Preparation method of precise miktoarm star polymer forming close packing spherical phase

Abstract

The invention provides a preparation method of an accurate miktoarm star polymer for forming a close packing spherical phase, and belongs to the technical field of high polymer materials. Based on an iterative growth method and a modular synthesis strategy, a series of discrete miktoarm star-shaped polymer libraries which have accurate chemical structures and single molecular weight and are based on polyhedral oligomeric silsesquioxane (POSS) are constructed; the miktoarm star polymer can form a hexagonal close packed spherical phase (HCP) with stable thermodynamics in the body self-assembly process. A series of isomerism polymers are designed for specific molecular parameters (such as volume fraction, topological structure, regional configuration and block number) to eliminate interference of other variables, and an ideal platform is provided for quantitatively researching the function of the molecular parameters in the self-assembly process. According to the method, the difference between experimental exploration and theoretical research can be bridged, the basic principle of self-assembly of the block copolymer can be deeply understood, and guidance is provided for reasonable design of novel functional polymer materials.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a method for preparing a precise hetero-arm star polymer that forms a densely packed spherical phase. Background Art

[0002] Block copolymers can spontaneously form various periodic structures at the nanoscale and have a wide range of applications in many fields. It is generally believed that the self-assembly behavior of linear block copolymers follows general principles and depends mainly on three variables: degree of polymerization (N), composition (f) and Flory-Huggins interaction parameter (χ). By adjusting these molecular parameters, classical phase structures such as lamellar phase (LAM), bicontinuous phase (DG), hexagonal columnar phase (HEX) and body-centered cubic spheroidal phase (BCC) can be easily obtained. The unconventional spheroidal phases discovered so far, including Frank-Kasper phase and quasicrystalline phase, have greatly expanded the diversity of nanostructures and stimulated research interest in this field. Despite the exciting progress, there is still a missing piece of the puzzle in the phase diagram of block copolymers. Classical phase theory predicts the existence of thermodynamically stable close-packed spherical phases (CPS) in a very narrow region near the order-disorder phase boundary, namely hexagonal close packing (HCP) and face-centered cubic packing (FCC). However, the CPS phase has not been directly observed in strictly single-component block copolymers in experiments, which makes people doubt the basic principles developed from ideal and uniform systems. At the same time, unlike the assumption that block copolymers have uniform chain lengths in theoretical calculations, the objects of experimental research are usually multi-component mixtures with a certain degree of dispersion. The existence of dispersion will not only cause inconsistencies between theory and experiment, affecting the understanding of the intrinsic mechanism of the self-assembly process, but will also be coupled with other variables, bringing great trouble to given quantitative research. However, due to the difficulty in preparing structurally precise samples, experimental research and verification of the formation of the above structures are relatively lacking. Summary of the invention

[0003] In order to solve the above technical problems, the present invention provides a method for preparing a precise hetero-arm star polymer that forms a densely packed spherical phase, and prepares POSS cores with different hydroxyl substitutions (VPOSS-OH, VPOSS-(OH)2, para-, meta-, ortho-VPOSS-2OH) by a "core-first" strategy. Then, discrete oligomeric lactic acid (oLA) is prepared by an iterative growth method. n , L) and oligodimethylsiloxane (oDMS m On this basis, oLA and oDMS homopolymers were grafted onto the POSS core using an efficient coupling reaction to obtain a series of discrete hetero-arm star polymers with precise structures.m -POSS-oLA n ), [7:2] hetero-arm star polymers of different symmetries (7oDMS m -POSS-oLA n1 / oLA n2 ) and [6:2] hetero-arm star polymers with different regio-configurations (para-, meta-, ortho-6oDMS m -POSS-oLA n1 / oLA n2 ). The study of the self-assembly of star polymers found that with the increase of oLA volume fraction, a transition from disordered phase to hexagonal columnar phase (HEX) and spherical phase (A15 and HCP) was observed. It is exciting that the phase difference of HCP phase reaches 0.19 to 0.39 (0.19 <f oLA <0.39). In addition, we also found that this hetero-arm star polymer with POSS as the core is a universal structure for forming HCP phases, and replacing polylactic acid with polyphenyllactic acid (oPL) blocks can also form stable HCP phases.

