KR102883175B1 - Polyhedral oligomeric silsesquioxane and its preparation method - Google Patents

Abstract

One embodiment of the present invention provides a polyhedral oligomeric silsesquioxane and a method for producing the same. The polyhedral oligomeric silsesquioxane according to one embodiment of the present invention is a siloxane bond-based structure with excellent thermal and chemical stability, and is a complex capable of introducing various physical and chemical properties, and an organic-inorganic hybrid body that introduces the advantages of organic substances into inorganic substances can exhibit previously unknown functional excellence.

Description

Polyhedral oligomeric silsesquioxane and its preparation method

The present invention relates to a polyhedral oligomeric silsesquioxane and a method for producing the same.

Polyhedral oligomeric silsesquioxane (POS) has an empirical formula of (RSiO _1.5 ) _n (n 6 And it is an organic-inorganic hybrid that can be expressed as R = hydrogen or organic functional group.

The above POSS can be structurally classified into ladder-type, (partial) cage-type, and amorphous, and each structure has different characteristics. Here, among the structural classifications, the cage-type POSS is a three-dimensional silica nanostructure hybrid having an inorganic silica inner core with a diameter of 1 nm to 3 nm composed of repeating siloxane (Si―O―Si) bonds, and an outer layer of an organic component introduced with various functional groups bonded to each vertex of the core.

The above cage-type POSS can be classified according to the reactivity of the side-chain organic functional groups. Specifically, it is classified into molecular silica when all side-chain organic functional groups are non-reactive, monofunctional POSS when one side-chain organic functional group is reactive, and multifunctional POSS when two or more side-chain organic functional groups are reactive.

Among these, the multifunctional octa-cage type POSS (T ₈ ; R ₈ Si ₈ O ₁₂ ) is the structure that is being most actively researched in the related field.

Multifunctional octa-cage POSSs with various side-chain organic functional groups exist, but representative examples primarily involve the introduction of aliphatic hydrocarbon or aromatic functional groups. Derivatization of limited side-chain organic functional groups ultimately limits the changes in physical and chemical properties.

In order to overcome various limitations and restrictions, including the problems mentioned above, research has been conducted recently on multifunctional octa-cage type POSS with functional groups such as halogen, amine, alcohol, nitrile, or isocyanate introduced, but actual application cases are extremely rare and scattered.

Therefore, to date, the development of multifunctional octa-cage-type POSS, despite its high research potential, has been limited to changing the length of the side-chain organic functional group or simply varying the introduced functional group.

Republic of Korea Patent Publication No. 2014-0035324

The technical problem to be achieved by the present invention is to provide a novel polyhedral oligomeric silsesquioxane material having a hexafluoroisopropanol terminal functional group structure and a method for producing the same.

The technical problems to be solved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by a person having ordinary skill in the technical field to which the present invention belongs from the description below.

To achieve the above technical task, one embodiment of the present invention provides a multifunctional polyhedral oligomeric silsesquioxane.

The multifunctional polyhedral oligomeric silsesquioxane according to one embodiment of the present invention is characterized by having a hexafluoroisopropanol functional group at the terminal and represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1, R is a hexafluoroisopropanol functional group represented by the following chemical formula 2,

[Chemical Formula 2]

In the above chemical formula 2, n is an integer from 0 to 10.

Additionally, according to one embodiment of the present invention, the hexafluoroisopropanol-based functional group may be included in an amount of 39 wt% to 57 wt% relative to the total content of the multifunctional polyhedral oligomeric silsesquioxane.

Additionally, according to one embodiment of the present invention, the multifunctional polyhedral oligomeric silsesquioxane may have hydrogen-bonding donor properties by including a hexafluoroisopropanol-based functional group.

In order to achieve the above technical task, another embodiment of the present invention provides a method for producing a multifunctional polyhedral oligomeric silsesquioxane.

The method for producing the multifunctional polyhedral oligomeric silsesquioxane according to one embodiment of the present invention comprises the steps of producing a mixture by adding octakis(dimethylsilyloxy)octasilsesquioxane, an aliphatic hydrocarbon having an olefin structure and hexafluoroisopropanol at the terminal, and a transition metal catalyst to an organic solvent; and

The method may include a step of producing a polyhedral oligomeric silsesquioxane (POSS) having a hexafluoroisopropanol terminal functional group structure by performing a hydrosilylation reaction through heat treatment on the above mixture.

