阅读说明：本技术 一种巨型分子及其制备方法 (Giant molecule and preparation method thereof ) 是由 何子明 董学会 甘展慧 周冬冬 于 2020-05-09 设计创作，主要内容包括：本发明公开了一种巨型分子及其制备方法。这种巨型分子的结构式选自式(Ⅰ)～(Ⅲ)中的至少一种：<Image he="170" wi="700" file="DDA0002483747240000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="113" wi="700" file="DDA0002483747240000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>式(Ⅰ)～(Ⅲ)中,A、B、C分别独立表示为多面体寡聚倍半硅氧烷；B与A、C均以酯键相连。这种巨型分子的制备方法包括如下步骤：1)巨型分子侧端前体及巨型分子中心前体的制备；2)巨型分子侧端化合物的制备与功能化修饰；3)制备中心未功能化的巨型分子；4)巨型分子中心的功能化修饰。本发明提供的一系列巨型分子与传统的多嵌段共聚物相比,分子序列与空间构型高度精确可控。本发明的制备方法可以从根本上实现巨型分子制备的可调控性,具有步骤简单、反应高效、条件温和等优点。(The invention discloses a giant molecule and a preparation method thereof. The giant molecule has a structural formula selected from at least one of formulas (I) to (III): in the formulas (I) to (III), A, B, C are respectively and independently expressed as polyhedral oligomeric silsesquioxane; both B and A, C are linked by an ester bond. The preparation method of the giant molecule comprises the following steps: 1) preparing a giant molecule side end precursor and a giant molecule center precursor; 2) preparing a giant molecule side end compound and performing functional modification; 3) preparing giant molecules with unfunctionalized centers; 4) functional modification of giant molecule center.Compared with the traditional multi-block copolymer, the series of giant molecules provided by the invention have highly accurate and controllable molecular sequence and spatial configuration. The preparation method can radically realize the adjustability of the giant molecule preparation, and has the advantages of simple steps, high reaction efficiency, mild conditions and the like.)

1. A giant molecule, comprising: the giant molecule has a structural formula selected from at least one of formulas (I) to (III):

in the formulas (I) to (III), A, B, C are respectively and independently expressed as polyhedral oligomeric silsesquioxane;

both B and A, C are linked by an ester bond.

2. The giant molecule of claim 1, wherein: the structural formula of A, C is respectively shown in formula (IV) and formula (V):

in the formulae (IV) and (V), R₁And R₃The alkyl is independently selected from C2-C3 alkyl with carboxyl at the tail end, or C2-C10 substituted alkyl with carboxyl at the tail end, and the substituted alkyl refers to that one or more carbon atoms on the alkyl are substituted by one functional group of ester group, pyridine and pyrone;

R₂and R₄Respectively and independently selected from C2-C18 straight chain or branched chain alkyl, C2-C10 straight chain or branched chain alkyl with one or more hydrogen atoms substituted by fluorine atoms, and C2-C6 straight chain or branched chain polyol;

in the formula (IV), m is 2-6;

in the formula (V), n is 2-6.

3. The giant molecule of claim 1, wherein: the structural formula of B is shown as a formula (VI):

in the formula (VI), R₅Selected from C2-C18 straight chain or branched chain alkyl, C2-C10 straight chain or branched chain alkyl with one or more hydrogen atoms substituted by fluorine atoms, C2-C6 straight chain or branched chain alkanol, C2-C6 straight chain or branched chain alkanoic acid, C2-C6 straight chain or branched chain polyalcohol and benzyl alcohol;

x＝2～6。

4. a preparation method of giant molecules is characterized in that: the method comprises the following steps:

1) preparation of giant molecule side end precursor and giant molecule center precursor

Mixing octavinyl polyhedral oligomeric silsesquioxane, first mercaptan, a photoinitiator and a solvent, and carrying out an ene-mercaptan reaction under illumination to obtain a giant molecule side end precursor and a giant molecule center precursor; the giant molecule side end precursor is monohydroxy heptavinyl polyhedral oligomeric silsesquioxane; the giant molecule center precursor comprises ortho-dihydroxyl hexavinyl polyhedral oligomeric silsesquioxane, meta-dihydroxyl hexavinyl polyhedral oligomeric silsesquioxane and para-dihydroxyl hexavinyl polyhedral oligomeric silsesquioxane;

