KR20100131904A - Process for preparing organic-inorganic hybrid graft polysilsesquioxane and graft polysilsesquioxane produced thereby - Google Patents

Abstract

PURPOSE: A method for preparing organic-inorganic hybrid graft polysilsesquioxane is provided to obtain polysilsesquioxanes with a highly functioned ladder structure by easily grafting various functional monomers to a side chain of polysilsesquioxane. CONSTITUTION: A method for preparing organic-inorganic hybrid graft polysilsesquioxane comprises a step for polymerizing one or more kinds of an unsaturated hydrocarbon-based monomer to a side chain of polysilsesquioxane represented by chemical formula 1 to form polysilsesquioxane with which a homopolymer or copolymer with the unsaturated hydrocarbon-based monomer at a side chain is grafted.

Description

Preparation Method of Organic-Inorganic Hybrid Graft Polysilsesquioxane and Graft Polysilsesquioxane Prepared by the Graft Polysilsesquioxane and Graft Polysilsesquioxane prepared by the same

The present invention relates to a method for preparing graft polysilsesquioxane and to graft polysilsesquioxane produced thereby, more particularly, to a single polymer consisting of one or more organic functional groups in the side chain of polysilsesquioxane or It relates to a method for producing graft polysilsesquioxane capable of grafting a copolymer and to graft polysilsesquioxane produced thereby.

Currently, research on new polymer materials is evolving toward functionalization by giving thermal, mechanical, and electrical properties to polymers, and it is appropriate to develop organic-inorganic hybrid materials with a hybrid structure of organic and inorganic materials. It is attracting attention as a new technology. The most important point in the production of organic-inorganic hybrid materials is that there should be no compatibility problems with organic, inorganic monomers or polymers, and that stability can be ensured without thermal gradient phenomenon. As a material that meets these scientific requirements, the high heat-resistant polysilsesquioxane proposed in many papers and patents has been in the spotlight. In particular, polysilsesquioxane-based materials are widely used in heat resistant materials, weather resistant materials, impact resistant materials, packaging materials, encapsulation materials, insulating materials, lubricants, release agents, and semi-gas permeable coatings in the form of oils, rubbers, resins, and the like. It is recognized as an extremely important polymer throughout the industry.

This organic functionalization method of polysilsesquioxane is to prepare a polysilsesquioxane having a ladder structure using a trifunctional silane monomer (eg, trialkoxysilane, trichlorosilane) in which the side chain is already functionalized. Method; After forming a polymer having a ladder structure by using a monomer having a reactor such as halogen or amine, it may be divided into a method of further functionalizing and functionalizing a side chain through a post reaction in a polymer state.

In the case of using the monomer in which the side chain is functionalized, the functionality of the functional group is fixed, and physical properties, chemical properties and the like can be adjusted only by controlling the molecular weight. In addition, if the size of the functional group becomes too large, it is difficult to control to have a perfect ladder structure in the polymerization reaction of trialkoxysilane or trichlorosilane, unreacted -OH interspersed in the middle of the polymer structure to promote gelation, This places many restrictions on reproducibility and functionality.

As a method for overcoming these shortcomings, a method of first preparing a ladder-type polysilsesquioxane having a reactive side chain and then further functionalizing the side chain portion through a reaction has been studied. In this case, since the main chain of the complete ladder structure can be secured in a stable state without defects, the gelation phenomenon can be prevented in the subsequent side chain functionalization reaction, and the functionalization of the side chain portion can be adjusted to a desired degree. However, since the side chain functionalization is performed in the form of the polymer, the structure of the polysilsesquioxane must be well controlled so that there is no unreacted -OH that can be interspersed in the middle of the chain for perfect side chain functionalization, and the method of the side chain functionalization is also a side reaction. In order to minimize the need to proceed with a precise polymerization method, it is recognized that these points are difficult to synthesize and manufacture has not been made many attempts.

Therefore, the present inventors have continually studied and experimented to overcome the limitations of the side chain functionalization of polysilsesquioxane, and as a result of the structural control, the polysilsesquioxane having a halogen side chain was formed in a regular ladder shape. By using this as an initiator of the living radical polymerization reaction, graft polymerization of unsaturated hydrocarbon monomers to the side chains of polysilsesquioxane by the Atom Transfer Radical Polymerization (ATRP) method, thereby making the side chains highly functionalized with various organic functional groups. One graft polysilsesquioxane has been reached in a stable and easy manner.

It is therefore an object of the present invention to provide a process for producing organic-inorganic hybrid graft polysilsesquioxanes having side chains grafted with organic functional groups. It is also an object of the present invention to provide an organic-inorganic hybrid graft polysilsesquioxane prepared by the above-mentioned preparation method.