[0004] In the first aspect, the present invention provides a hetero-arm star polymer 7oDMS m -POSS-oLA n The preparation method comprises the following preparation steps:

[0005] VPOSS-OH、TBDMS-oLA n -COOH and dimethylaminopyridine toluenesulfonate (DPTS) are dissolved in 4-6 mL dry dichloromethane, and then slowly added with 1,3-diisopropylcarbodiimide (DIC) after cooling to 0-5°C. After reacting for 20-28 hours, the solvent is removed; then toluene is added to dissolve, filtered, and rotary dried to obtain a crude product; the crude product is purified by preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n ;

[0006] VPOSS-oLA n and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule.

[0007] 7oDMS m -POSS-oLA n ;

[0008] VPOSS-OH, TBDMS-L in S01 nThe molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8;

[0009] The VPOSS-L n and oDMS m The molar ratio is 1:11-15;

[0010] The n is 28≤n≤64, and takes a value every 4; m is 5, 9, or 13.

[0011] In a second aspect, the present invention provides a hetero-arm star polymer 7oDMS m -POSS-2oLA n The preparation method comprises the following preparation steps:

[0012] VPOSS-OH, hydroxyl-protected 2,2-bis(hydroxymethyl)propionic acid and DPTS were dissolved in dry 8-10 mL dichloromethane, cooled to 0-5°C and then slowly added with DIC to react for 20-28 hours. After the reaction was completed, the crude product was filtered and the solvent was removed to obtain a crude product. The crude product was separated in a fast liquid preparative chromatograph, and the intermediate product obtained after separation and purification was dissolved in methanol and added Carry out the deprotection reaction of hydroxyl group for 5-7h; after the reaction is completed, filter the remaining And VPOSS-(OH)2 was separated and purified by rapid liquid preparative chromatography;

[0013] VPOSS-(OH)2、TBDMS-L n -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Then toluene was added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-2oLA n ;

[0014] VPOSS-2oLA n and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule.

[0015] 7oDMS m -POSS-2oLA n ;

[0016] The molar ratio of the VPOSS-OH, hydroxyl-protected 2,2-bis(hydroxymethyl)propionic acid, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8;

[0017] The VPOSS-(OH)2, TBDMS-L n The molar ratio of -COOH, DPTS, and DIC is 1:2.5-3.0:0.1-0.5:2.5-3.0;

[0018] The VPOSS-2oLA n and oDMS m The molar ratio is 1:11-15;

[0019] The n is 20, 24, 28; and m is 13.

[0020] In a third aspect, the present invention provides a hetero-arm star polymer 7oDMS m -POSS-oLA n1 / oLA n2 The preparation method comprises the following preparation steps:

[0021] VPOSS-(OH)2、TBDMS-L n1 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified using preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n1 (-OH);

[0022] VPOSS-oLA n1 (-OH), TBDMS-L n2 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified using preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n1 / oLA n2 ;

[0023] VPOSS-oLA n1 / oLA n2 and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule 7oDMSm -POSS-oLA n1 / oLA n2 ;

[0024] The VPOSS-(OH)2, TBDMS-L n1 The molar ratio of -COOH, DPTS, and DIC is 1: 0.8-1.2: 0.1-0.5: 1.5-1.8;

[0025] The VPOSS-oLA n1 (-OH), TBDMS-L n2 The molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8;

[0026] The VPOSS-oLA n1 / oLA n2 and oDMS m The molar ratio is 1:11-15;

[0027] The n1+n2=40, 48, 56; when n1+n2=40, n1=8, 12, 16; when n1+n2=48, n1=8, 12, 16, 20; when n1+n2=56, n1=8, 12, 16, 20, 24; m is 13.