2) preparation and functional modification of giant molecule side end compound

Carrying out esterification reaction on the giant molecule side end precursor obtained in the step 1), an acidifying agent and a catalyst in a solvent to obtain a carboxylated giant molecule side end precursor, then mixing the carboxylated giant molecule side end precursor, a second mercaptan, a photoinitiator and the solvent, and carrying out an ene-mercaptan reaction under illumination to obtain a giant molecule side end compound;

3) preparation of centrally unfunctionalized macromolecules

Carrying out esterification reaction on the giant molecule center precursor obtained in the step 1), the giant molecule side end compound obtained in the step 2) and a catalyst in a solvent, and carrying out esterification reaction on the obtained product and the giant molecule side end compound obtained in the step 2) and the catalyst in the solvent to obtain a giant molecule with an unfunctionalized center;

4) functional modification of giant molecule center

Mixing the giant molecule with the non-functionalized center obtained in the step 3), the third thiol, the photoinitiator and the solvent, and carrying out an ene-thiol reaction under illumination to obtain the giant molecule of any one of claims 1 to 3.

5. The method of claim 4, wherein the step of preparing the giant molecule comprises: the structural formula of the central compound of the giant molecule with the center not functionalized is shown as a formula (VII):

in the formula (VII), x is 2-6.

6. The method of claim 4, wherein the step of preparing the giant molecule comprises: in the step 1), the mol ratio of the octavinyl polyhedral oligomeric silsesquioxane to the first thiol to the photoinitiator is 1: (1.5-2): (0.05-0.5); the first mercaptan is at least one selected from 2-mercaptoethanol, 3-mercaptopropanol, 4-mercapto-1-butanol and 6-mercaptohexan-1-ol.

7. The method of claim 4, wherein the step of preparing the giant molecule comprises: in the step 2), the molar ratio of the giant molecule side end precursor, the acidifying agent and the catalyst is 1: (1-2): (0.05-0.5); the molar ratio of the carboxylated giant molecule side end precursor, the second thiol and the photoinitiator is 1: (9-12): (0.05-0.5); the second mercaptan is at least one of linear chain or branched chain mercaptan of C2-C18, 2, 2-trifluoroethanethiol, pentafluo-pentanethiol, 1H,2H, 2H-perfluorodecyl mercaptan and alpha-thioglycerol; the acidifier is at least one selected from carboxylic acid and acid anhydride.

8. The method of claim 4, wherein the step of preparing the giant molecule comprises: in any esterification reaction in the step 3), the molar ratio of the giant molecule side end compound to the giant molecule center precursor is (1-1.2): 1.

9. the method of claim 4, wherein the step of preparing the giant molecule comprises: in the step 4), the molar ratio of the central non-functionalized giant molecule to the third thiol to the photoinitiator is 1: (6-10): (0.05-0.5); the third mercaptan is at least one selected from the group consisting of C2-C18 straight chain or branched chain mercaptan, 2,2, 2-trifluoroethylmercaptan, pentafluoropentanethiol, 1H,2H, 2H-perfluorodecyl mercaptan, thioglycolic acid, 3-mercapto-1, 2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, 3-mercapto-2-methyl-1-pentanol, 3-mercapto-1-hexanol, 2-mercaptoethanol, 3-mercaptopropanol, alpha-thioglycerol, 2-mercaptobenzyl alcohol and 4-mercaptobenzyl alcohol.

10. Use of the giant molecule of any one of claims 1 to 3 in the fields of chip fabrication, energy, catalysis or biomedical engineering.

Technical Field

The invention relates to the technical field of organic compound synthesis, in particular to a giant molecule with precise sequence and space configuration and a preparation method thereof.

Background

Microphase separation of block copolymers has been extensively studied over the past several decades. Due to incompatibility among blocks, the block copolymer can generate microphase separation under specific induction conditions to form a highly ordered nano structure. In the self-assembly of block polymers, differences in sequence tend to result in differences in self-assembled structures. Meanwhile, researches show that in order to obtain a specific self-assembly structure with smaller characteristic dimension, a block polymer with lower polymerization degree and more accurate and uniform molecular weight can be selected by increasing the incompatibility of two blocks (namely increasing Flory-Huggins parameter chi). However, due to the limitation of the conventional polymerization reaction mechanism and the existence of uncontrollable factors such as impurities, the chain length, sequence and spatial configuration of the polymer are extremely difficult to be controlled comprehensively and accurately.

"giant molecule" refers to a macromolecule made up of precisely-constructed units ("nanoatoms") of nanometer dimensions linked by covalent bonds. Among them, "nanoatoms" are a class of caged molecules with precise chemical structure, nanometer size and rigid three-dimensional framework. Compared with the traditional block copolymer, the molecular weight, the sequence and the spatial structure of the giant molecule are more accurate and controllable.