According to one embodiment of the present invention, by graft polymerization of at least one type of unsaturated hydrocarbon monomer in the side chain of the polysilsesquioxane represented by the following formula (1), homopolymer or air composed of the unsaturated hydrocarbon monomer in the side chain A method for producing graft polysilsesquioxane is provided, wherein the coalesce forms grafted polysilsesquioxane.

[Formula 1]

In formula (1), R ₁ is selected from alkyl group having 1 to 12 carbon atoms, acryl group, benzyl group, phenyl group, thiophene and pyrrole group; R ₂ is selected from alkyl group, acryl group, benzyl group, phenyl group, thiophene, pyrrole group, allyl group, vinyl group, epoxy group, methacryl group and acryl; X ₁ is halogen of F, Cl, Br or I; X ₂ is said halogen or hydrogen; n is an integer from 10 to 10,000.

In an embodiment of the present invention, the unsaturated hydrocarbon monomer may be grafted to the side chain of the polysilsesquioxane of Chemical Formula 1 by atom transfer radical polymerization.

In an embodiment of the present invention, at least one or more of X ₁ and X ₂ may be the starting point of the atom transfer radical polymerization.

In an embodiment of the present invention, the graft polymerization of the unsaturated hydrocarbon-based monomer may be performed under a transition metal catalyst including ruthenium or copper. In addition, in the graft polymerization of the unsaturated hydrocarbon monomer, a ligand including at least one of amine and pyridine may be added.

In an embodiment of the present invention, the unsaturated hydrocarbon monomer may be a styrene monomer, an acrylate monomer or vinyl pyridine.

In an embodiment of the present invention, the copolymer may be a random copolymer, a block copolymer or an alternating copolymer.

According to embodiments of the present invention, a highly functionalized graft polysilsesquioxane may be provided having a side chain grafted to a homopolymer or copolymer comprising one or more types of unsaturated hydrocarbon-based monomers.

According to embodiments of the present invention, graft polysilsesquioxanes having a molecular weight distribution of 1 to 3 may be provided.

According to the production method according to the embodiment of the present invention, by using a polysilsesquioxane having a ladder structure in which the halogen element is introduced into the side chain as a macro initiator of the atom transfer radical polymerization, unsaturated hydrocarbon monomers are atom transfer radical polymerization method It can be easily grafted to the side chain of polysilsesquioxane.

In addition, according to the production method of the present invention, since two or more kinds of various organic functional groups can be grafted in a random, alternating or block copolymerized form, it is possible to provide a highly functionalized graft polysilsesquioxane having a side chain.

Furthermore, the graft polysilsesquioxane formed by the production method of the present invention exhibits excellent physical properties such as heat resistance, transparency and coating properties, and thus can be widely used in various fields.

Hereinafter, a method for preparing graft polysilsesquioxane according to an embodiment of the present invention will be described in detail.

According to an embodiment of the present invention, a polysilsesquioxane represented by the following general formula (1) having a halogen in the side chain is synthesized as a precursor of living radical polymerization, and at least one unsaturated hydrocarbon in the side chain of the polysilsesquioxane of the general formula (1) A method of graft polymerizing a monomer is provided to form a polysilsesquioxane grafted with a homopolymer or a copolymer of the unsaturated hydrocarbon monomer in the side chain.

[Formula 1]

In Formula 1, R ₁ is selected from an alkyl group having 1 to 12 carbon atoms, an acryl group, a benzyl group, a phenyl group, a thiophene and a pyrrole group, and R ₂ is an alkyl group, an acryl group, a benzyl group, a phenyl group, a thiophene, a pyrrole group , Allyl groups, vinyl groups, epoxy groups, methacryl groups, and acrylics. X ₁ is a halogen of F, Cl, Br or I, X ₂ is the halogen or hydrogen, n may be an integer of 10 to 10,000.

In the present invention, the "alkyl group" is a C1-C24 side chain or crushed alkyl group, such as a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, t-butyl group, and is cyclopropyl group, cyclo And a cycloalkyl group having 3 to 10 carbon atoms such as a pentyl group and a cyclohexyl group.

In an embodiment of the present invention, the polysilsesquioxane represented by Formula 1 is R ₁ and R ₂ may be different random copolymers or block copolymers.

In an embodiment of the present invention, the polysilsesquioxane represented by Chemical Formula 1 may have a number average molecular weight (Mn) in the range of about 1,000 to 100,000, and may have a molecular weight distribution (Mw / Mn) of 1 to 8. have.

In an embodiment of the present invention, the method for preparing polysilsesquioxane represented by Chemical Formula 1 may be briefly represented by the following Scheme 1.

Scheme 1

In Scheme 1, R is an alkyl group, and R ₁ , R ₂ , X ₁ , X ₂ are each as defined above.

