Process for the preparation of precise heteroarm star polymers forming a close-packed spheroid phase

Abstract

The application provides a preparation method of precision hetero-arm star-shaped polymers forming a close-packed spherical phase, and belongs to the technical field of polymer materials. Based on an iterative growth method and a modular synthesis strategy, a series of discrete hetero-arm star-shaped polymers based on polyhedral oligomeric silsesquioxane (POSS) with precise chemical structures and single molecular weights are constructed, and the hetero-arm star-shaped polymers can form a thermodynamically stable hexagonal close-packed spherical phase (HCP) in a bulk self-assembly process. The application designs a series of isomeric polymers for specific molecular parameters (such as volume fraction, topological structure, region configuration and block number) to eliminate the interference of other variables, and provides an ideal platform for quantitatively studying the role of the molecular parameters in the self-assembly process. The application can bridge the gap between experimental exploration and theoretical research, and will help to deeply understand the basic principles of block copolymer self-assembly, and provide guidance for rationally designing new functional polymer materials.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a preparation method of precise hetero-arm star-shaped polymers forming a close-packed spherical phase. BACKGROUND

[0002] Block copolymers can spontaneously form various periodic structures at the nanoscale, and have wide application value in many fields. It is generally believed that the self-assembly behavior of linear block copolymers follows the general principle, mainly depending on three variables: namely, the polymerization degree (N), the composition (f) and the 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 spherical phase (BCC) can be easily obtained. The very regular spherical phase, including Frank-Kasper phase and quasi-crystalline phase, greatly expands the diversity of nanostructures, and stimulates people's interest in the field. Although exciting progress has been made, there is still a missing piece in the phase diagram of block copolymers. The classical phase theory predicts that there is a thermodynamically stable close-packed spherical phase (CPS) in a very narrow region near the order-disorder phase boundary, namely hexagonal close-packed (HCP) and face-centered cubic packing (FCC). However, 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 of block copolymers with uniform chain length in theoretical calculations, the objects of experimental research are usually multi-component mixtures with certain dispersion. The existence of dispersion not only causes inconsistency between theory and experiment, affecting the understanding of the intrinsic mechanism of the self-assembly process, but also couples with other variables, bringing great difficulties to quantitative research. However, due to the difficulty in preparing structure-precise samples, the experimental research and verification on the formation of the above structures are relatively lacking. SUMMARY

[0003] To solve the above technical problems, the present application provides a preparation method of precise hetero-arm star-shaped polymers forming a close-packed spherical phase, which utilizes a "core-first" strategy to prepare different hydroxyl-substituted POSS cores (VPOSS-OH, VPOSS-(OH)2, para-, meta-, ortho-VPOSS-2OH). Then, an iterative growth method is used to prepare discrete oligo-lactic acid (oLA n , L) and oligo-dimethylsiloxane (oDMS m , S). On this basis, efficient coupling reactions are used to graft oLA and oDMS homopolymers onto the POSS core, obtaining a series of discrete hetero-arm star-shaped polymers with precise structure. The different fractions of the POSS core [7:1] hetero-arm star-shaped polymers (7oDMSm -POSS-oLA n ), [7:2] mikto-arm star polymers with different symmetries (7oDMS m -POSS-oLA n1 / oLA n2 ) and [6:2] mikto-arm star polymers with different regio- configurations (para-, meta-, ortho-6oDMS m -POSS-oLA n1 / oLA n2 ). The study of the self-assembly of the star polymer bulk found that with the increase of oLA volume fraction, the transition from disordered phase to hexagonal columnar phase (HEX) and spherical phase (A15 and HCP) was observed. It is exciting that the phase distance of HCP phase reaches 0.19 to 0.39 (0.19 < f oLA <0.39). In addition, we also found that this mikto-arm star polymer with POSS as the core is a general structure for forming HCP phase, and replacing polylactic acid with polyphenyl lactic acid (oPL) block can also form a stable HCP phase.

[0004] In a first aspect, the present application provides a preparation method of a mikto-arm star polymer 7oDMS m -POSS-oLA n , comprising the following preparation steps:

[0005] VPOSS-OH, TBDMS-oLA n -COOH and dimethylaminopyridine p-toluenesulfonate (DPTS) are dissolved in 4-6 mL of dry dichloromethane, and after cooling to 0-5℃, 1,3-diisopropyl carbodiimide (DIC) is slowly added. After the reaction for 20-28 h, the solvent is removed; then toluene is added for dissolution, suction filtration and rotary evaporation 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 are dissolved in 2-4 mL of dry toluene under a nitrogen atmosphere; then one drop of Karstedt's catalyst is added and stirred at 70-90℃ overnight. After the reaction is completed, the solvent is removed and then purified by preparative gel permeation chromatography to obtain the target molecule