Polyhedral oligomeric silsesquioxanes (POSS) are "nanoatoms" whose molecular skeleton is composed of silicon-oxygen (Si-O) junctions in an alternating manner. The POSS vertex angle has the spatial relative positions of ortho position, meta position and para position, and all can be modified with reactive or inert groups. The precise structural framework of polyhedral oligomeric silsesquioxanes makes it possible to construct a giant molecule with precise sequence and spatial configuration. In order to explore the influence of sequence and spatial isomerism on the self-assembly of the giant molecule, it is of great significance to synthesize the giant molecule with precise sequence and spatial configuration. Meanwhile, the self-assembly of the precise giant molecules can obtain nano patterns with smaller characteristic sizes than the traditional nano patterns, has potential advantages in the field of chip manufacturing, and has wide potential application in the fields of energy, catalysis, biomedical engineering and the like.

Disclosure of Invention

In order to overcome the problems of the conventional block polymers, one of the objects of the present invention is to provide a giant molecule with precise sequence and spatial configuration, the other of the objects of the present invention is to provide a method for preparing the giant molecule, and the third of the objects of the present invention is to provide the application of the giant molecule.

The invention concept of the invention is as follows: a giant molecule with precise sequence and space configuration can be obtained by modifying one or more specific groups on Si atoms at specific vertex angles of POSS and connecting a plurality of POSS according to a certain sequence and space structure.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the invention provides a giant molecule, the structural formula of which is selected from at least one of formulas (I) to (III):

in the formulas (I) to (III), A, B, C are respectively and independently expressed as polyhedral oligomeric silsesquioxane; both B and A, C are linked by an ester bond.

In the giant molecule of the invention, B is a giant molecule center compound and POSS is used_BRepresents; A. c is a compound at two ends of the giant molecule respectively, and POSS is used for the compound_A、POSS_CAnd (4) showing.

Formula (I) represents POSS_AAnd POSS_CRelative position of (2) as a center POSS_BOrtho-position of (a); formula (II) represents POSS_AAnd POSS_CRelative position of (2) as a center POSS_BMeta position of (a); formula (III) represents POSS_AAnd POSS_CRelative position of (2) as a center POSS_BAnd (4) contraposition. Side POSS_AAnd POSS_CAnd a central POSS_BAre connected by ester bonds.

Preferably, in such giant molecules, A (POSS)_A)、C(POSS_C) The structural formulas are respectively shown as formula (IV) and formula (V):

in the formulae (IV) and (V), R₁And R₃The alkyl is independently selected from C2-C3 alkyl with carboxyl at the tail end, or C2-C10 substituted alkyl with carboxyl at the tail end, and the substituted alkyl refers to that one or more carbon atoms on the alkyl are substituted by one functional group of ester group, pyridine and pyrone;

R₂and R₄Respectively and independently selected from C2-C18 straight chain or branched chain alkyl, C2-C10 straight chain or branched chain alkyl with one or more hydrogen atoms substituted by fluorine atoms, and C2-C6 straight chain or branched chain polyol;

in the formula (IV), m is 2-6;

in the formula (V), n is 2-6.

Preferably, in such giant molecules, B (POSS)_B) Has a structural formula shown in formula (VI):

in the formula (VI), R₅Selected from C2-C18 straight chain or branched chain alkyl, C2-C10 straight chain or branched chain alkyl with one or more hydrogen atoms substituted by fluorine atoms, C2-C6 straight chain or branched chain alkanol, C2-C6 straight chain or branched chain alkanoic acid, C2-C6 straight chain or branched chain polyalcohol and benzyl alcohol; x is 2-6.

The invention provides a preparation method of the giant molecule.

