),2.25-2.00(m,22.53H).x=22.53 / 3=7.5.

[0173] Step 6: Synthesize prepolymer SB-6-XY

[0174] Under argon protection, SB-5-6 and SB-3-6 were dissolved in 100 mL of dry acetonitrile, potassium carbonate was added, and the mixture was stirred at room temperature for 12 h. The salt was quickly removed by filtration, and the filtrate was collected in a reaction flask. The solvent was removed by vacuum distillation, and the product was washed three times with diethyl ether to obtain the intermediate product SB-6-XY. Its structure and degree of polymerization were determined by integrating the 1H NMR spectrum, as shown in Figure 15.

[0175] 1H NMR(500MHz, CDCl3)δ6.00-5.75(m,2H),5.40-5.10(m,4H),4.10-3.90(m,4H),3.80 -3.40(m,48.33H),2.90-2.45(m,9.23H),2.25-2.00(m,36.81H).x=y=34.55 / 6*2=6.

[0176] Step 7: Synthesis of the triblock polymer PDMS-PMOXA-Piperazine-PMOXA-PDMS(P2)

[0177] Compound S5-2 and dried compound SB-6-6-6 were dissolved in 30 mL of dry toluene under argon atmosphere. After complete dissolution, 120 μL of Karstedt Catalyst (Karstedt Catalyst, in Xylene, Pt ~2%, this catalyst is a commercial reagent, concentration expressed as Pt ~2%, purchased from Anaiji Chemicals) was added. The mixture was then heated to 70 °C and stirred at 80 °C for 72 h. The molar ratio of compound S5-2 to compound SB-6-XY (X=Y=6, n=14) was 3:1. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed three times with chloroform (10 mL). The solvent was removed by vacuum distillation to obtain a yellow solid crude product. The crude product was dissolved in 30 ml of ethanol and purified by percolation with more than 600 ml of ethanol (through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 2 kDa) for 5 days. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain the triblock PDMS-PMOXA-Piperazine-PMOXA-PDMS polymer P2. Its structure and degree of polymerization were determined by integral of 1H NMR (see Figure 16), with a yield of 35%. The GPC chromatogram is shown in Figure 17.

[0178] 1 H NMR (500MHz, CDCl3) δ4.10-3.20(m,46.38H),2.25-2.00(m,33.92H),0.55-0.40(m,1.18H),0.25--0.3(m,156.00H).x=y=34.90 / 6=5.7.

[0179] GPC (THF): Mw=2084g / mol, PD=1.181.

[0180] Example 3: Synthesis method of PDMS-PEG-PMOXA-PDMS

[0181] Step 1: Synthesize PDMS-H prepolymer S5-2. For details, please refer to Step 1 of Example 2.

[0182] Step 2, Synthesize prepolymer SC-3:

[0183] Under argon protection, compound SC-1 (2.24 g, 10 mmol) was dissolved in 100 mL of dry acetonitrile. 2-Methyloxazoline (12 eq. 120 mmol) was added at 80 °C, and the mixture was refluxed at 80 °C for 12 h. After cooling to room temperature, potassium carbonate (3 eq. 30 mmol) and SC-2 (3 eq. 30 mmol) were added. The mixture was stirred at room temperature for another 12 h. Inorganic salts were removed by filtration, and the solvent was removed by vacuum distillation to obtain the intermediate product SC-3. Its structure and degree of polymerization were determined by integrating the 1H NMR spectrum (see Figure 18).

[0184] 1 ¹H NMR (500MHz, CDCl₃) δ 3.65–3.40 (m, 44.82H), 2.55–2.45 (m, 1H), 2.37–2.30 (m, 4H), 2.25–2.20 (m, 2H), 2.20–2.00 (m, 32.72H). Degree of polymerization calculation: m = 32.72 / ³ = 11.

[0185] Step 3: Synthesis of the triblock polymer PDMS-PEG-PMOXA-PDMS(P3)

[0186] Compound S5-2 and dried compound SC-3 were dissolved in 30 mL of dry toluene under argon atmosphere. After complete dissolution, 120 μL of Karstedt Catalyst (Karstedt Catalyst, in Xylene, Pt ~2%, this catalyst is a commercial reagent, concentration expressed as Pt ~2%, purchased from Anaiji Chemicals) was added, and the mixture was heated to 80 °C and stirred at 80 °C for 72 h. The molar ratio of compound S5-2 to compound SC-3 (m = 12) was 3:1. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed three times with chloroform (10 mL). The solvent was removed by vacuum distillation to obtain a yellow solid crude product. The crude product was dissolved in 30 ml of ethanol and purified by percolation with more than 600 ml of ethanol (through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 2 kDa) for 5 days. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain the triblock PDMS-PEG-PMOXA-PDMS polymer P3. Its structure and degree of polymerization were determined by integral of 1H NMR (see Figure 19), with a yield of 60%. The GPC chromatogram is shown in Figure 20.