According to the production method according to Scheme 1, polysilsesquioxane represented by the formula (1) can be prepared by condensation polymerization of the hydrolyzate of the trialkoxy monomer. At this time, an alkali metal catalyst such as alkali metal hydroxide or a basic catalyst such as triethylamine can be used as the catalyst for condensation polymerization of silsesquioxane, and the polycondensation reaction can be carried out at a temperature of room temperature to 120 ° C.

According to the preparation method according to Scheme 1, polysilsesquioxane of the general formula (1) having a halogen element in the side chain and well controlled by a regular ladder structure can be synthesized without -OH group in the portion except the terminal.

In the embodiment of the present invention, the polysilsesquioxane represented by the formula (1) having a regular ladder structure, the side chain functionalized by R ₁ , R ₂ , X ₁ , X ₂ is a known method [A. WITTINGHAM et al., J. Organometallic Chem., 13, 125 (1968); H. BECKERS et al., J. Organometallic Chem., 316, 41 (1986); J. Frohn et al., J. Organometallic Chem., 506, 155 (1996)].

Polysilsesquioxanes of formula (1) can be used as macro initiators of atom transfer radical polymerization. In this case, at least one or more of X ₁ and X ₂ may be an initiation point of atomic transfer radical polymerization. That is, since at least one of X ₁ and X ₂ is halogen, it may be an initiation point of atomic transfer radical polymerization. Therefore, one or more types of unsaturated hydrocarbon monomers can be graft polymerized to the side chain of polysilsesquioxane of the general formula (1) by atom transfer radical polymerization. Accordingly, organic-inorganic hybrid polysilsesquioxanes in which side chains are grafted with various organic functional groups can be prepared.

In an embodiment of the present invention, when X ₁ and X ₂ of the general formula (1) is halogen, X ₁ and X ₂ is the starting point of living radical polymerization, unsaturated hydrocarbon-based monomers in both X ₁ and X ₂ bonded side chains Can be graft polymerized. In addition, in Formula 1, when X ₁ is halogen and X ₂ is hydrogen, unsaturated hydrocarbon monomers may be graft polymerized only on the side chain to which X ₁ is bonded.

In an embodiment of the present invention, one or more kinds of unsaturated hydrocarbon-based monomers may be graft polymerized to the side chain of Formula 1, and thus, polysilyl having a homopolymer or copolymer grafted to the side chains of the unsaturated hydrocarbon-based monomer. Sesquioxanes may be formed. The copolymer can be a block copolymer, an alternating copolymer or a random copolymer.

In the embodiment of the present invention, the unsaturated hydrocarbon monomer is not particularly limited as long as it has a monomer having an unsaturated bond suitable for atom transfer radical polymerization. For example, as the unsaturated hydrocarbon monomer, a styrene monomer, an acrylate monomer or a pyridine may be used.

In an embodiment of the present invention, the graft polymerization of the unsaturated hydrocarbon monomer by the atom transfer radical polymerization method may be performed under a transition metal catalyst. The transition metal catalyst may be Cu (I) Br, Cu (I) Cl, Cu (II) Br ₂ , Cu (II) Cl ₂ or Ru (II) (PPh ₃ ) ₃ Cl ₂ (Ph = C ₆ H ₅ Transition metal compound containing copper or ruthenium, such as) may be used, but is not limited thereto.

In an embodiment of the present invention, a ligand forming a complex with the transition metal catalyst may be used in the graft polymerization of the unsaturated hydrocarbon monomer. The ligand may be appropriately selected depending on the transition metal catalyst used. When using a transition metal compound containing copper or ruthenium as the transition metal catalyst, a ligand containing at least one of amine or pyridine may be added. Specific examples of the ligand may include Bpy (2,2'-Bipyridine), dNBpy, PMDETA (N, N, N ', N', N "-pentamethyldiethylenetriamine), NBu ₃ , NHBu ₂ or NH ₂ Bu. In addition, Al (Oi-Pr) ₃ (Aluminum isopropoxide) or MeAl (ODBP) ₂ may be used as a ligand.

In one exemplary embodiment of the present invention, a polysilsesquioxane represented by the following Chemical Formula 2 or Formula 3 is prepared by graft polymerizing a first unsaturated hydrocarbon-based monomer on the side chain of the polysilsesquioxane of Chemical Formula 1 can do.

[Formula 2]

(3)

In Formula 2 and _{3, R 1, R 2,} X 1, X 2 and n have the general formula (I) of _{R 1, R 2, X 1} , X 2 , and the same as n, and, R ₃ is the first unsaturated hydrocarbon-based monomer It is a repeating unit derived from the 1st hydrocarbon type monomer grafted to the side chain of polysilsesquioxane by the atom transfer radical polymerization method. m is an integer from 1 to 10,000. The degree of polymerization m may be adjusted differently depending on the field of application of the graft polysilsesquioxane, and may be adjusted to a degree of polymerization of 1 to 10,000 depending on the change in the reaction time.