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

[0008] VPOSS-OH, TBDMS-L nmolar ratio of COOH, DPTS, DIC is 1:1.5-1.8:0.1-0.5:1.5-1.8;

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

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

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

[0012] VPOSS-OH, hydroxyl-protected 2,2-bis(hydroxymethyl)propionic acid and DPTS are dissolved in dry 8-10 mL dichloromethane, and DIC is slowly added after cooling to 0-5°C, and the reaction is carried out for 20-28 h. After the reaction is completed, the crude product is obtained after filtration and removal of the solvent. The intermediate product obtained after separation and purification by rapid liquid preparation chromatography is dissolved in methanol, and hydroxyl deprotection reaction is carried out, and the reaction is carried out for 5-7 h. After the reaction is completed, the remaining is filtered, and VPOSS-(OH)2 is obtained by separation and purification using a rapid liquid preparation chromatograph.

[0013] VPOSS-(OH)2, TBDMS-L n -COOH and DPTS are dissolved in 8-10 mL dry dichloromethane, and DIC is slowly added after cooling to 0-5°C. After the reaction is carried out for 20-28 h, the solvent is removed. Then, toluene is added for dissolution, suction filtration and rotary drying to obtain a crude product. The crude product is purified by using a preparation grade gel permeation chromatograph to obtain the precursor VPOSS-2oLA n ;

[0014] VPOSS-2oLA n and oDMS m are dissolved in 2-4 mL dry toluene under a nitrogen atmosphere. Then, one drop of Karstedt's catalyst is added, and the reaction is carried out overnight at 70-90°C. After the reaction is completed, the solvent is removed, and the target molecule

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

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

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

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

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

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

[0021] Dissolving VPOSS-(OH)2, TBDMS-L n1 -COOH and DPTS in 8-10 mL dry dichloromethane, and slowly adding DIC after cooling to 0-5°C, removing the solvent after 20-28 h of reaction; then adding toluene for dissolution, suction filtration, and rotary drying to obtain a crude product; purifying the crude product using a preparative gel permeation chromatograph to obtain the precursor VPOSS-oLA n1 (-OH);

[0022] Dissolving VPOSS-oLA n1 (-OH), TBDMS-L n2 -COOH and DPTS in 8-10 mL dry dichloromethane, and slowly adding DIC after cooling to 0-5°C, removing the solvent after 20-28 h of reaction; then adding toluene for dissolution, suction filtration, and rotary drying to obtain a crude product; purifying the crude product using a preparative gel permeation chromatograph to obtain the precursor VPOSS-oLA n1 / oLA n2 ;

[0023] Dissolving VPOSS-oLA n1 / oLA n2 and oDMS m in 2-4 mL dry toluene under a nitrogen atmosphere; then adding one drop of Karstedt's catalyst and stirring overnight at 70-90°C, removing the solvent after the reaction is completed, and then purifying by a preparative gel permeation chromatograph to obtain the target molecule 7oDMSm -POSS-oLA n1 / oLA n2 ;

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

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

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

[0027] The n1+n2=40, 48, 56; wherein, 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 application provides a preparation method of a hetero-arm star polymer 6oDMS m -POSS-2oLA n , comprising the following preparation steps:

[0029] VPOSS-2OH, TBDMS-oLA n -COOH and DPTS are added to 3-5 mL of dry dichloromethane and stirred to dissolve, then cooled to 0-5℃, then DIC is slowly added and stirred at room temperature for 6-10 hours, after the reaction is completed, the solvent is removed and then dissolved in toluene, filtered and rotary dried to obtain a crude product, then the crude product is purified by using a preparative gel permeation chromatograph to obtain VPOSS-2oLA n ;

[0030] VPOSS-2oLA n and oDMS m are added to 3-5 mL of anhydrous toluene and stirred to dissolve, then one drop of Karstedt's catalyst is added and stirred at 70-90℃ overnight, after the reaction is completed, the solvent is removed, and then purified by a preparative gel permeation chromatograph to obtain 6oDMS m -POSS-2oLA n .

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

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

[0033] the regio-configuration of the VPOSS-2OH is para-, meta- and ortho-configuration, respectively.

