KR100851811B1 - Composites of silicon-containing polymers that encapsulate functional materials - Google Patents

Abstract

A functional silicon-containing polymer composite, a method for preparing the composite, and a functional polysilsesquioxane composite containing the polymer composite are provided to obtain desired chemical, physical and mechanical properties by controlling the kind and ratio of a functional group. A functional silicon-containing polymer composite comprises a silicon-containing polymer prepared by the polymerization of a monomer represented by the formula 1; and a functional material trapped in the polymer, wherein R1 is H, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aminoalkylaminoalkyl group, an aminoalkyl group, an arylamino group, an alkoxy group, an aryloxy group, an aminocycloalkyl group, an aminoalkenyl group, an aminocycloalkenyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an aminoallyl group, a hydroxyl group, an amino group, a nitro group, a sulfonyl group, a cyano group, a carboxyl group, a thiol group, or an ethylenediamine group; R2, R3 and R4 are independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aminoalkylaminoalkyl group, an aminoalkyl group, an aminocycloalkyl group, an aminoalkenyl group, an aminocycloalkenyl group, an aminoallyl group, a cyanoalkyl group, an ethylenediamine group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, an arylaminocarbonyl group, an alkoxy group, or an aryloxy group; and n is an integer of 0-5.

Description

Composites of Silicon-Containing Polymers that Encapsulate Functional Materials

1 is a schematic diagram showing a process for preparing a functional polysilsequioxane (PSQ) composite in the functional silicone-containing polymer of the present invention.

Figure 2a is a fluorescence micrograph showing the results of the production of polysilsesquioxane spherical complex modified with an amine group containing a fluorescent substance rhodamine 6G (rhodamine 6G).

Figure 2b is a fluorescence micrograph showing the results of the production of polysilsesquioxane spherical complex modified with an amine group containing a fluorescent material fluorescein (fluorescein).

Figure 3 is a photograph prepared by drying the PSQ spherical complex encapsulating the natural pigments gardenia yellow pigment, green pigment and red pigment.

Fig. 4a shows a fluorescein-polysilsesquioxane spherical complex, a complex in which a gold nanoparticle shell is formed in a fluorescein-polysilsesquioxane spherical complex, a rhodamine 6G-polysilsesquioxane spherical complex, A composite photo of gold nanoparticle shells formed on a min 6G-polysilsesquioxane spherical complex.

4B is a fluorescence micrograph of a fluorescein-polysilsesquioxane spherical complex and a complex in which a gold nanoparticle shell was formed.

4C is a fluorescence micrograph of a rhodamine 6G-polysilsesquioxane spherical complex and a complex in which a gold nanoparticle shell was formed.

5 is an electron micrograph of a polysilsesquioxane complex containing gold nanoparticles.

6 is an optical microscope (a) and a fluorescence microscope (b) image showing the results of the immune response using the PSQ complex conjugated with the antibody and conjugated with the fluorescent material.

The present invention relates to composites of silicone-comprising polymers containing various functional materials and methods for their preparation.

Among silicone-comprising polymers, polysilsequioxane compounds have been widely used in various industries as additives for imparting activity or extensibility. Among the polysilsesquioxane polymers, polymethylsilsesquioxane is used as a cosmetic raw material because of its unique properties such as excellent fluidity, luster and lubricity (see Japanese Patent Laid-Open Nos. 54-72300 and 60-13813). ).

As a method for producing spherical silicon particles, a method for obtaining spherical particles using organotrialkoxysilane and / or its hydrolyzate and an ammonia or amine organic solution (Japanese Patent Laid-Open No. 63-77940) is known, but the reaction is known. It is difficult to maintain the interface continuously, and the reaction rate is low because the opportunity for contact with alkali is considerably small, which is not a preferable manufacturing method in consideration of production efficiency.

As another example of the method for producing spherical silicon particles, there have been attempts to cause hydrolysis and polycondensation of silane monomers using a surfactant instead of the organic solvent (Japanese Patent Laid-Open Nos. 2000-169583 and 04- 33927), the process of making an emulsion with a surfactant is complex and it is difficult to constantly control the particle size of the emulsion.

As another example of the method for producing spherical silicon particles, water / alcohol solution is added to the organosilanetriol obtained by hydrolysis of organotrialkoxysilane or its condensate, and then added to the alkaline aqueous solution, and the average particle size is 1-10. Although there is a method of producing spherical particles of μm (Japanese Patent Laid-Open No. 10-363101), it is difficult to obtain particles having a small diameter by this method, and it takes a long time to obtain particles having a small diameter. There is a problem that the productivity is low.

As another example of the method for producing the spherical silicon particles, using an organotrialkoxysilane and an organo tetraalkoxysilane as an catalyst in the first step, the alkaline aqueous solution in the second step as a neutralizing agent and a polycondensation reaction catalyst Although there is a method (Japanese Patent Laid-Open No. 2001-192452) for producing spherical particles having an average particle diameter of 0.1-5 μm using the same, there is a problem of undergoing a complex multi-step reaction.

Republic of Korea Patent Publication No. 10-0586438 (Method for preparing polysilsesquioxane spherical particles using alkoxysilane compound containing amino group and polysilsesquioxane spherical particles) and Republic of Korea Patent Publication No. 10-2004-0014886 ( In a structure made of a hybrid material containing silica, a vinyl group, and an amine group, and a method of manufacturing the same), precursors such as vinyltrialkoxysilane, mercaptopropyltrialkoxysilane, and 3-aminopropylsiloxane can be used to form polysilsesquioxane spherical particles. Methods of making are described. The polysilsesquioxane spherical particles of the method as described above has the advantage that the production is simple and the active group can be generated only by the reaction of the precursor without additional reaction.

Republic of Korea Patent Publication No. 10-0596740 (polysilsesquioxane spherical particles having an ultraviolet absorber and a manufacturing method thereof) describes a method for the production of polysilsesquioxane spherical particles covalently bonded to an active group having an ultraviolet absorber. .

Methyl and phenylsilsesquioxane particles have been prepared and commercialized, but they are not chemically highly reactive and contain particles containing mercaptans, vinyl groups or chromophores that block UV rays, and mesogens that represent liquid crystals. The manufacturing technique is not known yet.

A dye refers to a colored substance that is dissolved in an aqueous solution or an organic solvent, dispersed as a single molecule, combined with a molecule such as a fiber, and colored. A pigment refers to a powder colorant that is insoluble in an aqueous solution or an organic solvent. Dyes and pigments can be used in a variety of fields such as fiber, rubber, paper, leather, plastics, food, cosmetics, as well as labels, photo pigments, dye lasers in the life sciences.