A preparation method of giant molecules comprises the following steps:

1) preparation of giant molecule side end precursor and giant molecule center precursor

Mixing octavinyl polyhedral oligomeric silsesquioxane, first mercaptan, a photoinitiator and a solvent, and carrying out an ene-mercaptan reaction under illumination to obtain a giant molecule side end precursor and a giant molecule center precursor; wherein the giant molecule side end precursor is monohydroxy heptavinyl polyhedral oligomeric silsesquioxane (VPOSS-OH); giant molecule center precursor (VPOSS-2OH) includes ortho-dihydroxyhexavinyl polyhedral oligomeric silsesquioxane (o-VPOSS-2OH), meta-dihydroxyhexavinyl polyhedral oligomeric silsesquioxane (m-VPOSS-2OH) and para-dihydroxyhexavinyl polyhedral oligomeric silsesquioxane (p-VPOSS-2 OH);

2) preparation and functional modification of giant molecule side end compound

Carrying out esterification reaction on the giant molecule side end precursor obtained in the step 1), an acidifying agent and a catalyst in a solvent to obtain a carboxylated giant molecule side end precursor (VPOSS-Ac), then mixing the carboxylated giant molecule side end precursor, a second thiol, a photoinitiator and the solvent, and carrying out an ene-thiol reaction under illumination to obtain a giant molecule side end compound (namely POSS)_AAnd POSS_C)；

3) Preparation of centrally unfunctionalized macromolecules

Carrying out esterification reaction on the giant molecule center precursor (VPOSS-2OH) obtained in the step 1), the giant molecule side end compound obtained in the step 2) and a catalyst in a solvent to obtain a product, and carrying out esterification reaction on the product, the giant molecule side end compound obtained in the step 2) and the catalyst in the solvent to obtain the giant molecule (POSS) with an unfunctionalized center_A-VPOSS_B-POSS_C)；

4) Functional modification of giant molecule center

Mixing the giant molecule with the center not functionalized obtained in the step 3), third mercaptan, a photoinitiator and a solvent, and carrying out an ene-mercaptan reaction under illumination to obtain the giant molecule (POSS)_A-POSS_B-POSS_C)。

Preferably, in the preparation method of the giant molecule, the central compound (VPOSS) of the giant molecule with the center not functionalized_B) The structural formula is shown as a formula (VII):

in the formula (VII), x is 2-6.

Preferably, in step 1) of the preparation method of the giant molecule, the molar ratio of the octavinyl polyhedral oligomeric silsesquioxane to the first thiol to the photoinitiator is 1: (1.5-2): (0.05-0.5).

Preferably, in step 1) of the preparation method of the giant molecule, the concentration of the octavinyl polyhedral oligomeric silsesquioxane in the solvent is 50 mg/mL-500 mg/mL.

Preferably, in step 1) of the preparation method of the giant molecule, the first thiol is at least one selected from the group consisting of 2-mercaptoethanol, 3-mercaptopropanol, 4-mercapto-1-butanol, and 6-mercaptohex-1-ol; further preferably, the first thiol is at least one selected from the group consisting of 2-mercaptoethanol and 3-mercaptopropanol.

Preferably, in step 2), the molar ratio of the giant molecule side end precursor, the acid and the catalyst is 1: (1-2): (0.05-0.5).

Preferably, in the step 2) esterification reaction of the preparation method of the giant molecule, the acidifying agent is selected from at least one of carboxylic acid and acid anhydride; the carboxylic acid is preferably a polycarboxylic acid; further preferably, the acidifying agent is selected from at least one of succinic anhydride, glutaric anhydride, 2, 4-pyridinedicarboxylic acid, and 4-pyrone-2, 6-dicarboxylic acid; still more preferably, the acidifying agent is selected from at least one of succinic anhydride and glutaric anhydride.

Preferably, in the step 2) esterification reaction, the catalyst is at least one selected from pyridine and 4-Dimethylaminopyridine (DMAP).

Preferably, in the step 2) of the preparation method of the giant molecule, the solvent is at least one selected from toluene, dimethyl sulfoxide and thionyl chloride. In some preferred embodiments of the present invention, the solvent used in the esterification reaction of step 2) is toluene.

Preferably, in the esterification reaction in the step 2) of the preparation method of the giant molecule, the reaction temperature is the reflux temperature of the solvent, and the reaction time is 4-48 h; further preferably, the esterification reaction temperature in the step 2) is 130 ℃ to 140 ℃, and the reaction time at the temperature is preferably 4h to 5 h.

Preferably, in step 2), the molar ratio of the carboxylated giant molecule side end precursor, the second thiol and the photoinitiator is 1: (9-12): (0.05-0.5).

Preferably, in step 2) of the preparation method of the giant molecule, the second thiol is at least one selected from the group consisting of C2-C18 linear or branched thiols, 2,2, 2-trifluoroethanethiol, pentafluoropentanethiol, 1H,2H, 2H-perfluorodecylthiol, and α -thioglycerol; further preferably, the second thiol is at least one selected from the group consisting of isopropyl thiol, n-butyl thiol, tert-butyl thiol, 1H,2H, 2H-perfluorodecyl thiol, and α -thioglycerol.