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

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

[0036] dissolving ortho-VPOSS-2OH, TBDMS-L n1 -COOH and DPTS in 8-10 mL dry dichloromethane, and slowly adding DIC after cooling to 0-5℃, removing the solvent after 20-28h of reaction; then adding toluene for dissolution, suction filtration, rotary drying to obtain a crude product; purifying the crude product using a preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 (-OH);

[0037] dissolving ortho-VPOSS-oLA n1 (-OH), TBDMS-L n2 -COOH and DPTS in 8-10 mL dry dichloromethane, and slowly adding DIC after cooling to 0-5℃, removing the solvent after 20-28h of reaction; then adding toluene for dissolution, suction filtration, rotary drying to obtain a crude product; purifying the crude product using a preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 / oLA n2 ;

[0038] dissolving ortho-VPOSS-oLA n1 / oLA n2 and oDMS mDMS under nitrogen atmosphere, then add one drop of Karstedt's catalyst and stir overnight at 70-90°C, after the reaction is completed, remove the solvent and then purify by preparative gel permeation chromatography to obtain the target molecule ortho-6oDMS m -POSS-oLA n1 / oLA n2 ;

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

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

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

[0042] The n1+n2=48, 56; wherein, 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 application provides a preparation method of a hetero-arm star polymer 7oDMS m -POSS-oPL n , comprising the following preparation steps:

[0044] Dissolve VPOSS-OH, TBDMS-oPL n -COOH and DPTS in 4-6 mL of dry dichloromethane, and after cooling to 0-5°C, slowly add 1,3-diisopropyl carbodiimide (DIC), remove the solvent after 20-28 h of reaction; then dissolve in toluene, filter, and rotary dry to obtain the crude product; purify the crude product using preparative gel permeation chromatography to obtain the precursor VPOSS-oPL n ;

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

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

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

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

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

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

[0051] (1) The present application successfully synthesizes a series of discrete hetero-arm star polymers with precise chemical structure and single molecular weight, providing an efficient and novel synthesis method for the precise construction of block copolymers, with high expandability.

[0052] (2) All the copolymers involved in the present application have precise composition and uniform chain length, which eliminates the composition uncertainty caused by traditional polymerization methods, and through the precise adjustment of special molecular parameters, a series of hetero-arm star polymers with different symmetry, different topological structure and different regional configuration 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 quantitative study of the role of the molecular parameter in the self-assembly process.

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

[0054] (4) In the present application, this hetero-arm star polymer with POSS as the core is a general structure for forming HCP phase, and other hydrophobic blocks can also form stable HCP phase by replacing polylactic acid. BRIEF DESCRIPTION OF DRAWINGS

[0055] Figure 1 is [7:1] hetero-arm star polymer 7oDMSm POSS-oLA n synthesis scheme of

[0056] Figure 2 [7:2] hetero-arm star polymer 7oDMS m POSS-2oLA n synthesis scheme of

[0057] Figure 3 [7:2] hetero-arm star polymer 7oDMS m POSS-oLA n1 POSS-oLA n2 synthesis scheme of

[0058] Figure 4 [6:2] hetero-arm star polymer ortho-6oDMS m POSS-2oLA n synthesis scheme of

[0059] Figure 5 [6:2] hetero-arm star polymer ortho-6oDMS m POSS-oLA n1 POSS-oLA n2 synthesis scheme of

[0060] Figure 6 [7:1] hetero-arm star polymer 7oDMS m POSS-oPL n synthesis scheme of

[0061] Figure 7 POSS-oLA n H NMR characterization (a), MALDI-ToF-MS characterization (b) and SEC characterization (c) of the precursor VPOSS-oLA 1

[0062] Figure 8 MALDI-ToF-MS characterization (a) and SEC characterization (b) of the hetero-arm star polymer 7oDMS 5-POSS-oLA n

[0063] Figure 9 Small angle X-ray scattering (SAXS) of the [7:1] hetero-arm star polymer 7oDMS m POSS-oLA n

[0064] Figure 10 ​​​Precursor made for Example 6, VPOSS-2oLA n 1 HNMR characterization (a), MALDI-ToF-MS characterization (b) and SEC characterization (c).

[0065] Figure 11 [6:2] Hetero-arm star polymer made for Example 11, 6oDMS 13 -POSS-2oLA n SAXS characterization of.

[0066] Figure 12 [6:2] Hetero-arm star polymer made for Example 12, ortho-6oDMS 13 -POSS-oLA n1 / oLA n2 SAXS characterization of.

[0067] Figure 13 Hetero-arm star polymer made for Example 13, 7oDMS 13 -POSS-oPL 32 SAXS characterization of.

[0068] Figure 14 Generalized schematic of hetero-arm star polymers. DETAILED DESCRIPTION

[0069] Various illustrative embodiments of the present application are now described in detail below. The described embodiments are not intended to limit the scope of the application, but rather are presented as a series of examples, some of which are utilized to describe the principles of the present application. The complete disclosure of the application is defined by the description of the embodiments.