[0187] 1 H NMR (500MHz, CDCl3) δ 6.25-6.0 (m, 2H), 5.75-5.50 (m, 4H), 3.75-3.25 (m, 27.40H), 2.25-1.99(m,24.79H),0.55-0.40(m,1.44H),0.20-0.00(m,156H.m=24.79 / 6=8.Dp 13-8-13.

[0188] GPC (DMF): Mw=2245g / mol, PD=1.352.

[0189] Example 4: Synthesis method of PDMS-PMOXA-PDMS

[0190] Step 1: Synthesize PDMS-H prepolymer S5-2. For details, please refer to Step 1 of Example 2.

[0191] Step 2, Synthesis of prepolymer SD-2:

[0192] Under argon protection, SD-1 (10 mmol) was dissolved in 100 mL of dry acetonitrile, and 2-methyloxazoline (12 eq. 120 mmol) was added at 80 °C. The mixture was then refluxed at 80 °C for 12 h. After removing the solvent by vacuum distillation, the intermediate product SD-2 was obtained. Its structure and degree of polymerization were determined by integrating the 1H NMR spectrum (see Figure 20).

[0193] 1 H NMR (500MHz, CDCl3) δ5.93-5.78(m,1H),5.26-5.10(m,2H),3.75-3.40(m,27.50H) ,3.05-2.95(m,2H),2.85-2.75(m,2H),2.65-2.30(m,8H),2.20-1.95(m,27.86H).

[0194] Degree of polymerization calculation: m = 27.86 / 3 = 9.

[0195] Step 3: Synthesis of the triblock polymer PDMS-PMOXA-PDMS(P4)

[0196] Compound S5-2 and dried compound SD-2 were dissolved in 30 mL of dry toluene under argon atmosphere. After complete dissolution, 120 μL of Karstedt Catalyst (Karstedt Catalyst, in Xylene, Pt ~2%, this catalyst is a commercial reagent, concentration expressed as Pt ~2%, purchased from Anaiji Chemicals) was added, and the mixture was heated to 80 °C and stirred at 80 °C for 72 h. The molar ratio of compound S5-2 to compound SD-2 (m = 12) was 3:1. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the solid was washed three times with chloroform (10 mL). The solvent was removed by vacuum distillation to obtain a yellow solid crude product. The crude product was dissolved in 30 ml of ethanol and purified by percolation with more than 600 ml of ethanol (through a regenerated cellulose membrane (Millipore, molecular weight cutoff of 2 kDa) for 5 days. The solvent was removed under reduced pressure, and the resulting polymer was dried under vacuum to obtain the triblock PDMS-PMOXA-PDMS polymer P4. Its structure and degree of polymerization were determined by integral of 1H NMR spectroscopy (see Figure 22), with a yield of 40%. The molecular weight was characterized by GPC chromatogram, as shown in Figure 23.

[0197] 1 ¹H NMR (500MHz, CDCl₃) δ 6.25-5.50 (m, 2H), 3.75-3.25 (m, 33.71H), 2.50-2.25 (m, 10H), 2.25-1.99 (m, 27.14H). Calculation of hydrophilic block polymerization degree: y = 27.14 / 6 = 9. Dp 13-9-13.

[0198] GPC (THF): Mw=2339g / mol, PD 1.305.

[0199] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to specific features, structures, materials, or characteristics described in connection with that embodiment or example, which are included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0200] Although embodiments of this application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting this application. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of this application.