Preferably, in the alkene-thiol reaction of step 2) of the preparation method of the giant molecule, the concentration of the carboxylated giant molecule side end precursor in the solvent is 1 mg/mL-150 mg/mL.

The preparation method of the giant molecule, step 3) is specifically that the POSS obtained in the step 1) is ortho-position, meta-position or para-position_BThe precursor VPOSS-2OH is respectively reacted with the POSS obtained in the step 2)_AThe catalyst is subjected to esterification reaction in a solvent to obtain ortho-or meta-or para-POSS_A-VPOSS_BThen POSS is added_A-VPOSS_BAnd step 2) to obtain POSS_CThe catalyst is esterified in a solvent to obtain the POSS with the ortho-position, meta-position or para-position giant molecule center not functionalized_A-VPOSS_B-POSS_C。

Preferably, in any one of the esterification reactions in step 3) of the preparation method of the giant molecule, the molar ratio of the giant molecule side end compound to the giant molecule center precursor is (1-1.2): 1; further preferably, the molar ratio of the giant molecule side end compound to the giant molecule center precursor is 1: 1.

preferably, in any esterification reaction in step 3), the molar ratio of the giant molecule side end compound to the catalyst is 1: (0.05-0.5).

Preferably, in any esterification reaction in step 3), the catalyst is at least one selected from pyridine and 4-Dimethylaminopyridine (DMAP).

Preferably, in any esterification reaction in step 3), the solvent is at least one selected from alkyl halide solvents, ether solvents, halogenated aromatic hydrocarbons, ester solvents and alcohol solvents; further preferably, the solvent is at least one selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran and trifluorotoluene. In some preferred embodiments of the present invention, the solvent for any one of the esterification reactions in step 3) is anhydrous dichloromethane or a mixed solvent of anhydrous tetrahydrofuran and anhydrous benzotrifluoride.

Preferably, the preparation method of the giant molecule, step 3), any esterification reaction is carried out at normal temperature; the time for the esterification reaction is preferably 12 to 48 hours, and more preferably 20 to 30 hours.

Preferably, the preparation method of the giant molecule further comprises adding a water loss agent in any esterification reaction in the step 3). The fluid loss agent is preferably a carbodiimide, such as at least one selected from the group consisting of N, N '-Diisopropylcarbodiimide (DIC) and N, N' -Dicyclohexylcarbodiimide (DCC). In some preferred embodiments of the present invention, the water loss agent is N, N' -diisopropylcarbodiimide.

Preferably, in any esterification reaction in step 3), the molar ratio of the giant molecule side end compound to the water loss agent is 1: (1-20).

Preferably, in step 4), the molar ratio of the central unfunctionalized giant molecule, the third thiol and the photoinitiator is 1: (6-10): (0.05-0.5).

Preferably, in step 4) of the method for preparing the giant molecule, the third thiol is at least one selected from the group consisting of C2-C18 linear or branched thiols, 2,2, 2-trifluoroethanethiol, pentafluoropentanethiol, 1H,2H, 2H-perfluorodecylthiol, thioglycolic acid, 3-mercapto-1, 2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, 3-mercapto-2-methyl-1-pentanol, 3-mercapto-1-hexanol, 2-mercaptoethanol, 3-mercaptopropanol, α -thioglycerol, 2-mercaptobenzyl alcohol, and 4-mercaptobenzyl alcohol; more preferably, the third thiol is at least one selected from the group consisting of isopropyl thiol, n-butyl thiol, 2-mercaptoethanol, 3-mercaptopropanol, tert-butyl thiol, 1H,2H, 2H-perfluorodecyl thiol, thioglycolic acid, and 3-mercapto-1, 2-propanediol.

Preferably, in step 4), the concentration of the central unfunctionalized giant molecule in the solvent is 1 mg/mL-100 mg/mL.

Preferably, in step 1), step 2) and step 4), the photoinitiator is at least one selected from 2, 2-dimethoxy-2-phenylacetophenone (DMPA), 1-hydroxycyclohexyl phenyl ketone and methyl benzoylformate. In some preferred embodiments of the present invention, the photoinitiator is 2, 2-dimethoxy-2-phenylacetophenone.

Preferably, in the step 1), the step 2) and the step 4), the solvent is at least one selected from alkyl halide solvents, ether solvents, halogenated aromatic hydrocarbons, ester solvents and alcohol solvents; more preferably, the solvent is at least one selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran, and trifluorotoluene. In some preferred embodiments of the present invention, the solvent in step 1), step 2) and step 4) is anhydrous tetrahydrofuran or a mixed solvent of anhydrous tetrahydrofuran and anhydrous benzotrifluoride.