In addition, according to one embodiment of the present invention, in the step of preparing the mixture,

The aliphatic hydrocarbon having hexafluoroisopropanol and an olefin structure at the terminal may be a compound represented by the following chemical formula 3.

[Chemical Formula 3]

In the above chemical formula 3, n is an integer from 0 to 10.

In addition, according to one embodiment of the present invention, in the step of preparing the mixture,

The content ratio of the above octakis(dimethylsilyloxy)octasilsesquioxane and the aliphatic hydrocarbon having hexafluoroisopropanol and an olefin structure at the terminal may be 1:8 to 1:10.

Additionally, according to one embodiment of the present invention, the transition metal catalyst may include a Karstedt catalyst.

Additionally, according to one embodiment of the present invention, the transition metal catalyst may be included in an amount of 1 mol% to 3 mol% relative to the entire mixture.

Additionally, according to one embodiment of the present invention, the concentration of the organic solvent may be 0.05 M to 0.1 M.

In addition, according to one embodiment of the present invention, in the step of manufacturing the polyhedral oligomeric silsesquioxane (POSS) having the hexafluoroisopropanol terminal functional group structure, the heat treatment may be performed at a temperature range of 100°C to 130°C.

In addition, according to one embodiment of the present invention, in the step of preparing the polyhedral oligomeric silsesquioxane (POSS) having the hexafluoroisopropanol terminal functional group structure, the hydrosilylation reaction may be performed for 72 to 100 hours.

According to one embodiment of the present invention, the polyhedral oligomeric silsesquioxane is a siloxane bond-based structure with excellent thermal and chemical stability, and is a complex capable of introducing various physical and chemical properties, and an organic-inorganic hybrid body that introduces the advantages of organic substances to inorganic substances can exhibit previously unknown functional excellence.

In addition, the polyhedral oligomeric silsesquioxane according to one embodiment of the present invention can be expected to have a functionalization strategy that causes changes in physical and chemical properties depending on the derivative structure, and can develop unique hydrogen-bonding donor properties by controlling hydrogen bonds or halogen bonds according to an approach from a non-covalent interaction perspective that is different from the conventional one.

Therefore, through this, it can be applied to fields in which polyhedral oligomeric silsesquioxane (POSS) was previously used, such as polymer chemistry, electronic/optical materials chemistry, pharmaceuticals, biochemistry, electrochemistry, energy chemistry, and catalytic chemistry.

The effects of the present invention are not limited to the effects described above, and should be understood to include all effects that can be inferred from the detailed description of the present invention or the composition of the invention described in the claims.

Figure 1 is a chemical reaction formula showing a method for producing a polyhedral oligomeric silsesquioxane according to one embodiment of the present invention.
Figure 2 is a chemical reaction formula showing a manufacturing method of a manufacturing example according to one embodiment of the present invention.
FIG. 3 is a ¹ H, ¹³ C, and ¹⁹ F NMR spectrum of a polyhedral oligomeric silsesquioxane according to an embodiment of the present invention.

Hereinafter, the present invention will be described with reference to the attached drawings. However, the present invention can be implemented in various different forms and is therefore not limited to the embodiments described herein. In the drawings, irrelevant parts have been omitted for clarity of description, and similar parts have been designated with similar reference numerals throughout the specification.

Throughout the specification, when a part is said to be "connected (connected, contacted, or coupled)" to another part, this includes not only cases where it is "directly connected," but also cases where it is "indirectly connected" with another member in between. Furthermore, when a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

The terminology used herein is merely used to describe specific embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprises" or "has" indicate the presence of a feature, number, step, operation, component, part, or combination thereof described in the specification, but do not exclude in advance the possibility of the presence or addition of one or more other features, numbers, steps, operations, components, parts, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings.

A multifunctional polyhedral oligomeric silsesquioxane according to one embodiment of the present invention is described.

A multifunctional polyhedral oligomeric silsesquioxane according to one embodiment of the present invention has a hexafluoroisopropanol-based functional group at the terminal of the polyhedral oligomeric silsesquioxane and is characterized by being represented by the following chemical formula 1.

[Chemical Formula 1]

In the above chemical formula 1,

The above R is a functional group represented by the following chemical formula 2,

[Chemical Formula 2]

In the above chemical formula 2, n is an integer from 0 to 10.