[0070] It should be understood that the terms used herein are merely descriptive, but that the application should not be construed as being limited thereto. In addition, with respect to numerical ranges in the present application, it is to be understood that every intervening value, to the upper and lower limits of the ranges stated is also specifically disclosed. Each smaller range between any stated range limits are also specifically disclosed. The upper and lower limits of these smaller ranges can independently be included or excluded in the range.

[0071] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although preferred methods and materials are described, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application. All documents mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the documents are cited. In the event of conflict between the present specification and any incorporated document, the present specification controls. ​

[0072] Many modifications and variations of the described implementations of the application can be made without departing from its spirit or scope, which will be apparent to those skilled in the art. Other implementations will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. The specification and examples given are exemplary only.

[0073] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or variations thereof, are intended to be open-ended terms that mean inclusion, but not limited to, and specific embodiments are provided for the purpose of exemplification only.

[0074] In the following examples, n is one or more of 28, 32, 36, 40, 44, 48, 56; each of the examples is synthesized and detected by using the method described in the example, see the corresponding figures of each example.

[0075] Example 1

[0076] Synthesis of VPOSS-oLA n

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

[0078] Example 2

[0079] Synthesis of 7oDMS5-POSS-oLA n

[0080] VPOSS-L n (0.049 mmol) and oDMS5 (300 mg, 0.69 mmol, 14 eq) were dissolved in 3 mL dry toluene under nitrogen atmosphere; then one 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 get the target molecule 7oDMS5-POSS-oLA n ;

[0081] Example 3 ​​

[0082] 7oDMS9-POSS-oLA n Synthesis of

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

[0084] Example 4

[0085] Synthesis of 13 7oDMS9-POSS-oLA n ;

[0086] VPOSS-L n (0.049 mmol) and oDMS 13 (708 mg, 0.69 mmol, 14 eq) were dissolved in 3 mL dry toluene under nitrogen atmosphere; then a drop of Karstedt’s catalyst was added and stirred overnight at 80 °C, after the reaction was completed, the solvent was removed and then purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS9-POSS-oLA 13 ; 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 dry 8 mL dichloromethane and cooled to 0 °C, then DIC (1.33 g, 10.5 mmol, 1.5 eq) was slowly added, and the reaction was carried out for 24 h, after the reaction was completed, the crude product was obtained after filtration and solvent removal; 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 hydroxyl deprotection reaction was carried out, and the reaction was carried out for 6 h; after the reaction was completed, the remaining was filtered and separated and purified by a fast liquid preparative chromatograph to obtain VPOSS-(OH)2;

[0090] Example 6

[0091] ​Synthesis of VPOSS-2oLA n

[0092] VPOSS-(OH)2(99 mg, 0.12 mmol), TBDMS-L n -COOH (0.36 mmol, 3 eq) and DPTS (18 mg, 0.06 mmol, 0.5 eq) were dissolved in 8 mL of dry dichloromethane and cooled to 0 °C before slowly adding DIC (45 mg, 0.36 mmol, 3 eq) and removing the solvent after 24 h of reaction; then dissolving in toluene, suction filtered, spin dried to obtain the crude product; the crude product was purified using preparative gel permeation chromatography to obtain the precursor VPOSS-2oLA n ;

[0093] Example 7

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

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

[0096] Example 8

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

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

[0099] Example 9

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

[0101] VPOSS-2oLA n ​​​​(0.02 mmol) and oDMS 13 (287 mg, 0.28 mmol, 14 eq) were dissolved in 3 mL of dry toluene under nitrogen atmosphere; then one drop of Karstedt’s catalyst was added and stirred overnight at 80 °C, after the reaction was completed, the solvent was removed and then 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 of

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

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

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

[0107] Example 11

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

[0109] VPOSS-2OH (para-, meta-, ortho-, 300 mg, 0.38 mmol) of different regioconfigurations, TBDMS- oLA n -COOH (0.98 mmol, 2.5 eq) and DPTS (56 mg, 0.19 mmol, 0.5 eq) were dissolved in 5 mL of dry dichloromethane and stirred, then cooled to 0 °C, 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 then dissolved in toluene, filtered, and rotary dried to obtain the crude product, which was then purified by preparative gel permeation chromatography to obtain VPOSS-2oLA n ;