In Formula 1, when X ₁ and X ₂ are halogen, since X ₁ and X ₂ serve as an initiation point of the atom transfer radical polymerization, the first unsaturated hydrocarbon monomer is graphed on both side chains to which X ₁ and X ₂ are bonded. Polymerization to form a polysilsesquioxane of formula (2).

In addition, the graft wherein X ₁ is halogen and X ₂ is a a hydrogen, X ₁ manyi therefore acts as a starting point for the atom transfer radical polymerization, X ₁ is-bonded side chains only in the first unsaturated hydrocarbon-based monomer in the formula (1) By polymerization, polysilsesquioxane of formula 3 may be formed.

In another exemplary embodiment of the present invention, the polysilsesquioxane represented by the following formula (4) or (5) by graft polymerization of the first and second unsaturated hydrocarbon monomers in the side chain of the polysilsesquioxane of formula (1) Can be formed. The first and second unsaturated hydrocarbon monomers may be different or the same.

[Formula 4]

[Chemical Formula 5]

Formula (4) and _{R 1, R 2, X 1} , X 2 and n 5 is the same as _{R 1, R 2, X 1} , X 2 , and n of formula 1, R ₃ is derived from a first unsaturated hydrocarbon-based monomer Is a repeating unit and R ₄ is a repeating unit derived from a second unsaturated hydrocarbon-based monomer, m is an integer of 1 to 10,000, u is an integer of 1 to 10,000. The m and u may be adjusted differently depending on the application of the graft polysilsesquioxane, and may be adjusted to a degree of polymerization of 1 to 10,000 depending on the change in the reaction time.

In the formula (1), when both X ₁ and X ₂ are reactive halogens, since X ₁ and X ₂ act as an initiation point of the atom transfer radical polymerization, the X ₁ and X ₂ are bound to the side chain to which X ₁ and X ₂ are bonded by the atom transfer radical polymerization method. Each of the first and second unsaturated hydrocarbon-based monomers may be graft polymerized to form a polysilsesquioxane of Formula 4.

In addition, in Formula 1, when X ₁ is halogen and X ₂ is hydrogen, since only X ₁ serves as an initiation point of atomic transfer radical polymerization, the first and second unsaturated hydrocarbon monomers in the side chain to which X ₁ is bonded May be graft polymerized to form a polysilsesquioxane of Formula 5.

In Formulas 4 and 5, R ₃ and R ₄ are hydrocarbon monomers grafted to the side chain of polysilsesquioxane by atom transfer radical polymerization. R ₃ and R ₄ may be grafted with regularity in a form arranged alternately with each other, or may be grafted freely in a random form. In addition, R ₃ and R ₄ may be grafted in the form of blocks that are each repeatedly arranged.

In another exemplary embodiment of the present invention, a method for preparing graft polysilsesquioxane includes graft polymerizing a first unsaturated hydrocarbon-based monomer in a side chain of polysilsesquioxane of Chemical Formula 1; And graft polymerizing the second unsaturated hydrocarbon monomer on the side chain of the polysilsesquioxane grafted with the first unsaturated hydrocarbon monomer. The manufacturing process of graft polysilsesquioxane according to another exemplary embodiment of the present invention may be made by a mechanism represented by Scheme 2 and Scheme 3, respectively.

Scheme 2

Scheme 3

In Schemes 2 and 3, M is a transition metal that acts as a catalyst in atom transfer radical polymerization, and may be copper or ruthenium. In addition, in reaction equations 2 and 3, k _p is the rate constant associated with the growth of the polymer, k _t is the rate constant associated with the termination of the polymer growth, and k _act and k _deact are the rate constants of the forward and reverse reactions in the atomic transfer radical polymerization reaction. to be.

In the primary atom transfer radical polymerization reaction according to Scheme 2, by reacting a polysilsesquioxane of the formula (1) with a transition metal catalyst containing a copper or ruthenium, a ligand and a first unsaturated hydrocarbon-based monomer, by reacting R _{3 to the} side chain The functional group of can form a polysilsesquioxane grafted. In the secondary atom transfer radical polymerization reaction according to Scheme 3, which is a subsequent reaction of the primary atom transfer radical polymerization reaction, a transition metal catalyst, a ligand and a second polymer are added to the polysilsesquioxane having a side chain to which the polymer of R ₃ is grafted. By adding an unsaturated hydrocarbon monomer and reacting, polysilsesquioxane by which the functional group of R <_4> was additionally graft-polymerized can be manufactured. In this case, as the second unsaturated hydrocarbon monomer, one having compatibility with a functional group of R ₃ is used.