Fluorescence is one of the luminescence phenomena emitted by electron transfer when the excited material returns to the ground state. Fluorescent dye refers to a dye that fluoresces. Representative fluorescent dyes include fluorescein (green fluorescence) and rhodamine (red fluorescence). Fluorescent dyes are used to give fluorescent colors to plastics, textiles and inks, and are used as raw materials for organic fluorescent pigments for labels, advertisements and art crafts. Fluorescent dyes are also widely used as markers for the detection of biomolecules such as tissues, cell staining, DNA and proteins in the life sciences.

The organic fluorescent dye has a disadvantage in that it is difficult to observe for a long time due to a photobleaching phenomenon in which the luminescence sensitivity decreases when exposed to light, and a short molecule does not have sufficient luminescent effect.

Quantum dots are semiconducting materials such as CdSe and ZnS, which cannot be stably dispersed in aqueous solutions, and products whose surface is modified with hydrophilic materials are used in the life sciences (Invtrogen, USA). However, quantum dots have the disadvantage that the manufacturing process is complicated and very expensive.

A method of improving the photobleaching phenomenon of organic fluorescent dyes is to use a polymer such as polystyrene as a carrier of the fluorescent material. This method swells the polymeric spherical particles with an organic solvent in order for the fluorescent dye to enter the spherical particles. Products using this method are already commercialized (Bangs Laboratories Inc., USA). When the polymer is used, the spherical particles may swell and leak of the fluorescent dye, and the hydrophobic property of the surface may be strong to cause aggregation, and the density is low, so that the recovery of the particle size is difficult.

US 2006/228554 discloses a method of using silica as a coating for wrapping fluorescent materials to overcome the disadvantages of polymer carriers such as polystyrene. When silica is used, it is possible to improve the aggregation phenomenon of the polystyrene polymer, and since the density is larger than that of polystyrene, the particles can be recovered by a simple method such as centrifugation. Microemulsion using water, oil, and surfactants is used to make silica-coloured silica. However, since there is no active group on the surface of the silica, after the production of the silica particles must be connected to the active group through a separate chemical reaction, there is a disadvantage that the manufacturing method is complicated and takes a long time.

A method for producing polysilsesquioxanes as silicone-comprising polymers in the form of complexes with functional materials such as fluorescents or dyes has not yet been proposed.

On the other hand, the alkyl trialkoxy silane, dialkoxy dialkyl silane, and is called a tetraalkoxysilane is hydrolyzed and run the condensed material each formed silsesquioxane, siloxane and silica, each of which _{(SiO 1 .5 R) n,} (SiOR 2 ) _n , (SiO ₂ ) _n . Silsesquioxanes, siloxanes and silicas can be made into plates or spheres and used as powders or for the coating of various materials.

Throughout this specification, numerous papers and patent documents are referenced and their citations are indicated. The disclosures of cited papers and patent documents are incorporated herein by reference in their entirety, and the level of the technical field to which the present invention belongs and the contents of the present invention are more clearly explained.

The present inventors have tried to develop a polymer capable of stably encapsulating or encapsulating functional materials such as fluorescent materials, dyes, magnetic particles, and metal particles. The present invention has been completed by confirming that the containing polymer not only stably captures the functional material, but also that the silicone-comprising polymer comprising the functional material can be economically produced through a simple process.

It is therefore an object of the present invention to provide a composite of functional silicone-comprising polymers.

Another object of the present invention is to provide a method for preparing a composite of a functional silicone-containing polymer.

Other objects and advantages of the present invention will become apparent from the following detailed description, claims and drawings.

According to one aspect of the present invention, the present invention relates to a functional silicone-containing polymer comprising (a) silicone-containing polymeric spheres and (b) a functional material encapsulated within the silicone-containing polymer. In the complex, the silicone-containing polymer provides a complex of functional silicone-containing polymer, characterized in that formed by the polymerization reaction of the monomer represented by the following formula (1):

Formula 1

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, carboxyl, thiol or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aminoalkylaminoalkyl group, an aminoalkyl group, an aminocycloalkyl group, an aminoalkenyl group, an aminocycloalkenyl group, an aminoallyl group, a cyano alkyl group, or ethylene diamine, alkyloxy-carbonyl, aryloxy-carbonyl, alkyl amino carbonyl, aryl amino carbonyl group, an alkoxy or aryloxy group, the R _2, R ₃ R _4, at least two of the dogs alkoxy, arylamino or aryloxy group, n is an integer from 0 to 5.

According to another aspect of the invention, the invention provides a process for the preparation of a polymer of a functional silicone-comprising polymer comprising the following steps:

(a) mixing the monomer and functional material represented by the following Chemical Formula 1; And

Formula 1

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, carboxyl, thiol or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aminoalkylaminoalkyl group, an aminoalkyl group, an aminocycloalkyl group, an aminoalkenyl group, an aminocycloalkenyl group, an aminoallyl group, a cyano alkyl group, or ethylene diamine, alkyloxycarbonyl, aryloxy Brassica carbonyl, alkyl amino carbonyl, aryl amino carbonyl group, an alkoxy or aryloxy group, the R _2, R ₃ R ₄ and at least two of the alkoxy, aryl, amino or an aryloxy group, n is an integer from 0 to 5;

(b) inducing a polymerization reaction of the monomer to prepare a silicone-containing polymer containing the functional material.

The present inventors have tried to develop a polymer material capable of stably encapsulating or encapsulating functional materials such as fluorescent materials, dyes, magnetic particles, and metal particles. It has been found that the containing polymer not only stably captures the functional material, but also makes it possible to economically prepare silicone-polymers comprising the functional material through a simple process.

The monomer of Formula 1 serves as a catalyst and comonomer in the reaction to prepare a silicon-containing polymer.

As used herein, the term “alkyl group” as used to define a silicone-comprising polymer of Formula 1 means a straight or pulverized saturated hydrocarbon group, for example methyl, ethyl, propyl, isobutyl, pentyl, hexyl, heptyl, Octyl, nonyl, decyl, undecyl, tridecyl, pentadecyl and heptadecyl, and the like. Preferably, the alkyl group is a C ₁ -C ₄ straight or branched alkyl group.

The term “cycloalkyl group” means a cyclic hydrocarbon group such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term “alkenyl group” refers to a straight or branched unsaturated hydrocarbon group, preferably C ₂ -C ₆ straight or branched alkenyl, which is a hydrocarbon group having 2 to 6 carbon atoms having at least one double bond, for example, Tenyl, vinyl, propenyl, allyl, isopropenyl, butenyl, isobutenyl, t -butenyl, n -pentenyl and n -hexenyl.