[0028] In a fourth aspect, the present invention provides a hetero-arm star polymer 6oDMS m -POSS-2oLA n The preparation method comprises the following preparation steps:

[0029] VPOSS-2OH, TBDMS-oLA n -COOH and DPTS were added to 3-5 mL of dry dichloromethane, stirred and dissolved, and then cooled to 0-5 ° C, and then DIC was slowly added and stirred at room temperature for 6-10 hours. After the reaction was completed, the solvent was removed and toluene was added to dissolve, filtered, and rotary dried to obtain a crude product, which was then purified by preparative gel permeation chromatography to obtain VPOSS-2oLA n ;

[0030] VPOSS-2oLA was prepared under argon atmosphere. n and oDMS m Add 3-5 mL of anhydrous toluene and stir to dissolve, then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is completed, remove the solvent and purify by preparative gel permeation chromatography to obtain 6oDMS. m -POSS-2oLA n .

[0031] The VPOSS-2OH, TBDMS-oLA n The molar ratio of -COOH, DPTS, and DIC is 1:2.5-3.0:0.1-0.5:2.5-3;

[0032] The VPOSS-2oLA n and oDMS m The molar ratio is 1:11-15;

[0033] The regional configurations of the VPOSS-2OH are para-, meta- and ortho-configurations.

[0034] The n is 24, 28, 32, and the m is 5, 9, 13.

[0035] In a fifth aspect, the present invention provides a hetero-arm star polymer ortho-6oDMS m -POSS-oLA n1 / oLA n2 The preparation method comprises the following preparation steps:

[0036] ortho-VPOSS-2OH, TBDMS-L n1 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 (-OH);

[0037] ortho-VPOSS-oLA n1 (-OH), TBDMS-L n2 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 / oLA n2 ;

[0038] ortho-VPOSS-oLA n1 / oLA n2 and oDMS mDissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule ortho-6oDMS m -POSS-oLA n1 / oLA n2 ;

[0039] The ortho-VPOSS-2OH, TBDMS-L n1 The molar ratio of -COOH, DPTS, and DIC is 1: 0.8-1.2: 0.1-0.5: 1.5-1.8;

[0040] The ortho-VPOSS-oLA n1 (-OH), TBDMS-L n2 The molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8;

[0041] The ortho-VPOSS-oLA n1 / oLA n2 and oDMS m The molar ratio is 1:11-15;

[0042] The n1+n2=48, 56; when n1+n2=48, n1=4, 8, 12, 16, 20; when n1+n2=56, n1=4, 8, 12, 16, 20, 24; m is 13.

[0043] In a sixth aspect, the present invention provides a hetero-arm star polymer 7oDMS m -POSS-oPL n The preparation method comprises the following preparation steps:

[0044] VPOSS-OH、TBDMS-oPL n -COOH and DPTS were dissolved in 4-6 mL dry dichloromethane, cooled to 0-5 °C, and then 1,3-diisopropylcarbodiimide (DIC) was slowly added. After the reaction was continued for 20-28 hours, the solvent was removed. Then toluene was added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-oPL n ;

[0045] VPOSS-oPL n and oDMS mDissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule.

[0046] 7oDMS m -POSS-oPL n ;

[0047] The VPOSS-OH, TBDMS-oPL n The molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8;

[0048] The VPOSS-P n and oDMS m The molar ratio is 1:11-15;

[0049] The n is 28, 32, 36; and m is 13.

[0050] The beneficial effects of the present invention include at least:

[0051] (1) The present invention successfully synthesized a series of discrete hetero-arm star polymers with precise chemical structures and single molecular weights, providing an efficient and novel synthesis method for the precise construction of block copolymers with high scalability.