As such, as a result of atom transfer radical polymerization according to Schemes 2 and 3, polysilsesquioxane in which the block copolymer of R ₃ and R ₄ is grafted to the side chain may be prepared.

Further, in another exemplary embodiment of the present invention, by simultaneously adding the first and second unsaturated hydrocarbon-based monomers by graft polymerization of the first and second unsaturated hydrocarbon-based monomers to the side chain of the polysilsesquioxane of formula (1) Polysilsesquioxanes in which the random copolymers of R ₃ and R ₄ are grafted to the side chain can be prepared.

According to the preparation method according to the embodiment of the present invention, a single polymer composed of one type of unsaturated hydrocarbon monomer, or a random copolymer, alternating copolymer or block copolymer composed of two or more kinds of unsaturated hydrocarbon monomers is formed on the side chain of the polysilyl chloride. Sesquioxanes may be provided. The graft polysilsesquioxane formed by the preparation method according to the embodiment of the present invention has a number average molecular weight (Mn) in the range of 5,000 to 1,000,000, and may have a molecular weight distribution (Mn / Mw) in the range of 1 to 3. have.

According to the production method according to the embodiment of the present invention, polysilsesquioxane having a side chain in which various kinds of functional groups are grafted according to the type of unsaturated hydrocarbon monomer used in the atom transfer radical copolymerization reaction can be prepared. . By the production method according to the embodiment of the present invention, a functional group (functional group) that can be grafted to the side chain of polysilsesquioxane includes an amine group, a phosphine group, a halogen group, an alcohol group, a sulfone group, a ketone group, an aldehyde Groups, nitrile groups, carboxylic acid groups, acyl chloride groups, ester groups, vinyl groups, aryl groups, allene groups, anhydride groups, amide groups and the like can be included.

In addition, since at least one of X ₁ and X _{2, which} are the side chain ends of the graft polysilsesquioxane formed by the production method of the present invention, is halogen, a functional group may be further added to the side chain through a post reaction. Therefore, according to the manufacturing method of this invention, the quantity and kind of the functional group graft-polymerized to the side chain of polysilsesquioxane can be adjusted easily. This can provide high molecular weight organic-inorganic hybrid graft polysilsesquioxanes with highly functionalized side chains.

In addition, the graft polysilsesquioxane formed by the production method of the present invention is a polymer having a highly regular ladder structure, and since gelling does not occur during the polymerization process, a general organic solvent such as toluene, xylene, benzene and chloro Aromatic hydrocarbons such as benzene; Halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethylene, trichloroethylene and trichloroethane; Ethers such as tetrahydrofuran (THF), 1,4-dioxane, diethyl ether and dibutyl ether; Ketones such as acetone, methyl ethyl ketone and methyl ether ketone; Esters such as butyl acetate, ethyl acetate and methyl acetate; It is very excellent in dissolution characteristics in general organic solvents such as dimethylformamide.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only for illustrating the present invention, and the scope of the present invention is not limited by these examples.

Example 1: Preparation of polystyrene-g-polysilsesquioxane

(1) Synthesis of polysilsesquioxane to be used as a macro-initiator

Tetrahydrofuran (40 g) and distilled water (24 g) for HPLC were prepared, and potassium hydroxide (0.2 g) as a catalyst was dissolved therein and stirred for 20 minutes. Chlorobenzyltrimethoxysilane (0.4 mol) was added dropwise to the mixed solution prepared in advance as a trialkoxy monomer, followed by stirring. After completion of the addition, the reaction proceeds, and the completion time is completed based on the point at which the molecular weight no longer increases through gel permeation chromatography (GPC). Then, by using a solvent that can dissolve the silsesquioxane-based material without mixing with water such as chloroform, methylene chloride, toluene, xylene, and the like by purification by fractional distillation to have a reactive group of Cl in the side chain terminal Polysilsesquioxane represented by was obtained.

[Formula 6]

The structure of the synthesized polysilsesquioxane of Chemical Formula 6 was analyzed by ¹ H NMR, ²⁹ Si NMR (Spuls method) and FT-IR, and the analysis results are shown in FIGS. 1 and 2. In addition, GPC measurement results of the polysilsesquioxane of Chemical Formula 6 are shown in FIG. 3.

In the ¹ H NMR spectrum shown in Figure 1, the peak of the CH ₂ group bonded to Cl appeared in the 4.1 ~ 4.7ppm section, the peak of CH of the phenyl group was detected in a wide range of 6.2 ~ 7.8 ppm. In the ²⁹ Si NMR spectrum, the peak of SiO _1.5 bond was detected in the range of -75 to -82 ppm, and the peak of the silanol group (Si-O) at the terminal was detected in the range of -67 to -72 ppm.

In the FT-IR spectrum of FIG. 2, the resonance peaks of the phenyl group were detected at 1420, 1600, and 3000 cm ⁻¹ , respectively, and SiO _1.5 bonds were detected as two strong peaks at 950 to 1200 cm ⁻¹ .