The term “aryl group” means a substituted or unsubstituted monocyclic or polycyclic carbon ring which is wholly or partially unsaturated, and is preferably monoaryl or biaryl. It is preferable that monoaryl has 5-6 carbon atoms, and it is preferable that biaryl has 9-10 carbon atoms. Most preferably said aryl is substituted or unsubstituted phenyl. When monoaryl, such as phenyl, is substituted, substitutions may be made by various substituents at various positions, but preferably halo, hydroxy, nitro, cyano, C ₁ -C ₄ Substituted or unsubstituted straight or branched chain alkyl, C ₁ -C ₄ Straight or branched alkoxy, alkyl substituted sulfanyl, phenoxy, C ₃ -C ₆ cycloheteroalkyl or substituted or unsubstituted amino groups.

The term “aminoalkyl” refers to a —NH ₂ group bonded to a parent molecular moiety through an alkylene group, for example 2-amino-1-ethylene, 3-amino-1-propylene and 2-amino -1-propylene and the like. The term “arylamino” refers to an aryl radical substituted by an amino radical and includes, for example, phenylamino, 1-naphthylamino, diphenylamino and the like.

The term “alkoxy” means an —Oalkyl group and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, pentyloxy and hexyloxy, and the like. do.

The term "aryloxy" refers to the group "aryl-O?" And includes, for example, phenoxy and naphthoxy and the like.

The term “aminocycloalkyl” refers to a cycloalkyl radical substituted by an amino radical. The term "aminoalkenyl" refers to an alkenyl radical substituted by an amino radical. The term “aminocycloalkenyl” refers to a cycloalkenyl radical substituted by an amino radical.

The term "alkyloxycarbonyl" means a -C (O) -O-alkyl group, and the term "aryloxycarbonyl" means a -C (O) -O-aryl group.

The term "alkylaminocarbonyl" refers to an alkylamino group bonded to a parent molecular moiety through a carbonyl group, for example methylaminocarbonyl, ethylaminocarbonyl, iso-propylaminocarbonyl, and the like. Include. The term "arylaminocarbonyl" refers to an arylamino group bonded to the parent molecular moiety through a carbonyl group.

The term “aminoallyl” refers to an —NH ₂ group bonded to an allyl group. The term “cyano alkyl” refers to a —CN group bonded to the parent molecular moiety through an alkylene group.

According to a preferred embodiment of the invention, the silicone-comprising polymers of the invention can combine various functional groups. For example, hydroxy, amino, nitro, sulfonyl, cyano, carboxyl, thiol, amine groups and vinyl groups can be combined to modify the silicone-comprising polymers. More preferably, the silicone-comprising polymer of the present invention is modified with at least one functional group selected from the group consisting of amine groups, thiol groups, vinyl groups, cyano groups and carboxyl groups.

According to a preferred embodiment of the invention, the silicone-comprising polymer-bonded functional groups are formed in the silicone-comprising polymer simultaneously with the preparation of the silicone-comprising polymer. In other words, when producing a modified silicon-containing polymer, it can be prepared in one step reaction without going through several steps. Moreover, since the reaction can be carried out at room temperature without heating or cooling, the modified silicone-comprising polymer can be easily produced without a thermostat. This functional group introduction strategy allows for the rapid and economical preparation of the production of silicone-comprising polymers with functional groups attached.

The functional groups are formed in three-dimensional forms, such as the surface or inside of spheres, formed by the silicon-comprising polymer.

These functionalized silicone-containing polymers differ greatly in chemical, physical and mechanical properties compared to polymers without functional groups. For example, by bonding functional groups to silicone-containing polymers, surface properties, hardness, strength, hydrophilicity (lipophilic), swelling, elasticity, extensibility, softening point, heat resistance, refractive index, redox potential, electronegative The degree (polarity), density and size of the internal space will vary. Thus, functional groups can be bonded to silicone-comprising polymers to control the chemical / physical and mechanical properties described above.

In addition, the functional groups bonded to the silicone-comprising polymer allow the silicone-comprising polymer to induce an oxidation / reduction reaction. For example, when the amine group is bonded as a functional group to the silicon-comprising polymer, it is possible to catalyze the reduction reaction in the sphere formed by the silicon-comprising polymer. More specifically, the silicon-reacted, including the addition of the gold element supply source HAuCl ₄ in the polymer, the silicon-the HAuCl ₄ silicon internally contains polymer, silicone having an amino group when an absorption of gold nanoparticles in the containing polymer containing polymer It is reduced by the amine groups present in it to form gold nanoparticles, and also a shell by the gold nanoparticles is made on the surface of the silicon-comprising polymer. That is, the silicon-comprising polymer of the present invention in which amine groups are bound allows gold nanoparticles to be formed in the polymer with only HAuCl ₄ without the aid of a reducing agent such as sodium citrate.

In addition, the functional groups bonded to the silicon-comprising polymers allow for the conjugation of other useful molecules to the surface of the silicon-comprising polymers. The molecule that can be conjugated to the silicon-comprising polymer is not particularly limited, and is preferably a biomolecule selected from the group consisting of proteins, peptides, DNA, RNA, peptide nucleic acid (PNA), carbohydrates, lipids, and the like. to be.

Conjugation of other molecules to functional groups bound to the silicone-comprising polymers of the invention can be carried out according to methods well known in the art. For example, in the case of silicon-comprising polymer particles bound to amine groups, a linker containing an aldehyde group (eg, glutaraldehyde) may be used to conjugate with a protein (eg, an antibody) following the amine-aldehyde reaction. . Alternatively, a bifunctional linker such as NHS ( N- hydroxysuccinimide) -ester may be used to conjugate with a thiol-containing molecule. According to such a method, a protein such as an antibody or a biomolecule such as a DNA having an amine or a thiol group introduced therein can be conjugated to a silicon-containing polymer. In addition, in the case of the amine group bound to the silicone-containing polymer, it is converted into a carboxyl group by reacting with a substance such as succinic anhydride, which is then reacted with a dicyclohexylcarbodiimide (EDC) and then conjugated with a biomolecule containing an amine group. You can.

According to a preferred embodiment of the present invention, the functional material collected inside the silicone-comprising polymer is a fluorescent substance, a pigment, a metal particle or a magnetic particle.