[0052] (2) All copolymers involved in the present invention have precise composition and uniform chain length, eliminating the composition uncertainty caused by traditional polymerization methods. Through the precise adjustment of special molecular parameters, hetero-arm star polymers with different symmetries, different topological structures and different regional configurations are obtained. A series of isomeric polymers are designed for specific molecular parameters to eliminate the interference of other variables, providing an ideal platform for quantitatively studying the role of the molecular parameters in the self-assembly process.

[0053] (3) In the present invention, the arm-shaped star polymer with inorganic nanoparticles (polyhedral oligomeric silsesquioxane, POSS) as the core can self-assemble to form a stable hexagonal close-packed spherical phase, and the phase range reaches 0.19 to 0.39 (0.19 <f oLA <0.39).

[0054] (4) In the present invention, the hetero-arm star polymer with POSS as the core is a universal structure for forming an HCP phase. Replacing polylactic acid with other hydrophobic blocks can also form a stable HCP phase. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] Figure 1 [7:1] hetero-arm star polymer 7oDMSm -POSS-oLA n Synthesis route map.

[0056] Figure 2 [7:2] hetero-arm star polymer 7oDMS m -POSS-2oLA n Synthesis route map.

[0057] Figure 3 [7:2] hetero-arm star polymer 7oDMS m -POSS-oLA n1 / oLA n2 Synthesis route map.

[0058] Figure 4 [6:2] hetero-arm star polymer 6oDMS with different regional configurations m -POSS-2oLA n Synthesis route map.

[0059] Figure 5 [6:2] hetero-arm star polymer ortho-6oDMS m -POSS-oLA n1 / oLA n2 Synthesis route map.

[0060] Figure 6 [7:1] hetero-arm star polymer 7oDMS m -POSS-oPL n Synthesis route map.

[0061] Figure 7 The precursor VPOSS-oLA prepared in Example 1 n of 1 H NMR characterization chart (a), MALDI-ToF-MS characterization chart (b) and SEC characterization chart (c).

[0062] Figure 8 The hetero-arm star polymer 7oDMS5-POSS-oLA prepared in Example 2 n MALDI-ToF-MS characterization diagram (a) and SEC characterization diagram (b).

[0063] Fig. 9 The [7:1] hetero-arm star polymer 7oDMS prepared in Examples 2, 3, and 4 m -POSS-oLA n Small angle X-ray scattering (SAXS) pattern.

[0064] Fig.10The precursor VPOSS-2oLA prepared in Example 6 n of 1 H NMR characterization chart (a), MALDI-ToF-MS characterization chart (b) and SEC characterization chart (c).

[0065] Fig.11 The [6:2] hetero-arm star polymer 6oDMS prepared in Example 11 13 -POSS-2oLA n SAXS characterization diagram.

[0066] Fig.12 The [6:2] hetero-arm star polymer ortho-6oDMS prepared in Example 12 13 -POSS-oLA n1 / oLA n2 SAXS characterization diagram.

[0067] Fig.13 The hetero-arm star polymer 7oDMS prepared in Example 13 13 -POSS-oPL 32 SAXS characterization diagram.

[0068] Fig.14 A comprehensive schematic diagram of hetero-arm star polymers. DETAILED DESCRIPTION

[0069] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0070] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0071] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0072] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present application description and examples are exemplary only.

[0073] The terms "include", "including", "have", "contain", etc. used in this article are open-ended terms, which mean including but not limited to; room temperature refers to 25±2°C; all raw materials used are commercially available unless otherwise specified.

[0074] In the following embodiments, the value of n is one or more of 28, 32, 36, 40, 44, 48, and 56; the methods described in each embodiment are used for synthesis and detection, and details are shown in the corresponding drawings of each embodiment.

[0075] Example 1

[0076] VPOSS-oLA n Synthesis

[0077] VPOSS-OH (200 mg, 0.28 mmol), TBDMS-L n -COOH (0.42mmol, 1.5eq) and dimethylaminopyridine toluenesulfonate (DPTS, 41mg, 0.14mmol, 0.5eq) were dissolved in 5mL dry dichloromethane, and then slowly added with 1,3-diisopropylcarbodiimide (DIC, 53mg, 0.42mmol, 1.5eq) after cooling to 0°C. After 24h of reaction, the solvent was removed; then toluene was added to dissolve, filtered, and rotary dried to obtain a crude product; the crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-L n .