Referring to the GPC graph shown in Figure 3, it can be seen that the peak of the polysilsesquioxane of the formula (6) appeared between 30-40 minutes.

(2) Synthesis of polystyrene-g-polysilsesquioxane

0.25 g (1.21 mmol) of polysilsesquioxane, 6.93 ml (60.5 mmol) of styrene, a transition metal catalyst, 0.2681 g (2.7023 mmol) of CuCl, dNbpy 2.06 g (5.41 mmol) of ligand, 10 ml of toluene was stirred for 5 minutes in an argon atmosphere, and then polymerized at 80 ° C. for 2 hours to synthesize polystyrene-g-polysilsesquioxane represented by Chemical Formula 7, in which styrene was grafted to the side chain.

[Formula 7]

The structure of the polysilsesquioxane of Chemical Formula 7 was analyzed by ¹ H NMR, and the analysis results are shown in FIG. 4. In the ¹ H NMR spectrum shown in FIG. 4, the CH peak of the phenyl group derived from styrene was detected as two peaks in a wide range of 6.5 to 7.1 ppm, and the peak of the CH-Cl group remaining at the side chain end after the reaction was 4.2 Small amounts were detected at ˜4.5 ppm.

In addition, the consumption of styrene used in the preparation process of the polysilsesquioxane of Chemical Formula 7 was measured according to the reaction time of the atomic transfer radical polymerization, and from this, the conversion rate of styrene according to the reaction time was calculated. Indicated. Further, when the GPC was measured for the polymer after reacting the reactants before the atomic transfer radical polymerization reaction of styrene (0 o'clock) for 30 minutes and 3 hours, the GPC graph is shown in FIG. 6.

Looking at the conversion rate of styrene according to the reaction time shown in Figure 5, it can be seen that as the reaction time of the atomic transfer radical polymerization increases the consumption of styrene, the conversion rate of styrene increased.

Referring to the GPC graph of FIG. 6, it can be seen that the longer the reaction time of the atomic transfer radical polymerization, the faster the peak was detected. This is because, as the reaction time increases, the amount of styrene grafted to the side chain of polysilsesquioxane increases, thereby increasing the molecular weight of polysilsesquioxane.

Example 2: Synthesis of poly (n-butyl) acrylate-g-polysilsesquioxane

0.287 g (1.389 mmol) of polysilsesquioxane, a macro initiator synthesized in Example 1, 20 ml (0.1389 mol) of n-butyl acrylate, 0.1375 g (1.389 mmol) of CuCl, 1.13536 g (2.78 mmol) of dNbpy, and toluene After stirring 14.4 ml for 5 minutes in an argon atmosphere, polymerization was performed at 80 ° C. for 3 hours to synthesize poly (n-butyl) acrylate-g-polysilsesquioxane represented by the following Formula 8.

[Formula 8]

The structure of the polysilsesquioxane of Chemical Formula 8 was analyzed by ¹ H NMR, and the analysis results are shown in FIG. 7. In the ¹ H NMR spectrum shown in FIG. 7, the peak of COOCH ₂ derived from n-butylacrylate was found at 4.1 ppm, and the following -CH ₂ CH ₂ CH ₃ peaks were detected at 0.8, 1.4, and 1.6 ppm, respectively.

In addition, the consumption of n-butyl acrylate used in the preparation of the polysilsesquioxane of the formula (8) was measured according to the reaction time of the atom transfer radical polymerization, from which the conversion rate of n-butyl acrylate according to the reaction time was calculated. This is illustrated in FIG. 8. Furthermore, if the GPC was measured for the polymer after reacting the reactant before (0 hour) with n-butyl acrylate for 2 hours, 3.2 hours and 20 hours, the GPC graph is shown in FIG. 9.

Looking at the conversion rate of n-butyl acrylate according to the reaction time shown in Figure 8, it can be seen that the conversion rate of n-butyl acrylate increases as the reaction time of the atom transfer radical polymerization increases.

Referring to the GPC graph shown in FIG. 9, it can be seen that the longer the reaction time is, the faster the peak is detected. This is because the longer the reaction time of the atom transfer radical polymerization, the more the amount of n-butyl acrylate grafted to the side chain of the polysilsesquioxane, the molecular weight of the polysilsesquioxane increased.

Example 3: Synthesis of polystyrene-r-poly (n-butyl) acrylate-g-polysilsesquioxane

0.287 g (1.389 mmol) of polysilsesquioxane, which is a macro initiator synthesized in Example 1, 10 ml (0.0695 mol) of n-butyl acrylate, 7.95 ml (0.0695 mol) of styrene, and 0.1375 g (1.389 mmol) of CuCl , 1.13536 g (2.78 mmol) of dNbpy and 14.4 ml of toluene were stirred in an argon atmosphere for 5 minutes, and then polymerized at 80 ° C. for 8 hours to synthesize graft polysilsesquioxane represented by the following formula (9).