Examples of the fluorescent material are fluorescein (fluorescein), fluoresein isothiocyanate (FITC), rhodamine 6G (rhodamine 6G), rhodamine B (rhodamine B), TAMRA (6-carboxy-tetramethyl-rhodamine), Cy-3, Cy-5, Texas Red, Alexa Fluor, DAPI (4,6-diamidino-2-phenylindole), Coumarin and the like. Examples of such pigments include gardenia, eosin, phenol red, bromophenol blue, m-cresol purple, bromocresol purple and the like. Examples of the metal particles include gold, silver, platinum, palladium and iron. Examples of the magnetic particles include paramagnetic particles (eg, Gd (III), Mn (II), Cu (II), Cr (III), Fe (II), Fe (III), Co (II), Er (II), Ni (II), Eu (III) and Dy (III)) and superparamagnetic particles (eg magnetite, Fe ₃ O ₄ , γ-Fe ₂ O ₃ , manganese ferrite, cobalt ferrite and Nickel ferrite) and the like.

According to a more preferred embodiment of the invention, the functional material is gold nanoparticles, and the surface of the silicon-comprising polymer has a gold nanoparticle shell formed thereon.

According to a preferred embodiment of the invention, the silicone-comprising polymer of the invention is a polysilsesquioxane-based polymer.

When the silicone-containing polymer of the present invention is a polysilsesquioxane-based polymer, preferably, the polysilsesquioxane-based polymer is formed by polymerization of a monomer represented by the following formula (2).

Formula 2

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and n is an integer from 0 to 5.

More preferably, in Formula 2, R ₁ is an alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, alkyloxycarbo Nyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, amino, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ are independently of each other an alkyl group, cyclo Alkyl group, an alkenyl group, or an aryl group, n is an integer of 1-3.

When preparing the polysilsesquioxane particles, various alkyltrialkoxysilanes may be used as monomers or precursors, for example, methyltrimethoxysilane, methyltriethoxysilane, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aryltrimethoxysilane, aryltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, N-methyl-3 -Aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3- Aminopropyltriethoxysilane, 4-aminocyclotrimethoxysilane, 4-aminocyclotri Ethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, and the like can be used for the production of polysilsequioxane. In addition, various polysilsesquioxane particles may be prepared using as a precursor trimethoxysilane or triethoxysilane having a desired functional group.

As a specific example, poly silse quinolyl dioxane having an amine-for producing a polymer of the series (that is, if the amine compound is located in R _1, R _2, R ₃ or R _4, preferably R ₁ in the general formula (2)) In this case, various monomers can be used, preferably aminoalkyltrialkoxysilane is used, more preferably 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3- Aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-amino Propyltriethoxysilane, 4-aminocyclotrimethoxysilane, 4-aminocyclotriethoxysilane, p-aminophenyltrimethoxysilane and p-aminophenyltriethoxysilane are used, and reactivity and ease of handling Considering 3-aminopropyltrimethoxysilane and N- (2-a No-ethyl) -3-aminopropyl trimethoxysilane is most preferred.

On the other hand, when preparing a silicone-containing polymer, in particular polysilsequioxane, an alkaline solution may be used as another catalyst in addition to the compound of Formula 1 or 2 used as a catalyst to further shorten the reaction time. It is preferable to use the compound of Formula 1 or 2 as a self catalyst without adding the above.

The size of the silicone-containing polymer used in the present invention is not particularly limited, and the size can be appropriately adjusted by changing various conditions such as the time of polymer formation reaction, the amount of monomer (precursor), the amount of solvent and the addition of surfactant. have. The particle size of the silicone-comprising polymer is between several tens of nm and tens of microns.

Surfactants that can control the particle size and particle size distribution of the silicone-containing polymer are not particularly limited, and for example, sorbitan trioleate, sorbitan sesquiorate, sorbitan sesquistearate, sorbitan monostearate Glycerol fatty acid esters such as sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, glycerin monostearate, glycerin monooleate, diglycerin diorate, diglycerin monoorate, diglycerin monostearate Pentaerythritol fatty acid esters such as polyglycerol fatty acid esters such as tetraglycerol monoorate and tetraglycerol monostearate, pentaerythritol monostearate, pentaerythrito monopalmitate, propylene glycol monostearate, and propylene glycol mono Laurate Diethylene glycol fatty acid ester, such as propylene glycol fatty acid ester, diethylene glycol monostearate, and diethylene glycol monolaurate, polysaccharide fatty acid ester, such as sucrose tristearate, sucrose palmitate, and sucrose dilaurate, cetyl Liaminobromide and the like can be used. Preferably, Tween which is fatty acid ester, such as polyoxyethylene sorbitan, Span which is sorbitan fatty acid ester, and cetyl triamino bromide are used.

The silicone-comprising polymers, in particular polysilsesquioxanes, used in the present invention may have a variety of shapes, and preferably have a spherical shape. When the silicone-containing polymer of the present invention, in particular polysilsesquioxane, has a spherical shape, there is an advantage that the uniformity or homogeneity of the particles of the polymer of the present invention is greatly improved. In addition, these spherical particles have the advantage of increasing the chance of collision with other molecules (ie reaction opportunities) than particles of other shapes, and is also very advantageous for trapping functional materials therein.

According to another aspect of the present invention, the present invention provides a composite of a functional silicone-comprising polymer comprising (a) polysilsesquioxane and (b) a functional material trapped inside of the polysilsesquioxane, wherein the poly Silsesquioxane has a spherical shape and is formed by polymerization of a monomer represented by Formula 2, wherein the functional material is a complex of functional polysilsesquioxane, characterized in that it is a fluorescent material or gold nanoparticles. to provide:

Formula 2

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and n is an integer from 0 to 5.

The polysilsesquioxane complex of the present invention is particularly suitable for capturing fluorescent material.

The silicone-comprising polymers of the present invention, in particular the polysilsesquioxane spherical particles, include alcohol solvents such as methanol, ethanol, isopropanol and butanol; Ether alcohol solvents such as ethylene glycol methyl ether, ethylene glycol ethyl ether and propylene glycol ethyl ether; Ether solvents such as diethyl ether, tetrahydrofuran and dioxane; Ketone solvents such as acetone and methyl ethyl ketone; water; And it is possible to prepare under a mixed solvent thereof, it is preferable to use water as the solvent in terms of cost and ease of handling.

As mentioned above, the composite of the functional silicone-comprising polymer of the present invention is prepared through a very simple process.

For example, when preparing a composite of a functional silicone-containing polymer containing a fluorescent substance or a dye, a precursor of the silicone-containing polymer and a fluorescent substance or a pigment are mixed and left at room temperature for a certain time to contain a fluorescent substance or a pigment. Composites of functional silicone-comprising polymers are produced spontaneously. That is, a complex of a functional silicone-containing polymer containing a fluorescent substance or a pigment may be prepared in only one step.

This simple process is surprising when compared to the complex processes of the prior art.