[0078] Example 2

[0079] 7oDMS5-POSS-oLA n Synthesis

[0080] VPOSS-L n (0.049mmol) and oDMS5 (300mg, 0.69mmol, 14eq) were dissolved in 3mL dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS5-POSS-oLA n ;

[0081] Example 3

[0082] 7oDMS9-POSS-oLA n Synthesis

[0083] VPOSS-L n (0.049mmol) and oDMS9 (503mg, 0.69mmol, 14eq) were dissolved in 3mL dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS9-POSS-oLA n ;

[0084] Example 4

[0085] 7oDMS 13 -POSS-oLA n Synthesis

[0086] VPOSS-L n (0.049mmol) and oDMS 13 (708 mg, 0.69 mmol, 14 eq) was dissolved in 3 mL of dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS 13 -POSS-oLA n ;

[0087] Example 5

[0088] Synthesis of VPOSS-(OH)2

[0089] VPOSS-OH (5.0 g, 7 mmol), hydroxyl-protected 2,2-bis(hydroxymethyl)propionic acid (1.83 g, 10.5 mmol, 1.5 eq) and DPTS (1.03 g, 3.5 mmol, 0.5 eq) were dissolved in 8 mL of dry dichloromethane, cooled to 0°C and slowly added with DIC (1.33 g, 10.5 mmol, 1.5 eq) and reacted for 24 h. After the reaction was completed, the crude product was filtered and the solvent was removed to obtain a crude product. The crude product was separated in a fast liquid preparative chromatograph, and the intermediate product obtained after separation and purification was dissolved in methanol and added Carry out the deprotection reaction of hydroxyl group for 6h; after the reaction is completed, filter the remaining And VPOSS-(OH)2 was separated and purified by rapid liquid preparative chromatography;

[0090] Example 6

[0091] VPOSS-2oLA n Synthesis

[0092] Combine VPOSS-(OH)2 (99mg, 0.12mmol), TBDMS-L n -COOH (0.36mmol, 3eq) and DPTS (18mg, 0.06mmol, 0.5eq) were dissolved in 8mL dry dichloromethane, cooled to 0°C and then slowly added with DIC (45mg, 0.36mmol, 3eq). After 24h of reaction, the solvent was removed; then toluene was added to dissolve, filtered and rotary dried to obtain a crude product; the crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-2oLA n ;

[0093] Example 7

[0094] 7oDMS5-POSS-2oLA n Synthesis

[0095] VPOSS-2oLA n (0.02mmol) and oDMS5 (121mg, 0.28mmol, 14eq) were dissolved in 3mL dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS5-POSS-oLA n ;

[0096] Example 8

[0097] 7oDMS9-POSS-2oLA n Synthesis

[0098] VPOSS-2oLA n (0.02mmol) and oDMS9 (204mg, 0.28mmol, 14eq) were dissolved in 3mL dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS9-POSS-oLA n ;

[0099] Example 9

[0100] 7oDMS 13 -POSS-2oLA n Synthesis

[0101] VPOSS-2oLA n(0.02mmol) and oDMS 13 (287 mg, 0.28 mmol, 14 eq) was dissolved in 3 mL of dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS 13 -POSS-oLA n ;

[0102] Example 10

[0103] 7oDMS 13 -POSS-oLA n1 / oLA n2 Synthesis

[0104] VPOSS-(OH)2 (496 mg, 0.6 mmol), TBDMS-L n1 -COOH (0.6mmol, 1eq) and DPTS (88mg, 0.3mmol, 0.5eq) were dissolved in 8mL dry dichloromethane, cooled to 0°C and slowly added with DIC (76mg, 0.6mmol, 1eq). After 24h of reaction, the solvent was removed; then toluene was added to dissolve, filtered and rotary dried to obtain a crude product; the crude product was purified by preparative gel permeation chromatography to obtain the intermediate product VPOSS-oLA n1 (-OH);