Polyhedral oligomeric silsesquioxane (POS) refers to a siloxane material with a three-dimensional structure, generally (RSiO _1.5 ) _n (n 6 And it is expressed as a molecular formula in the form of R = hydrogen or organic functional group.

In addition, the above POSS is being widely studied as an organic-inorganic hybrid nano-scale material because the silicon-oxygen bond forms the basic form of the molecule as an inorganic frame, and R can be composed of various organic groups.

In addition, since the molecular diameter of the above POSS is in the range of several nanometers, it exhibits quantum size effects, quantum surface effects, quantum interface effects, etc., and due to these quantum characteristics, the POSS material can have unique physical and chemical properties in various areas such as thermal conductivity, electrical conductivity, optics, magnetism, hydrophilicity, lipophilicity, etc., and it also allows for the introduction of these properties to the surface of polymers, etc.

In particular, since POSS's basic form is composed of a silicon-oxygen bond (silsesquioxane form), its molecular structure is physically and chemically very stable, and it has high heat resistance and flame resistance.

In addition, under high temperature and high pressure conditions, the inorganic frame of POSS can be decomposed to form a separate coating layer by generating silica (SiO ₂ ), so it can very faithfully perform its role as a protective layer.

In addition, since various functional groups can be bonded to silicon atoms in the basic silsesquioxane structure of POSS, it is easy to impart various new properties depending on the structure of the introduced organic group.

The present invention is characterized in that the basic silsesquioxane structure of the POSS includes a hexafluoroisopropanol group as a functional group.

The above hexafluoroisopropanol group is a functional group having two CF ₃ groups, and is characterized by having higher acidity than general alcohol.

At this time, since the hexafluoroisopropanol group has an electron-deficient structure, it can activate the molecule by non-covalent interaction with a molecule including an electron-rich functional group (e.g., a carbonyl group), and thus can act as a catalyst in an organic synthesis (e.g., an addition reaction) process.

Therefore, the hexafluoroisopropanol functional group can play a role in increasing the lipid solubility of silsesquioxane and enhancing the recognition effect for molecules containing electron-rich functional groups due to hydrogen bond donating function.

At this time, R according to one embodiment of the present invention is characterized by being represented by the following chemical formula 2.

[Chemical Formula 2]

In the above chemical formula 2, n is an integer from 0 to 10.

At this time, the hexafluoroisopropanol may be included in an amount of 39 wt% to 57 wt% relative to the total content of the multifunctional polyhedral oligomer silsesquioxane.

At this time, if the content of the hexafluoroisopropanol is less than 39 wt%, there may be a problem of insufficient bonding of the hexafluoroisopropanol functional group to the polyhedral oligomer silsesquioxane terminal, and if it exceeds 57 wt%, there may be a problem of reactivity of the hydrogen silication reaction. Therefore, the content of the hexafluoroisopropanol of the present invention was set to 39 wt% to 57 wt%.

Therefore, the polyhedral oligomeric silsesquioxane according to one embodiment of the present invention is characterized by having an octa-cage type polyhedral oligomeric silsesquioxane structure, excellent thermal stability and chemical stability, and the ability to have a recognition effect on molecules including electron-rich functional groups, including hexafluoroisopropane functional groups.

Referring to FIG. 2, a method for producing a multifunctional polyhedral oligomer silsesquioxane of the present invention is described.

Figure 2 is a chemical reaction formula showing a manufacturing method of a manufacturing example according to one embodiment of the present invention.

Referring to FIG. 2, a method for producing a multifunctional polyhedral oligomeric silsesquioxane according to an embodiment of the present invention may include the steps of: preparing a mixture by adding octakis(dimethylsilyloxy)octasilsesquioxane, an aliphatic hydrocarbon having an olefin structure and hexafluoroisopropanol at the terminal, and a transition metal catalyst to an organic solvent; and performing a hydrosilylation reaction through heat treatment on the mixture, thereby producing a polyhedral oligomeric silsesquioxane (POSS) having a hexafluoroisopropanol terminal functional group structure.

In the first step, a step of preparing a mixture may be included by introducing octakis(dimethylsilyloxy)octasilsesquioxane, an aliphatic hydrocarbon having an olefin structure at the terminal and hexafluoroisopropanol, and a transition metal catalyst into an organic solvent.

At this time, the aliphatic hydrocarbon having hexafluoroisopropanol and an olefin structure at the terminal may be a compound represented by the following chemical formula 3.