Claims

1. A method for preparing amphiphilic BAB triblock polymers, characterized in that, include: Using Karstedt as a catalyst, the compound shown in formula (I) and the compound shown in formula (II) were subjected to an addition reaction to obtain the amphiphilic BAB triblock polymer; wherein: The structure of the compound shown in formula (I) is as follows: The structure of the compound shown in formula (II) is as follows: Each R1 is independently selected from C 1～6 Alkyl groups, or 6- to 10-membered aromatic groups; R2 is selected from C 1～6 Alkyl groups, or 6- to 10-membered aromatic groups; R3 is selected from -R 3a - or -R 3a -LR 3b -, where each R 3a Each group is independently selected from polyamide-imide (PAI) groups. Polyoxyalkylene oxide (POXA) L is selected from -O-, Each R 3b Each is independently selected from H or C. 1～6 Alkyl groups, each x being independently selected from 3 to 15; R4 is selected from Each R6 is independently selected from C 1～6 Alkyl groups, or 6- to 10-membered aromatic groups; Each R7 is independently selected from C 1～6 alkyl; Each R8 is independently selected from C 1～6 Alkyl or acetyl groups; Each R9 is independently selected from C 1～6 Alkylene; n is any integer between 20 and 40; m is selected from any integer between 3 and 12; q is selected from integers between 0 and 10.

2. The method according to claim 1, characterized in that, The amphiphilic BAB triblock polymer has the structure shown in Formula III: R5 is selected from C 2～10 Alkylene Each R6 is independently selected from C 1～6 Alkyl groups, 6- to 10-membered aromatic groups; Each R7 is independently selected from C 1～6 alkyl; Each R8 is independently selected from C 1～6 Alkyl, acetyl; Each R9 is independently selected from C 1～6 Alkylene.

3. The method according to any one of claims 1 to 2, characterized in that, R3 is selected from polyamide-imide (PAI) and polyoxyalkylene (POXA).

4. The method according to claim 1, characterized in that, The method includes one or more of the following conditions: 1) The molar ratio of the compound shown in formula (I) to the compound shown in formula (II) is (1.8–2.5):1; 2) The temperature of the addition reaction is 60℃~80℃; 3) The addition reaction takes place over a period of 20 to 30 hours; 4) The solvent in the addition reaction is selected from at least one of toluene, tetrahydrofuran, and DMF.

5. The method according to claim 1, characterized in that, The compound represented by formula (I) was obtained in the following manner: S1. The compound shown in formula (Ia) is reacted with the compound shown in formula (Ib) to obtain the compound shown in formula (Ic); S2. The compound shown in formula (Ic) is subjected to a halogenation reaction with the compound shown in formula (Id) to obtain the compound shown in formula (I); 6. The method according to claim 5, characterized in that, The method includes one or more of the following conditions: 1) The first reaction was carried out under DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) conditions; 2) The molar ratio of the compound shown in formula (Ia) to the compound shown in formula (Ib) is (5-10):1; 3) The temperature of the first reaction is 25℃~35℃; 4) The reaction time for the first reaction is 60-80 hours; 5) The solvent in the first reaction is selected from tetrahydrofuran; 6) The acid-binding agent in the halogenation reaction is selected from pyridine; 7) The molar ratio of the compound shown in formula (Ic) to the compound shown in formula (Id) is 1:(3-8).

7. The method according to claim 1, characterized in that, The compound represented by formula (II) is obtained by the following method: Under inert gas conditions, compound 1 and compound 2 were subjected to a capping reaction to obtain the compound shown in formula (II); Compound 1 is selected from polyethylene glycol (PEG), polyoxazoline (POXA), polyethylene oxide (PEO), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), polyacrylamide (PAM), polymethyl methacrylate (PMMA), poly(N,N-dimethylacrylamide) (PDMA), polyalkylene imide (PAI), and polyhydroxyalkyl acrylate (PHPMA). Compound 2 is selected from 8. The method according to claim 7, characterized in that, The method includes one or more of the following conditions: 1) The molar ratio of compound 1 to compound 2 is 1:(1.5–2.5); 2) The capping reaction is carried out under strong alkaline solution conditions; 3) The solvent for the end-capping reaction is selected from at least one of tetrahydrofuran and diethyl ether.

9. The method according to claim 8, characterized in that, The strong alkaline solution is selected from NaH.

10. An amphiphilic BAB triblock polymer, characterized in that, It is prepared by the method described in any one of claims 1-9.

11. Use of the amphiphilic BAB triblock polymer prepared according to any one of claims 1-9 or the amphiphilic BAB triblock polymer according to claim 9 in the preparation of vesicles or biomimetic membranes.

12. A vesicle, wherein, The vesicles comprise an amphiphilic BAB triblock polymer prepared according to the method of any one of claims 1-9 or the amphiphilic BAB triblock polymer of claim 10.

13. A biomimetic membrane, wherein, The biomimetic membrane comprises an amphiphilic BAB triblock polymer prepared according to the method of any one of claims 1-9 or the amphiphilic BAB triblock polymer of claim 10.

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