Preferably, in step 1), step 2) and step 4), the irradiation is ultraviolet irradiation. The wavelength of the ultraviolet light is preferably 365 nm.

Preferably, the preparation method of the giant molecule comprises the steps of 1), 2) and 4), wherein the illumination time is 10-50 min. Further preferably, the illumination time in the step 1) is 30-50 min; the time of any one of the light irradiation in the step 2) is 25 min-30 min; the illumination time in the step 3) is 17 min-22 min.

Preferably, the preparation method of the giant molecule further comprises a step of purification and separation after the reaction of each step of step 1), step 2), step 3) and step 4), wherein the purity is improved by purification and separation, and the purification and separation method comprises, but is not limited to, chromatography, extraction, dissolution precipitation separation, filtration, reduced pressure distillation, and the like. Further preferably, in step 2), step 3) and step 4), the giant molecule is purified by silica gel column or by preparative liquid chromatography HPLC.

The invention also provides the application of the giant molecule in the fields of chip manufacturing, energy, catalysis or biomedical engineering.

The invention has the beneficial effects that:

compared with the traditional multi-block copolymer, the series of giant molecules provided by the invention have highly accurate and controllable molecular sequence and spatial configuration. The preparation method can radically realize the adjustability of the giant molecule preparation, and has the advantages of simple steps, high reaction efficiency, mild conditions and the like.

Specifically, compared with the prior art, the invention has the following advantages:

1) the invention successfully constructs a giant molecule with accurate sequence and space configuration, and has wide potential application in the fields of chip manufacture, energy, catalysis, biomedical engineering and the like;

2) the giant molecule with precise sequence and spatial configuration prepared by the invention can contain various different functional groups, which is beneficial to showing richer self-assembly behaviors;

3) the preparation method has the characteristics of simple steps, high reaction efficiency and mild conditions.

Drawings

FIG. 1 is a structural diagram of a giant molecule according to example 1 of the present invention;

FIG. 2 is a structural diagram of the giant molecule of example 2 of the present invention;

FIG. 3 is a structural diagram of the giant molecule of example 3 of the present invention;

FIG. 4 is a schematic diagram of the giant molecule preparation step 1 according to example 1 of the present invention;

FIG. 5 is a schematic diagram of the giant molecule preparation step 2 according to example 1 of the present invention;

FIG. 6 is a schematic diagram of steps 3 and 4 of preparing the giant molecule according to example 1 of the present invention;

FIG. 7 shows the giant molecule center of the present inventionPolyhedral oligomeric silsesquioxane POSS_BNuclear magnetic silicon spectrum of (1);

FIG. 8 is a nuclear magnetic hydrogen spectrum of APOSS-p-VPOSS-OH (a), APOSS-p-VPOSS-FPOSS (b) and APOSS-p-DPOSS-FPOSS (c) in example 1 of the present invention;

FIG. 9 is a mass spectrum of APOSS-p-DPOSS-FPOSS in example 1 of the present invention.

Detailed Description

The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either conventionally commercially available or may be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.

DMPA described in the examples below represents 2, 2-dimethoxy-2-phenylacetophenone, DMAP represents 4-dimethylaminopyridine, and DIC represents N, N' -diisopropylcarbodiimide.

FIG. 1 is a giant molecular structure diagram of example 1 (APOSS-p-DPOSS-FPOSS). FIG. 2 is a giant molecular weight structural diagram of example 2 (APOSS-m-DPOSS-FPOSS). FIG. 3 is a giant molecular weight structural diagram of example 3 (APOSS-o-DPOSS-FPOSS). The following will further describe the specific preparation method in connection with examples 1 to 3.

The molar masses of the compounds are referred to below: the VPOSS-2OH molar mass is 787.97 g/mol; the VPOSS-OH molar mass is 709.96 g/mol; the VPOSS-Ac molar mass is 809.97 g/mol; the APOSS-Ac molar mass is 1440.32 g/mol; the mol mass of FPOSS-Ac is 4169.86 g/mol; the molar mass of APOSS-VPOSS-OH is 2210.28 g/mol; the molar mass of APOSS-VPOSS-FPOSS is 6362.13 g/mol; the molar mass of APOSS-DPOSS-FPOSS was 7010.28 g/mol.