[0105] VPOSS-oLA n1 (-OH)(0.6mmol), TBDMS-L n2 -COOH (0.9mmol, 1.5eq) and DPTS (88mg, 0.3mmol, 0.5eq) were dissolved in 8mL dry dichloromethane, cooled to 0°C and then slowly added with DIC (114mg, 0.9mmol, 1.5eq). After 24h of reaction, the solvent was removed; then toluene was added to dissolve, filtered, and rotary dried to obtain a crude product; the crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n1 / oLA n2 ;

[0106] VPOSS-oLA n1 / oLA n2 (0.05mmol) and oDMS 13(770 mg, 0.75 mmol, 15 eq) was dissolved in 3 mL of dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS 13 -POSS-oLA n1 / oLA n2 ;

[0107] Embodiment 11

[0108] 6oDMS 13 -POSS-2oLA n Synthesis

[0109] VPOSS-2OH (para-, meta-, ortho-, 300 mg, 0.38 mmol), TBDMS-oLA n -COOH (0.98 mmol, 2.5 eq) and DPTS (56 mg, 0.19 mmol, 0.5 eq) were added to 5 mL of dry dichloromethane and stirred to dissolve, then cooled to 0°C, and then DIC (123 mg, 0.98 mmol, 2.5 eq) was slowly added and stirred at room temperature for 8 hours. After the reaction was completed, the solvent was removed and toluene was added to dissolve, filtered, and rotary dried to obtain a crude product, which was then purified by preparative gel permeation chromatography to obtain VPOSS-2oLA n ;

[0110] S10. VPOSS-2oLA was added under argon atmosphere. n (0.026mmol) and oDMS 13 (400 mg, 0.39 mmol, 15 eq) was added to 3 mL of anhydrous toluene and stirred to dissolve, and then a drop of Karstedt's catalyst was added and stirred at 80 ° C overnight. After the reaction was completed, the solvent was removed and then purified by preparative gel permeation chromatography to obtain 6oDMS m -POSS-2oLA n .

[0111] Example 12

[0112] ortho-6oDMS 13 -POSS-oLA n1 / oLA n2 Synthesis

[0113] Combine ortho-VPOSS-2OH (237mg, 0.3mmol), TBDMS-L n1-COOH (0.3mmol, 1eq) and DPTS (44mg, 0.15mmol, 0.5eq) were dissolved in 8mL dry dichloromethane, cooled to 0°C and then slowly added with DIC (38mg, 0.3mmol, 1eq). After 24h of reaction, the solvent was removed; then toluene was added to dissolve, filtered, and rotary dried to obtain a crude product; the crude product was purified by preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 (-OH);

[0114] ortho-VPOSS-oLA n1 (-OH)(0.2mmol),TBDMS-L n2 -COOH (0.3mmol, 1.5eq) and DPTS (29mg, 0.1mmol, 0.5eq) were dissolved in 8mL dry dichloromethane, cooled to 0°C and then slowly added with DIC (37mg, 0.3mmol, 1.5eq). After 24h of reaction, the solvent was removed; then toluene was added to dissolve, filtered and rotary dried to obtain a crude product; the crude product was purified by preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 / oLA n2 ;

[0115] ortho-VPOSS-oLA n1 / oLA n2 (0.026mmol) and oDMS 13 (400 mg, 0.39 mmol, 15 eq) was dissolved in 3 mL of dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule ortho-6oDMS 13 -POSS-oLA n1 / oLA n2 ;