[Chemical Formula 3]

In the above chemical formula 3, n is an integer from 0 to 10.

The content ratio of the above octakis(dimethylsilyloxy)octasilsesquioxane and the aliphatic hydrocarbon having hexafluoroisopropanol and an olefin structure at the terminal may be 1:8 to 1:10.

At this time, if the content ratio of the octakis(dimethylsilyloxy)octasilsesquioxane and the aliphatic hydrocarbon having hexafluoroisopropanol and an olefin structure at the terminal is less than 1:8, there may be a problem of insufficient bonding of the hexafluoroisopropanol functional group to the terminal of the polyhedral oligomer silsesquioxane, and if it exceeds 1:10, there may be a problem of reactivity of the hydrosilylation reaction, so the content ratio may be 1:8 to 1:10.

Additionally, in the present invention, the transition metal catalyst may include a Karstedt catalyst.

At this time, the transition metal catalyst may be included in an amount of 1 mol% to 3 mol% relative to the entire mixture.

Additionally, the organic solvent used in the present invention may include toluene.

At this time, the concentration of the organic solvent is characterized as being 0.05 M to 0.1 M.

Specifically, the present invention can be carried out by adding octakis(dimethylsilyloxy)octasilsesquioxane (1 equivalent, 0.3 mmol) and toluene (anhydrous, 0.05 M, 6 ml) to a flame-dried round-bottom flask equipped with a magnetic stirring bar and a reflux condenser and filled with argon gas; and adding an aliphatic hydrocarbon (10 equivalents) based on homoallylic alcohol having a hexafluoroisopropanol and an olefin structure at each end and a Karlstedt catalyst (1 mol%) to prepare a mixture.

In the second step, a step of performing a hydrosilylation reaction through heat treatment on the mixture may be included to produce a polyhedral oligomeric silsesquioxane (POSS) having a hexafluoroisopropanol terminal functional group structure.

The above hydrosilylation reaction is a reaction that breaks the pi bond of a functional group containing a double or triple bond and bonds hydrogen and silicon to each atom. It is generally widely used for alkenes (C=C) and alkynes (C≡C) containing carbon-carbon pi bonds, but it can also be applied to ketone (C=O) or imine (C=N) functional groups containing heteroatoms.

The hydrogen silicification reaction of the present invention can be performed through heat treatment, and the heat treatment can be performed at a temperature range of 100°C to 130°C.

In addition, the hydrogen silicification reaction of the present invention is characterized in that it is performed for 72 to 100 hours.

Hereinafter, the present invention will be described in more detail through manufacturing examples and experimental examples. These manufacturing examples and experimental examples are intended solely to illustrate the present invention, and the scope of the present invention is not limited by these manufacturing examples and experimental examples.

Manufacturing example: Manufacturing of multifunctional polyhedral oligomeric silsesquioxane

Referring to FIG. 2, a method for producing a multifunctional polyhedral oligomer silsesquioxane is described.

First, install a magnetic stirring bar and a reflux condenser, and add octakis(dimethylsilyloxy)octasilsesquioxane (1 equivalent, 0.3 mmol) and toluene (anhydrous, 0.05 M, 6 ml) to a flame-dried round-bottom flask filled with argon gas.

Next, a mixture was prepared by adding hexafluoroisopropanol and homoallylic alcohol-based aliphatic hydrocarbons having an olefin structure (10 equivalents) and a Karlstedt catalyst (1 mol%) to each terminal.

Next, the mixture was subjected to a hydrosilication reaction through heat treatment at 110°C for 72 hours to produce a polyhedral oligomeric silsesquioxane (POSS) having a hexafluoroisopropanol terminal functional group structure.

Next, the polyhedral oligomeric silsesquioxane (POSS) was cooled to room temperature, activated charcoal (100 g/mol) was added, and stirred at room temperature for 12 hours.

Afterwards, the reaction mixture was filtered through Celite ^® 545 and concentrated under reduced pressure.

The residue was further dried in an oven at 120°C for 12 hours, resulting in the corresponding composite being obtained as a brown wax.

Experimental example

In this experimental example, the synthesis of the polyhedral oligomeric silsesquioxane (POSS) was confirmed through ¹ H NMR analysis of Figure 3.

FIG. 3 is a ¹ H, ¹³ C, and ¹⁹ F NMR spectrum of a polyhedral oligomeric silsesquioxane according to an embodiment of the present invention.