In addition, when preparing a composite of a functional silicon-containing polymer containing metal particles or magnetic particles, the silicon-containing polymer may be prepared by treating a source of a metal or magnetic element with a silicon-containing polymer prepared using a precursor of the silicon-containing polymer. Metal particles and magnetic particles can be prepared inside the polymer to conveniently prepare a composite of functional silicone-comprising polymers containing metal particles or magnetic particles.

For example, when preparing a composite of a silicon-containing polymer containing gold nanoparticles, hydrochloric acid (Hydrogen tetrachloroaurate trihydrate (HAuCl ₄ -3H ₂ O)) was added to a silicon-containing polymer prepared using a precursor of the silicon-containing polymer. By adding and heating at a high temperature (about 60 ° C.) for a certain time, a composite of a silicon-containing polymer containing gold nanoparticles can be obtained. That is, the composite of the silicone-comprising polymer of the present invention containing gold nanoparticles does not require a reducing agent that is commonly used. In addition to gold chloride, silver nitrate (AgNO ₃ ), chloroplatinic acid (Hydrogen hexachloroplatinate (IV) hydrate, HPtCl ₆ -H ₂ O), sodium tetrachloropalladate (II), NaPdCl ₄ ), acetylacetonate iron (II) and acetyl Using acetonate iron (III), a composite of a silicon-comprising polymer containing metal particles or magnetic particles can be easily obtained.

Another method of preparing a composite of silicon-comprising polymers containing gold nanoparticles may employ a method in which an aqueous solution of gold chloride and a precursor of the silicon-comprising polymer are reacted with each other at any temperature and pressure.

Another method of obtaining a complex of gold nanoparticles and a silicon-containing polymer is a method of preparing gold nanoparticles, which is commonly used in the art, and includes a silicon-containing polymer containing gold nanoparticles and amine groups formed by treating a reducing agent with a pH 7.0- Mixing in the 10.0 range. Methods for making gold nanoparticles can be used in the literature, including those described by Hayat (Hayat, M. A. Colloidal Gold, Principles, Methods and Applications; Academic Press: New York, 1989.). Or by Jana, NR or the like, known as seed growth, in which small-sized gold nanoparticles are bonded to a silicon-containing polymer including an amine group and shell growth is added by adding a gold chloride ion solution (Jana). (NR; Gearheart, L .; Murphy, CJ Evidence for Seed-Mediated Nucleation in the Chemical Reduction of Gold Salts to Gold Nanoparticles.Chem. Mater. 2001, 13, 2313-2322.).

Similarly, a method of preparing spheres from silicon-comprising polymers in already formed gold nanoparticle colloids can be used to prepare silicone resin spheres containing gold nanoparticles.

As mentioned above, the composite of the silicone-comprising polymer of the present invention has a variety of applications.

For example, when an antibody is conjugated to a complex of a silicone-comprising polymer of the invention, the complex of the invention can be used for various immunoassays. Immunoassays can be performed according to various immunoassays or immunostaining protocols developed in the prior art. The immunoassay or immunostaining format may include radioimmunoassay, radioimmunoprecipitation, immunoprecipitation, ELISA (enzyme-linked immunosorbent assay), capture-ELISA, inhibition or hardwood analysis, sandwich analysis, flow cytometry, immunofluorescence staining. And immunoaffinity tablets. The immunoassay or method of immunostaining is described in Enzyme Immunoassay , ET Maggio, ed., CRC Press, Boca Raton, Florida, 1980; Gaastra, W., Enzyme-linked immunosorbent assay (ELISA), in Methods in Molecular Biology , Vol. 1, Walker, JM ed., Humana Press, NJ, 1984; And Ed Harlow and David Lane, Using Antibodies: A Laboratory Manual , Cold Spring Harbor Laboratory Press, 1999, which is incorporated herein by reference.

For example, when radioimmunoassays are performed using the conjugates of the present invention conjugated with antibodies, radioisotopes (eg, C ¹⁴ , I ¹²⁵ , P ^32). And Antibodies labeled S ³⁵ ) can be used to detect specific proteins.

When performing an immunoassay using the complex of the present invention conjugated with an antibody, the complex of the present invention can be used as a label or a support of a primary antibody or a secondary antibody. The binding to the antigen can be detected using a signal from a functional substance containing the complex of the present invention, such as a fluorescent substance, a dye, a metal particle or a magnetic particle.

On the other hand, the complex of the present invention is a cell and tissue examination using a fluorescence microscope, the detection of reactants by DNA polymerization reaction, molecular imaging (molecular imaging), biochips, biosensors, fibers, rubber, paper, leather, plastics, food, cosmetics And dye lasers.

The features and advantages of the present invention are summarized as follows:

(Iii) The present invention utilizes silicone-containing polymers made of specific monomers as a means of stably collecting functional materials.

(Ii) The composite of the silicone-comprising polymer of the present invention having a functional group can be made to have desired chemical, physical and mechanical properties by adjusting the type and content of functional groups.

(Iii) The complex of the silicone-containing polymer of the present invention having a functional group can proceed the oxidation / reduction reaction inside the complex using the oxidation / reduction potential of the functional group. This advantage works very advantageously when producing complexes containing gold nanoparticles.

(Iii) The complex of the silicone-comprising polymer of the present invention having a functional group can bind various other molecules through the functional group, which greatly increases the applicability of the complex of the present invention.

(Iii) The composite of the functional silicone-containing polymer of the present invention containing a fluorescent substance or a pigment may be prepared in one step, and the composite of the present invention containing a metal particle or magnetic particle may be prepared through a very simple process. Can be.

(Iii) The complex of the present invention can be used for immunoassay, cell and tissue examination using fluorescence microscope, detection of reactants by DNA polymerization reaction, molecular imaging, biochip, biosensor, fiber, rubber, paper, leather, plastic, food, It can be used in cosmetics and dye lasers.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention. .

Example

Example  One: An amine group  Contains fluorescent substance Polysilsesquioxane  Preparation of Spherical Complexes

20 mL of 25 μM Rhodamine 6-G (Aldrich, USA) and 1 mL of methyltrimethoxysilane (Aldrich, USA) and 3-aminopropyltrimethoxysilane, respectively, in 25 μM Fluorescein (Aldrich, USA) (Aldrich, USA) 0.1 mL was added, mixed well and left at room temperature for at least 2 hours. The resulting polysilsesquioxane spherical complex contains an amine group and is pink for rhodamine and light green for fluorescein. After centrifugation at 10,000 g for 10 minutes to recover the spherical complex, the precipitate was washed three times or more with distilled water until the supernatant became clear. Spherical complexes were observed under a fluorescence microscope (Olymphus IX-71, USA) to identify polysilsesquioxane spherical complexes exhibiting fluorescence (FIGS. 2A and 2B).