[Formula 9]

The structure of the polysilsesquioxane of Chemical Formula 9 was analyzed by ¹ H NMR, and the analysis results are shown in FIG. 10. In the ¹ H NMR spectrum shown in FIG. 10, the phenyl group CH peak derived from styrene was detected as two peaks in a wide range of 6.7 to 7.6 ppm, and the peak of COOCH ₂ derived from n-butylacrylate was found at 3.8 ppm. Widely appeared, the following CH ₂ CH ₂ CH ₃ peak was detected at 0.8, 1.4 and 1.6 ppm, respectively.

In addition, polysilsesquioxane of Chemical Formula 9 was measured by GPC, and the measurement results are shown in FIG. 11. Referring to the GPC graph shown in FIG. 11, it can be seen that the peak of polysilsesquioxane of the formula (9) was detected in 25 to 35 minutes. The graft polymerization of styrene and n-butyl acrylate shows that the molecular weight of the polysilsesquioxane of the formula (9) is higher than the molecular weight of the polysilsesquioxane of the formula (6).

1 is a ¹ H NMR and ²⁹ Si NMR spectra of the polysilsesquioxane of Chemical Formula 6 synthesized in Example 1 of the present invention.

2 is an FT-IR spectrum of the polysilsesquioxane of Chemical Formula 6 synthesized in Example 1 of the present invention.

3 is a GPC graph of the polysilsesquioxane of Chemical Formula 6 synthesized in Example 1 of the present invention.

4 is a ¹ H NMR spectrum of the polysilsesquioxane of Chemical Formula 7 synthesized in Example 1 of the present invention.

Figure 5 is a graph showing the conversion of the styrene (Time-Conversion) according to the reaction time of the atomic transfer radical polymerization in the preparation process of the polysilsesquioxane of formula 7 according to Example 1 of the present invention.

FIG. 6 is a graph of GPC measured for polysilsesquioxane polymerized with a reactant before atom transfer radical polymerization for 30 minutes and 3 hours in the process of preparing polysilsesquioxane of Chemical Formula 7 according to Example 1 of the present invention to be.

7 is a ¹ H NMR spectrum of the polysilsesquioxane of Formula 8 synthesized in Example 2 of the present invention.

8 is a graph showing the conversion rate of n-butyl acrylate according to the reaction time of atomic transfer radical polymerization in the preparation process of polysilsesquioxane of formula 8 according to Example 2 of the present invention.

9 is a GPC measured for the polysilsesquioxane after the polymerization of the reactants before the polymerization reaction for 2, 3.2 and 20 hours in the process of preparing the polysilsesquioxane of the formula (8) according to Example 2 of the present invention It is a graph.

10 is a ¹ H NMR spectrum of the polysilsesquioxane of Formula 9 synthesized in Example 3 of the present invention.

FIG. 11 is a GPC graph of the polysilsesquioxane of Formula 9 synthesized in Example 3 of the present invention. FIG.

Claims (19)

The polysilsesquioxane in which the homopolymer or copolymer consisting of the unsaturated hydrocarbon monomer in the side chain is grafted by graft polymerization of at least one unsaturated hydrocarbon monomer in the side chain of the polysilsesquioxane represented by the following formula (1) Method for producing a graft polysilsesquioxane, characterized in that to form a. [Formula 1]

In Formula 1, R ₁ is selected from an alkyl group having 1 to 12 carbon atoms, an acryl group, a benzyl group, a phenyl group, a thiophene and a pyrrole group, R ₂ is selected from alkyl group, acrylic group, benzyl group, phenyl group, thiophene, pyrrole group, allyl group, vinyl group, epoxy group, methacryl group and acryl, X ₁ is halogen of F, Cl, Br or I, X ₂ is the halogen or hydrogen, n is an integer from 10 to 10,000. The method of claim 1, The unsaturated hydrocarbon monomer is a production method, characterized in that the grafted on the side chain of the polysilsesquioxane of the formula (1) by atom transfer radical polymerization method. The method of claim 1, The graft polymerization of the unsaturated hydrocarbon-based monomers is carried out under a transition metal catalyst containing ruthenium or copper. The method of claim 3, wherein The transition metal catalyst may be Cu (I) Br, Cu (I) Cl, Cu (II) Br ₂ , Cu (II) Cl ₂ or Ru (II) (PPh ₃ ) ₃ Cl ₂ (Ph = C ₆ H ₅ ) Production method characterized in that. The method of claim 1, In the graft polymerization of the unsaturated hydrocarbon-based monomer, a method comprising the addition of a ligand comprising at least one of amine and pyridine. The method of claim 1, wherein the unsaturated hydrocarbon monomer is a styrene monomer, an acrylate monomer, or a vinyl pyridine. The method of claim 1, wherein the copolymer is a random copolymer, a block copolymer or an alternating copolymer. The method of claim 1, A method for producing a polysilsesquioxane represented by the following formula (2) or (3) by graft polymerization of a first unsaturated hydrocarbon monomer on the side chain of polysilsesquioxane of formula (1). [Formula 2]