[0110] S10. VPOSS-2oLA n (0.026 mmol) and oDMS 13 (400 mg, 0.39 mmol, 15 eq) were dissolved in 3 mL of anhydrous toluene and stirred, then one drop of Karstedt’s catalyst was added dropwise and stirred overnight at 80 °C, 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] ortho-VPOSS-2OH (237 mg, 0.3 mmol), TBDMS-L n1-COOH (0.3 mmol, 1 eq) and DPTS (44 mg, 0.15 mmol, 0.5 eq) were dissolved in 8 mL of dry dichloromethane and cooled to 0 °C before slowly adding DIC (38 mg, 0.3 mmol, 1 eq). After 24 h of reaction, the solvent was removed; then toluene was added for dissolution, suction filtered, and spin dried to obtain the crude product; the crude product was purified using preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 (-OH);

[0114] ortho-VPOSS-oLA n1 (-OH) (0.2 mmol), TBDMS-Cl (0.1 mL, 0.6 mmol, 3 eq) and DMAP (10 mg, 0.08 mmol, 0.4 eq) were dissolved in 8 mL of dry dichloromethane and cooled to 0 °C before slowly adding DIC (37 mg, 0.3 mmol, 1.5 eq). After 24 h of reaction, the solvent was removed; then toluene was added for dissolution, suction filtered, and spin dried to obtain the crude product; the crude product was purified using preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n2 -COOH (0.3 mmol, 1.5 eq) and DPTS (29 mg, 0.1 mmol, 0.5 eq) were dissolved in 8 mL of dry dichloromethane and cooled to 0 °C before slowly adding DIC (37 mg, 0.3 mmol, 1.5 eq). After 24 h of reaction, the solvent was removed; then toluene was added for dissolution, suction filtered, and spin dried to obtain the crude product; the crude product was purified using preparative gel permeation chromatography to obtain the precursor ortho-VPOSS-oLA n1 / oLA n2 ;

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

[0116] Example 13

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

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

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

[0120] The above only the preferred embodiments of the present application, and is not intended to limit the present application, for those skilled in the art, the present application can have various changes and variations. Any modification, equivalent replacement, improvement, etc. within the spirit and principles of the present application, should be included in the scope of protection of the present application.

Claims

1. Hetero-arm star polymer 7oDMS m - POSS-oLA n a process for the preparation of Comprising the following preparation steps: VPOSS-OH, TBDMS-oLA n -COOH and dimethylaminopyridine p-toluenesulfonate DPTS were dissolved in 4-6 mL dry dichloromethane and cooled to 0-5 ℃, then 1,3-diisopropylcarbodiimide DIC was slowly added, and after the reaction for 20-28 h, the solvent was removed; then toluene was added for dissolution, suction filtration, and rotary drying to obtain the crude product; the crude product was purified by preparative gel permeation chromatography to obtain the precursor VPOSS-oLA n ; VPOSS-oLA n and oligomeric dimethylsiloxane oDMS m Dissolved in 2-4 mL dry toluene under nitrogen atmosphere; then a drop of Karstedt’s catalyst was added and stirred overnight at 70-90 °C, after the reaction was completed, the solvent was removed and then purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS m -POSS-oLA n ; said VPOSS-OH, TBDMS-oLA n molar ratio of -COOH, DPTS, DIC is 1 : 1.5-1.8: 0.1-0.5: 1.5-1.8; The VPOSS-oLA n and oDMS m in a molar ratio of 1:11-15; The n is 32≤n≤56, taking a value every 4 intervals; m is 9, 13; The reaction process is: 。 2. Hetero-arm star polymer 7oDMS m - POSS-oPL n The process for the preparation of a compound of formula Comprising the following preparation steps: VPOSS-OH, TBDMS-oPL n -COOH and dimethylaminopyridine p-toluenesulfonate DPTS were dissolved in 4-6 mL dry dichloromethane and cooled to 0-5 °C before slowly adding 1,3-diisopropylcarbodiimide DIC, after the reaction for 20-28 h, the solvent was removed; then dissolved in toluene, suction filtered, rotary dried to obtain the crude product; the crude product was purified using preparative gel permeation chromatography to obtain the precursor VPOSS-oPL n ; VPOSS-oPL n and oligomeric dimethylsiloxane oDMS m Dissolved in 2-4 mL of dry toluene under nitrogen atmosphere; then a drop of Karstedt’s catalyst was added and stirred overnight at 70-90 °C, after the reaction was completed, the solvent was removed and then purified by preparative gel permeation chromatography to obtain the target molecule 7oDMS m -POSS-oPL n ; said VPOSS-OH, TBDMS-oPL n molar ratio of -COOH, DPTS, DIC is 1 : 1.5-1.8: 0.1-0.5: 1.5-1.8; The VPOSS-oPL n and oDMS m at a molar ratio of 1:11-15; The n is 32; m is 13; The reaction process is: 。

Images