As can be seen in Figures 2a-2b, the fluorescent material-polysilsesquioxane spherical complex shows a very strong fluorescence, and the photobleaching phenomenon did not appear even when exposed to light for a long time.

Example  2: An amine group  Free fluorescent substance Polysilsesquioxane  Preparation of Spherical Composites

After mixing 50 µL of 3 wt% Rhodamine 6G ethanol solution and 0.1 mL of methyltrimethoxysilane, 10 µL of triethylamine was added thereto, followed by stirring for 2 hours. After centrifugation at 10,000 g for 10 minutes to recover the spherical complex, the precipitate was washed three times or more with distilled water until the supernatant became clear. Spherical complexes were observed under a fluorescence microscope to identify polysilsesquioxane spherical complexes exhibiting fluorescence.

Example  3: An amine group  Natural Colors Containing Polysilsesquioxane  Preparation of Spherical Complexes

1 mL of methyltrimethoxysilane and 0.1 mL of 3-aminopropyltrimethoxysilane were added to 20 mL of aqueous solution of Gardenia pigment with natural pigment, and then mixed well and left at room temperature for 2 hours or more. After centrifugation at 10,000 g for 10 minutes to recover the spherical complex, the precipitate was washed three times or more with distilled water until the supernatant became clear and dried at room temperature (FIG. 3).

As can be seen in Figure 3, by preparing a spherical complex of natural pigments yellow, green, red gardenia and polysilse squioxane spherical complex was able to obtain a complex corresponding to each color in a powder state.

Example  4: fluorescent material coated with gold nanoparticles- Polysilsesquioxane  Manufactured on spherical complex

Gold chloride ions (HAuCl _4, Aldrich, USA) were added to the polysilsesquioxane spherical composite containing fluorescein and rhodamine 6G prepared in Example 1 to 0.01%, and then heated at 60 ° C. for 48 hours. After centrifugation at 10,000 g for 5 minutes to recover the spherical complex, the supernatant was washed three times with distilled water to obtain a red to purple hybrid (FIG. 4).

As can be seen in Figure 4, the hybrids are red to purple in the visible region and when observed under a fluorescence microscope, the particles coated with gold nanoparticles on the fluorescein and polysilsesquioxane spherical complex is green, Rhodamine and The particles coated with the gold nanoparticles on the polysilsesquioxane spherical composite showed red fluorescence, and the overall fluorescence intensity was reduced than the particles prepared in Example 1 due to the coating of the gold nanoparticles.

Example  5: containing gold nanoparticles Polysilsesquioxane  Direct Preparation of Spherical Complexes

0.5 mL of vinyltrimethoxysilane was added to 5 mL of an aqueous solution containing 0.01% of gold chloride ions, followed by stirring. Then, 0.05 mL of 3-aminopropyltrimethoxysilane was added thereto, vigorously stirred for about 20 seconds, and left to stand. Spherical particles containing the particles are formed. The particles thus obtained have the feature that the surface is somewhat smooth (FIG. 5).

Example  6: with gold nanoparticles Rhodamine  Contained Polysilsesquioxane  Direct Preparation of Spherical Complexes

0.5 mL of methyltrimethoxy silane was added to 5 mL of an aqueous acid solution containing 0.01% of gold chloride ion and 1 mL of an aqueous 0.1% solution of rhodamine, followed by stirring. Then, 0.05 mL of 3-aminopropyltrimethoxysilane was added thereto for about 20 seconds. After stirring vigorously, spherical particles containing gold nanoparticles and rhodamine are formed. The sphere thus obtained has a shape similar to that of FIG. 5 and shows fluorescence.

Example  7: containing gold in the presence of gold colloidal particles Polysilsesquioxane  Preparation of Spherical Complexes

0.5 mL of vinyl trimethoxy silane and 0.05 mL of 3-aminopropyltrimethoxysilane were added to 5 mL of a colloidal solution containing 0.1% of 3 nm gold particles, stirred vigorously for about 20 seconds, and left to contain gold nanoparticles. Spherical particles are formed.

Example  8: gold in the presence of gold colloidal particles and Rhodamine  Containing Polysilsesquioxane  Preparation of Spherical Complexes

Mix 1 mL of a colloidal solution containing 0.1% of 3 nm gold particles with 1 mL of an aqueous solution containing 0.1% of rhodamine 6G, and add 0.5 mL of methyl trimethoxy silane and 0.05 mL of 3-aminopropyl trimethoxysilane to 5 mL. After stirring vigorously for about 20 seconds and left to form spherical particles containing gold nanoparticles.

Example  9: Sulfone  Pigment containing Polysilsesquioxane  Preparation of Spherical Complexes

Methyl in 20 mL aqueous solution of phenol red, bromophenol blue, m-Cresol Purple or Bromocresol Purple pigments containing sulfone groups as pigments After adding 1 mL of trimethoxysilane and 0.1 mL of 3-aminopropyltrimethoxysilane, the mixture was well mixed and left at room temperature for at least 1 hour. The resulting polysilsesquioxane spherical complex was phenol red for red, bromophenol blue for indigo blue, m-cresol purple for indigo blue, bromocresol purple for bromocresol purple It is indigo blue. After centrifugation at 10,000 g for 10 minutes to recover the spherical complex, the precipitate was washed three times or more with distilled water until the supernatant became clear.

Example  10: An amine group  And Vinyl  Magnetic particles containing Polysilsesquioxane  Preparation of Spherical Complexes

1 g and 2.7 g of FeCl ₂ · 4H ₂ O and FeCl ₃ · 6H ₂ O, respectively, were dissolved in 5 mL of water, which was then stirred while heating to 70-100 ° C. To this was added 5 mL of concentrated ammonia water at a time and stirring continued for 30 minutes. 3 mL of water was added to the obtained iron oxide, 0.5 mL of which was mixed with 20 mL of cyclohexane, 1 g of Tween 80 was added, and well dispersed by an ultrasonic mill. 0.3 mL of vinyltrimethoxysilane and 30 μL of aminopropyltrimethoxysilane were added to the mixture, and left for 3 hours to form a magnetic particle-polysilsequioxane sphere containing an amine group of about 0.7 μm.