[0116] Embodiment 13

[0117] 7oDMS 13 -POSS-oPL n Synthesis

[0118] VPOSS-OH (200 mg, 0.28 mmol), TBDMS-P n-COOH (0.42mmol, 1.5eq) and DPTS (41mg, 0.14mmol, 0.5eq) were dissolved in 6mL dry dichloromethane, cooled to 0°C and then slowly added with DIC (53mg, 0.42mmol, 1.5eq). After 24h of reaction, the solvent was removed; then toluene was added to dissolve, filtered and rotary dried to obtain a crude product; the crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-P n ;

[0119] VPOSS-P n (0.026mmol) and oDMS 13 (400 mg, 0.39 mmol, 15 eq) was dissolved in 3 mL of dry toluene under nitrogen atmosphere; then a drop of Karstedt's catalyst was added and stirred at 80°C overnight. After the reaction was completed, the solvent was removed and purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS 13 -POSS-oPL n ;

[0120] The above description is only the preferred embodiment of the present application and is not intended to limit the present application. For those skilled in the art, the present application may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. Hetero-arm star polymer 7oDMS m -POSS-oLA n The preparation method is characterized in that The method comprises the following preparation steps: VPOSS-OH、TBDMS-oLA n -COOH and dimethylaminopyridine toluenesulfonate are dissolved in 4-6 mL dry dichloromethane, cooled to 0-5°C, and then 1,3-diisopropylcarbodiimide is slowly added. After reacting for 20-28 hours, the solvent is removed; then toluene is added to dissolve, filtered, and rotary dried to obtain a crude product; the crude product is purified by preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n ; VPOSS-oLA n and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule 7oDMS m -POSS-oLA n ; VPOSS-OH, TBDMS-oLA in S01 n The molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8; The VPOSS-oLA n and oDMS m The molar ratio is 1:11-15; The n is 28≤n≤64, and takes a value every 4; m is 5, 9, or 13.

2. Hetero-arm star polymer 7oDMS m -POSS-2oLA n The preparation method is characterized in that The method comprises the following preparation steps: VPOSS-OH, hydroxyl-protected 2,2-bis(hydroxymethyl)propionic acid and DPTS were dissolved in dry 8-10 mL dichloromethane, cooled to 0-5°C and then slowly added with DIC to react for 20-28 hours. After the reaction was completed, the crude product was filtered and the solvent was removed to obtain a crude product. The crude product was separated in a fast liquid preparative chromatograph, and the intermediate product obtained after separation and purification was dissolved in methanol and added Carry out the deprotection reaction of hydroxyl group for 5-7h; after the reaction is completed, filter the remaining And VPOSS-(OH)2 was separated and purified by rapid liquid preparative chromatography; VPOSS-(OH)2、TBDMS-oLA n -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Then toluene was added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-2oLA n ; VPOSS-2oLA n and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule 7oDMS m -POSS-2oLA n ; The molar ratio of the VPOSS-OH, hydroxyl-protected 2,2-bis(hydroxymethyl)propionic acid, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8; The VPOSS-(OH)2, TBDMS-L n The molar ratio of -COOH, DPTS, and DIC is 1:2.5-3.0:0.1-0.5:2.5-3.0; The VPOSS-2oLA n and oDMS m The molar ratio is 1:11-15; The n is 20, 24, 28; and m is 13.

3. Hetero-arm star polymer 7oDMS m -POSS-oLA n1 / oLA n2 The preparation method is characterized in that The method comprises the following preparation steps: VPOSS-(OH)2、TBDMS-L n1 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified using preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n1 (-OH); VPOSS-oLA n1 (-OH), TBDMS-L n2 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified using preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n1 / oLA n2 ; VPOSS-oLA n1 / oLA n2 and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule 7oDMS m -POSS-oLA n1 / oLA n2 ; The VPOSS-(OH)2, TBDMS-L n1 The molar ratio of -COOH, DPTS, and DIC is 1: 0.8-1.2: 0.1-0.5: 1.5-1.8; The VPOSS-oLA n1 (-OH), TBDMS-L n2 The molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8; The VPOSS-oLA n1 / oLA n2 and oDMS m The molar ratio is 1:11-15; The n1+n2=40, 48, 56; when n1+n2=40, n1=8, 12, 16; when n1+n2=48, n1=8, 12, 16, 20; when n1+n2=56, n1=8, 12, 16, 20, 24; m is 13.