Referring to the above Figure 3, the ¹ H, ¹³ C, and ¹⁹ F NMR spectrum analysis data of the above manufacturing example are as follows.

¹ H NMR (500 MHz, CDCl ₃ , Me ₄ Si) shows δ2.86 (s, 6H), 2.04 - 1.86 (m, 16H), 1.68 - 1.46 (m, 16H), 0.71 - 0.56 (m, 16H), 0.15 (s, 48H), ¹³ C NMR (126 MHz, CDCl ₃ , Me ₄ Si) is δ123.13 (q, J = 287.8 Hz), 76.09 (m), 33.70, 17.84, 15.61, -0.64, ¹⁹ F NMR (470 MHz, CDCl ₃ ) is δ-76.70 (s, 48F) am.

Referring to the above Figure 3, it can be confirmed that a multifunctional polyhedral oligomeric silsesquioxane having a hexafluoroisopropanol functional group at the end of the polyhedral oligomeric silsesquioxane was produced.

The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

The scope of the present invention is indicated by the claims described below, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims (11)

It has a hexafluoroisopropanol functional group at the terminal and is represented by the following chemical formula 1.
A multifunctional polyhedral oligomeric silsesquioxane characterized in that the above hexafluoroisopropanol-based functional group is included in an amount of 39 wt% to 57 wt% based on the total content of the multifunctional polyhedral oligomeric silsesquioxane:
[Chemical Formula 1]

In the above chemical formula 1, R is a hexafluoroisopropanol functional group represented by the following chemical formula 2,
[Chemical Formula 2]

In the above chemical formula 2, n is an integer from 0 to 10.
delete In the first paragraph,
The above multifunctional polyhedral oligomeric silsesquioxane is characterized by having hydrogen-bonding donor properties by including a hexafluoroisopropanol-based functional group. A step of preparing a mixture by adding octakis(dimethylsilyloxy)octasilsesquioxane, an aliphatic hydrocarbon having an olefin structure and hexafluoroisopropanol at the terminal, and a transition metal catalyst to an organic solvent; and
A step of producing a polyhedral oligomeric silsesquioxane (POSS) having a hexafluoroisopropanol terminal functional group structure by performing a hydrosilylation reaction through heat treatment on the above mixture; including,
In the step of preparing the above mixture,
By setting the content ratio of the above octakis(dimethylsilyloxy)octasilsesquioxane and the aliphatic hydrocarbon having hexafluoroisopropanol and olefin structure at the terminal to 1:8 to 1:10,
A method for producing a multifunctional polyhedral oligomeric silsesquioxane, characterized in that the above hexafluoroisopropanol-based functional group is included in an amount of 39 wt% to 57 wt% based on the total content of the multifunctional polyhedral oligomeric silsesquioxane. In paragraph 4,
In the step of preparing the above mixture,
A method for producing a multifunctional polyhedral oligomeric silsesquioxane, characterized in that the aliphatic hydrocarbon having a hexafluoroisopropanol and olefin structure at the terminal is a compound represented by the following chemical formula 3:
[Chemical Formula 3]

In the above chemical formula 3, n is an integer from 0 to 10. delete In paragraph 4,
A method for producing a multifunctional polyhedral oligomeric silsesquioxane, characterized in that the above transition metal catalyst comprises a Karstedt catalyst. In paragraph 4,
A method for producing a multifunctional polyhedral oligomeric silsesquioxane, characterized in that the above transition metal catalyst is included in an amount of 1 mol% to 3 mol% relative to the entire mixture. In paragraph 4,
A method for producing a multifunctional polyhedral oligomeric silsesquioxane, characterized in that the concentration of the organic solvent is 0.05 M to 0.1 M. In paragraph 4,
In the step of manufacturing polyhedral oligomeric silsesquioxane (POSS) having the above hexafluoroisopropanol terminal functional group structure,
A method for producing a multifunctional polyhedral oligomeric silsesquioxane, characterized in that the above heat treatment is performed in a temperature range of 100°C to 130°C. In paragraph 4,
In the step of manufacturing polyhedral oligomeric silsesquioxane (POSS) having the above hexafluoroisopropanol terminal functional group structure,
A method for producing a multifunctional polyhedral oligomeric silsesquioxane, characterized in that the above hydrosilylation reaction is performed for 72 to 100 hours.