Example  11: magnetic An amine group  Containing Polymethylsilsesquioxane

Polymethylsilsesquioxane spheres containing amine groups having a diameter of about 2 μm were prepared from a mixture of 3-aminopropyltrimethoxysilane, methyltrimethoxysilane and water weight ratio 1:10:30. 0.1 g of the spheres were mixed with a solution of 1 mL of FeCl ₂ · 4H ₂ O and FeCl ₃ · 6H ₂ O, respectively, and 5 g of water dissolved in 5 mL of water, and left at 70 ° C. for 3 hours. The resulting spheres were precipitated by centrifugation and washed with a small amount of water. The spheres were recovered by centrifugation again and dried at room temperature. The dried sphere was heated to 80 ° C., ammonia water heated to 80 ° C. was added thereto, and the resulting sphere was centrifuged and dried to obtain a polymethylsilsesquioxane sphere containing a magnetic amine group.

Example  12: with fluorescent material An amine group  Containing Polysilsesquioxane By shell Captured  Magnetic particles

0.5 g of methyltrimethoxysilane and 3-aminopropyl were mixed with 2 g of Triton-X 100, 0.5 mL of the iron oxide dispersion solution prepared in Example 6, 10 μL of a 3 wt% Rhodamine G solution, and 10 mL of cyclohexane. 30 μL of trimethoxysilane was mixed and stirred for 24 hours. After allowing the mixture to precipitate, the formed spheres were precipitated, followed by decanting the cyclohexane of the upper layer to the maximum, and 2 mL of a water: ethanol 1: 1 mixture was added thereto, followed by centrifugation to separate the spheres. A sphere surrounded by polysilsesquioxane containing a substance and an amine group was obtained.

Example  13: With gold particles  Surrounded by fluorescent material An amine group  Containing Polysilsesquioxane  By shell Captured  Magnetic particles

When 1 mL of 20 nm gold nanoparticle colloidal solution (British Biocell International, UK) was added to 1 mL of the water mixture in which the spheres obtained in Example 8 were dispersed, a polysilcee containing a phosphor and an amine group immediately surrounded by gold particles was added. Magnetic particles collected with the quoxane shell could be obtained.

Example  14: Gold particles With fluorescent materials An amine group  Containing Polysilsesquioxane By shell Captured  Magnetic particles

1 mL of 0.01 M HAuCl ₄ solution was mixed with 1 mL of the water mixture in which the spheres obtained in Example 8 were dispersed, and when left overnight at 60 ° C., the magnetic particles were collected by a polysilsesquioxane shell containing gold particles, a fluorescent substance and an amine group. Particles could be obtained.

Example  15: An amine group  Contains fluorescent substance Polysilsesquioxane  Conjugation of Spherical Complexes to Antibodies

10 mL of carbonate buffer solution (pH 9.5) was added to the rhodamine-polysilsesquioxane spherical complex precipitate containing the amine group prepared in Example 1, and then dispersed by sonication. The dispersion was then centrifuged at 10,000 g for 10 minutes to wash the precipitate twice in the same manner. 10 mL of glutaaldehyde (10%) was added to the washed particles and allowed to react at room temperature for 1 hour. After centrifugation at 10,000 g for 10 minutes, the precipitate was washed twice with carbonate buffer (pH 9.5) to remove the residue, followed by mouse IgG antibody (Mouse) dissolved in carbonate buffer (pH 9.5). 5 mL of IgG antibody, Arista Biologicals, USA) was added and allowed to react at room temperature for 2 hours. At this time, the concentration of the added antibody was about 1-10% of the polysilsesquioxane sphere content. The reaction was centrifuged again at 10,000 g for 10 minutes, and then 10 mL of carbonate buffer solution (pH 9.5) containing 0.1 M ethanolamine was added thereto, followed by reaction at room temperature for 30 minutes to terminate the reaction. After centrifugation at 10,000 g for 10 minutes, 1 mL of phosphate buffer containing 1% bovine serum albumin was added to the precipitate and refrigerated.

Example  16: An amine group  Magnetic particles containing Polysilsesquioxane  Conjugation of Spherical Complexes to Antibodies

10 mL of carbonate buffer solution (pH 9.5) was added to the magnetic particle-polysilsequioxane spherical composite precipitate prepared in Example 6, dispersed by sonication, and the particles were washed twice using a magnet. 10 mL of glutaaldehyde (10%) was added to the washed magnetic particle-polysilsequioxane spherical complex and reacted at room temperature for 1 hour. The reaction product was centrifuged at 10,000 g for 10 minutes, and then the precipitate was washed twice with carbonate buffer (pH 9.5) to remove the residue. Goat anti-mouse IgG antibody dissolved in carbonate buffer (pH 9.5) in the precipitate. (Goat anti-mouse IgG antibody, Arista Biologicals, USA) 5 mL was added and reacted at room temperature for 2 hours. At this time, the concentration of the added antibody was about 1-10% of the polysilsesquioxane sphere content. The reaction was centrifuged again at 10,000 g for 10 minutes, and then 10 mL of carbonate buffer solution (pH 9.5) containing 0.1 M ethanolamine was added thereto, followed by reaction at room temperature for 30 minutes to terminate the reaction. After centrifugation at 10,000 g for 10 minutes, 1 mL of phosphate buffer containing 1% bovine serum albumin was added to the precipitate and refrigerated.

Example  17: antibody-fluorescent material- Polysilsesquioxane  Spherical Complexes and Antibodies-Magnetic Particles- Polysilsesquioxane  Immune Response Using Complex

To 10 μl of goat anti mouse IgG-magnetic particle-polysilsequioxane complex prepared in Example 12, 1 mL of phosphate buffer solution (pH 7.2) containing 0.05% Tween 20 and 1% bovine serum albumin was added and mixed. 20 μl of the mouse IgG-rhodamine-polysilsequioxane spherical complex prepared in Example 11 was added thereto and reacted at room temperature for 1 hour. The reaction was washed three times with a phosphate buffer solution containing 0.05% Tween 20 using a magnet, followed by antibody-fluorescent material-polysilsequioxane spherical complex and antibody-magnetic particle-polysilsequioxane complex by light and fluorescence microscopy. The combination of was confirmed (FIG. 6).

As shown in FIG. 6, the goat anti mouse IgG-magnetic particle-polysilsequioxane complex recognizes the mouse IgG of the mouse IgG-rhodamine-polysilsequioxane spherical complex as an antigen to form an antigen-antibody aggregate. Could.

As described in detail above, the present invention utilizes a silicone-containing polymer made of a specific monomer as a means of stably collecting a functional material, and the composite of the silicone-containing polymer of the present invention having a functional group is characterized by the type and content of functional groups. By adjusting, it is possible to have the desired chemical, physical and mechanical properties. On the other hand, the complex of the silicone-containing polymer of the present invention having a functional group can bind various other molecules through the functional group, which greatly increases the applicability of the complex of the present invention. The composite of the functional silicone-comprising polymer of the present invention containing a fluorescent substance or a pigment can be prepared in one step, and the composite of the present invention containing a metal particle or magnetic particle can be prepared through a very simple process. The complexes of the present invention include immunoassays, cell and tissue examination using fluorescence microscopy, detection of reactants by DNA polymerization, molecular imaging, biochips, biosensors, fibers, rubber, paper, leather, plastics, food, cosmetics and pigments. Laser and the like.