4. Different regional configurations of hetero-arm star polymers 6oDMS m -POSS-2oLA n The preparation method is characterized in that The method comprises the following preparation steps: VPOSS-2OH, TBDMS-oLA n -COOH and DPTS were added with 3-5 mL of dry dichloromethane, stirred to dissolve, and then cooled to 0-5°C, and then DIC was slowly added and stirred at room temperature for 6-10 hours. After the reaction was completed, the solvent was removed and toluene was added to dissolve, filtered, and rotary dried to obtain a crude product, which was then purified by preparative gel permeation chromatography to obtain VPOSS-2oLA n ; VPOSS-2oLA was added under nitrogen atmosphere. n and oDMS m Add 3-5 mL of anhydrous toluene and stir to dissolve, then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is completed, remove the solvent and purify by preparative gel permeation chromatography to obtain 6oDMS. m -POSS-2oLA n . The VPOSS-2OH, TBDMS-oLA n The molar ratio of -COOH, DPTS, and DIC is 1:2.5-3.0:0.1-0.5:2.5-3.0; The VPOSS-2oLA n and oDMS m The molar ratio is 1:11-15; The regional configurations of the VPOSS-2OH are para-, meta- and ortho-configurations. The n is 24, 28, 32; the m is 5, 9, 13.

5. Hetero-arm star polymer ortho-6oDMS m -POSS-oLA n1 / oLA n2 The preparation method is characterized by comprising the following preparation steps: ortho-VPOSS-2OH, TBDMS-L n1 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 (-OH); ortho-VPOSS-oLA n1 (-OH), TBDMS-L n2 -COOH and DPTS were dissolved in 8-10 mL dry dichloromethane, cooled to 0-5°C and then slowly added with DIC. After reacting for 20-28 hours, the solvent was removed. Toluene was then added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 / oLA n2 ; ortho-VPOSS-oLA n1 / oLA n2 and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule ortho-6oDMS m -POSS-oLA n1 / oLA n2 ; The ortho-VPOSS-2OH, TBDMS-L n1 The molar ratio of -COOH, DPTS, and DIC is 1: 0.8-1.2: 0.1-0.5: 1.5-1.8; The ortho-VPOSS-oLA n1 (-OH), TBDMS-L n2 The molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8; The ortho-VPOSS-oLA n1 / oLA n2 and oDMS m The molar ratio is 1:11-15; The n1+n2=48, 56; when n1+n2=48, n1=4, 8, 12, 16, 20; when n1+n2=56, n1=4, 8, 12, 16, 20, 24; m is 13.

6. Hetero-arm star polymer 7oDMS m -POSS-oPL n The preparation method is characterized in that The method comprises the following preparation steps: VPOSS-OH、TBDMS-oPL n -COOH and DPTS were dissolved in 4-6 mL dry dichloromethane, cooled to 0-5 °C, and then 1,3-diisopropylcarbodiimide (DIC) was slowly added. After the reaction was continued for 20-28 hours, the solvent was removed. Then toluene was added to dissolve, filtered, and rotary dried to obtain a crude product. The crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-oPL n ; VPOSS-oPL n and oDMS m Dissolve in 2-4 mL dry toluene under nitrogen atmosphere; then add a drop of Karstedt's catalyst and stir at 70-90°C overnight. After the reaction is complete, remove the solvent and purify by preparative gel permeation chromatography to obtain the target molecule. 7oDMS m -POSS-oPL n ; The VPOSS-OH, TBDMS-oPL n The molar ratio of -COOH, DPTS, and DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8; The VPOSS-oPL n and oDMS m The molar ratio is 1:11-15; The n is 28, 32, 36; and m is 13.

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