(3)

In the above formula R _1, R _2, X _1, X ₂ and n have the general formula (I) of R _1, R _2, X _1, X _2, and the same as n, and, R ₃ is the repeating units derived from a first unsaturated hydrocarbon-based monomer, m is an integer from 1 to 10,000. The method of claim 1, A method for producing a polysilsesquioxane represented by the following formula (4) or (5) by graft polymerization of the first and second unsaturated hydrocarbon monomers on the side chain of the polysilsesquioxane of the formula (1). [Formula 4]

[Chemical Formula 5]

In the above formula _{R 1, R 2, X 1} , X 2 and n have the general formula (I) of _{R 1, R 2, X 1} , X 2 , and the same as n, and, R ₃ and R ₄ is from the first and the second unsaturated hydrocarbon-based monomer Each is a derived repeating unit, m is an integer from 1 to 10,000 and u is an integer from 1 to 10,000. The method of claim 9, wherein the manufacturing method is Graft polymerizing a first unsaturated hydrocarbon-based monomer on a side chain of the polysilsesquioxane of Chemical Formula 1; And And graft polymerizing the second unsaturated hydrocarbon monomer to the side chain of the polysilsesquioxane grafted with the first unsaturated hydrocarbon monomer. The method of claim 9, The first and second unsaturated hydrocarbon-based monomers are added simultaneously to the side chain of the polysilsesquioxane of the formula (1), characterized in that the first and second unsaturated hydrocarbon-based monomers in a random form. The method of claim 9, The first and second unsaturated hydrocarbon-based monomers, characterized in that different from each other. The method of claim 1, Polysilsesquioxane represented by the formula (1) is R ₁ and R ₂ is a different production method, characterized in that the random copolymer or block copolymer. As a polysilsesquioxane in which one or more types of unsaturated hydrocarbon monomers are graft-polymerized in the side chain of polysilsesquioxane represented by the following formula (1), Graft polysilsesquioxane, characterized in that the homopolymer or copolymer comprising the unsaturated hydrocarbon monomer has a grafted side chain. [Formula 1]

In Formula 1, R ₁ is selected from an alkyl group having 1 to 12 carbon atoms, an acryl group, a benzyl group, a phenyl group, a thiophene and a pyrrole group, R ₂ is selected from alkyl group, acrylic group, benzyl group, phenyl group, thiophene, pyrrole group, allyl group, vinyl group, epoxy group, methacryl group and acryl, X ₁ is halogen of F, Cl, Br or I, X ₂ is the halogen or hydrogen, n is an integer from 10 to 10,000. 15. The method of claim 14, Graft polysilsesquioxane, characterized in that the unsaturated hydrocarbon monomer is a styrene monomer, an acrylate monomer or vinyl pyridine. 15. The method of claim 14, The copolymer is a graft polysilsesquioxane, characterized in that the random copolymer, block copolymer or alternating copolymer. 15. The method of claim 14, Graft polysilsesquioxane, characterized in that the molecular weight distribution of the graft polysilsesquioxane is 1 to 3. The method of claim 14, wherein the graft polysilsesquioxane is Graft polysilsesquioxane, characterized in that the polysilsesquioxane represented by the following formula (2) or (3) graft-polymerized in the side chain of the polysilsesquioxane of formula (1). [Formula 2]

(3)

In each formula above, R _1, R _2, X _1, X ₂ and n have the general formula (I) of R _1, R _2, X _1, X _2, and the same as n, and, R ₃ is the repeating units derived from a first unsaturated hydrocarbon-based monomer, m is an integer from 1 to 10,000. The method of claim 14, wherein the graft polysilsesquioxane Graft polysilyl, characterized in that the polysilsesquioxane represented by the following formula (4) or (5) by graft polymerization of the first and second unsaturated hydrocarbon monomers in the side chain of the polysilsesquioxane of formula (1) Sesquioxane. [Formula 4]

[Chemical Formula 5]

In the above formula _{R 1, R 2, X 1} , X 2 and n have the general formula (I) of _{R 1, R 2, X 1} , X 2 , and the same as n, and, R ₃ and R ₄ is from the first and the second unsaturated hydrocarbon-based monomer Each is a derived repeating unit, m is an integer from 1 to 10,000 and u is an integer from 1 to 10,000.

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