Having described the specific part of the present invention in detail, it is apparent to those skilled in the art that the specific technology is merely a preferred embodiment, and the scope of the present invention is not limited thereto. Thus, the substantial scope of the present invention will be defined by the appended claims and equivalents thereof.

Claims (24)

In a composite of (a) a silicone-containing polymer and (b) a functional silicone-containing polymer comprising a functional material trapped inside the silicone-containing polymer, the silicone-containing polymer is represented by the formula: A composite of a functional silicone-comprising polymer formed by the polymerization of a monomer represented by 1: Formula 1

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, carboxyl, thiol or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aminoalkylaminoalkyl group, an aminoalkyl group, an aminocycloalkyl group, an aminoalkenyl group, an aminocycloalkenyl group, an aminoallyl group, a cyano alkyl group, ethylenediamine, alkyloxy-carbonyl, aryloxy-carbonyl, alkyl amino carbonyl, aryl amino carbonyl group, an alkoxy or aryloxy group, the R _2, R ₃ R _4, at least two of the dogs alkoxy, arylamino or aryloxy group, n is an integer from 0 to 5. The silicone-containing polymer of claim 1, wherein the silicone-containing polymer has at least one functional group selected from the group consisting of amine groups, thiol groups, vinyl groups, cyano groups, and carboxyl groups. Composite of polymers. The composite of functional silicone-containing polymers according to claim 1, wherein the silicone-containing polymer is polysilsesquioxane. The composite of the functional silicone-containing polymer according to claim 3, wherein the polysilsesquioxane is formed by polymerization of a monomer represented by the following Chemical Formula 2: Formula 2

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and n is an integer from 0 to 5. The method according to claim 4, wherein R ₁ is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aminoalkylaminoalkyl group, an aminoalkyl group, an arylamino group, an aminocycloalkyl group, an aminoalkenyl group, an aminocycloalkenyl group, alkyloxycarbonyl, Aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ Are independently an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and n is an integer of 1-3. 5. The composite of functional silicone-comprising polymers according to claim 4, wherein the polysilsesquioxane has a spherical shape. The composite of functional silicone-containing polymer according to claim 1, wherein the functional material is a fluorescent material, a pigment, a metal particle or a magnetic particle. 3. A composite of functional silicone-containing polymers according to claim 2, wherein the functional groups are formed on the silicone-containing polymer simultaneously with the preparation of the silicone-containing polymer. 3. The silicone-containing polymer of claim 2, wherein the silicone-containing polymer comprises a biomolecule selected from the group consisting of protein, peptide, DNA, RNA and PNA, wherein the biomolecule is conjugated to the silicone-containing polymer via the functional group. A composite of functional silicone-comprising polymers, characterized in that it is conjugated. 8. The composite of functional silicon-containing polymers according to claim 7, wherein the functional material is gold nanoparticles and the surface of the silicon-containing polymer has a gold nanoparticle shell formed thereon. In a composite of a functional silicone-comprising polymer comprising (a) polysilsesquioxane and (b) a functional material trapped inside of the polysilsesquioxane, the polysilsesquioxane has a spherical shape Formed by the polymerization of the monomer represented by the following formula (2), the functional material is a complex of functional polysilsesquioxane, characterized in that the fluorescent material or gold nanoparticles: Formula 2

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and n is an integer from 0 to 5. 12. The complex of functional polysilsesquioxanes according to claim 11, wherein the functional material is a fluorescent material. A method of making a composite of a functional silicone-containing polymer comprising the following steps: (a) mixing the monomer and functional material represented by the following Chemical Formula 1; And Formula 1

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, carboxyl, thiol or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aminoalkylaminoalkyl group, an aminoalkyl group, an aminocycloalkyl group, an aminoalkenyl group, an aminocycloalkenyl group, an aminoallyl group, a cyano alkyl group, or ethylene diamine, alkyloxy-carbonyl, aryloxy-carbonyl, alkyl amino carbonyl, aryl amino carbonyl group, an alkoxy or aryloxy group, the R _2, R ₃ R ₄ and at least two of the alkoxy, aryl, amino or an aryloxy group, n is an integer from 0 to 5; (b) inducing a polymerization reaction of the monomer to prepare a silicone-containing polymer containing the functional material. The method of claim 13, wherein the silicone-comprising polymer has at least one functional group selected from the group consisting of amine groups, thiol groups, vinyl groups, cyano groups, and carboxyl groups. The method of claim 13, wherein the silicone-comprising polymer is polysilsesquioxane. The method according to claim 15, wherein the polysilsesquioxane is formed by polymerization of a monomer represented by the following Chemical Formula 2: Formula 2

In the above formula, R ₁ is hydrogen, alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, alkoxy group, aryloxy group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, Alkyloxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ are each independently an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group, and n is an integer from 0 to 5. The method according to claim 16, wherein R ₁ is an alkyl group, cycloalkyl group, alkenyl group, aryl group, aminoalkylaminoalkyl group, aminoalkyl group, arylamino group, aminocycloalkyl group, aminoalkenyl group, aminocycloalkenyl group, alkyloxycarbonyl, Aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl group, aminoallyl group, hydroxy, amino, nitro, sulfonyl, cyano, thiol, carboxyl or ethylenediamine, R ₂ , R ₃ and R ₄ Are independently alkyl, cycloalkyl, alkenyl or aryl groups, and n is an integer from 1 to 3. 17. The method of claim 16, wherein the polysilsesquioxane has a spherical shape. The method of claim 13, wherein the functional material is a fluorescent material, a dye, a metal particle, or a magnetic particle. 15. The method of claim 14, wherein the functional group is formed on the silicone-comprising polymer concurrently with the preparation of the silicone-comprising polymer. 15. The method of claim 14, wherein the method comprises: (c) conjugation of a biomolecule selected from the group consisting of proteins, peptides, DNA, RNA, PNA, carbohydrates and lipids to the silicon-containing polymer via the functional group. The method further comprises the step of). 20. The method of claim 19, wherein the functional material is gold nanoparticles and the surface of the silicon-comprising polymer is formed with a gold nanoparticle shell. The method of claim 13, wherein step (b) is carried out under water or a mixed solution of water and alcohol. 14. A method according to claim 13, wherein step (b) is carried out by leaving the mixture of step (a) without any treatment.

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