KR20120106357A - Bridged organosilica precursor having amphiphilic polymeric chain and nano particle using thereof - Google Patents

Abstract

PURPOSE: An organic silica precursor with hydrophilic segments and hydrophobic segments and silica/amphiphilic polymer composite nanoparticles using the same are provided to obtain the silica nanoparticles with water dispersibility and various hydrophilic substance supporting ability. CONSTITUTION: An organic silica precursor with a hydrophilic segment and a hydrophobic segment has a structure of chemical formula 1. The molecular weight of polyethylene glycol is 600-15,000. A method for preparing a bridged organic silica precursor comprises: a step of stirring and reacting polypropylene triol or glycerol with diisocyanate of toluene diisocyante, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, or tolidine diisocyanate in a molar ratio of 1:3; a step of adding two or more of methoxy(polyethylene oxy)propyltrimethoxy silane, hydroxymethyl triethoxy silane, aminopropyl triethoxy silane, bis(trimethoxysilane siylypropyl)amine, and (3-glycidoxypropyl)trimethoxy silane in a molar ratio of 1:1; and a step of further adding polyethylene oxide and stirring.

Description

Bridged organosilica precursors having amphiphilic polymer chains and silica / amphiphilic polymer composite nanoparticles using the same and methods for preparing the same {Bridged organosilica precursor having amphiphilic polymeric chain and nano particle using thereof}

The present invention relates to a bridged organoalkoxysilane having a hydrophilic segment and a hydrophobic segment at the same time, and a synthesis thereof. It relates to a silica / amphiphilic polymer composite nanoparticles having a water dispersibility and a method for producing the same.

Currently, silica nanoparticles are used in a wide variety of fields. For example, it is used as an inorganic nano filler to improve the impact resistance and heat resistance of polymers and organic materials, is used as an essential component of cosmetics, and is widely used as a viscosity control material of paints. Recently, it is widely applied as a nano sensor or drug carrier in biotechnology.

Silica nanoparticles must be dispersed in nano size to organic materials such as cosmetics and polymers in order to exhibit this function, and nano size dispersion must be maintained without aggregation in in-vivo state. Therefore, various methods have been tried to increase nano dispersibility of silica nanoparticles. These attempts can be broadly divided into two types: (1) surface treatment of commercialized silica nanoparticles, and (2) organic alkoxysilanes containing hydrophilic or hydrophobic organic materials. The surface treatment method of commercialized silica nanoparticles reacts a polymer or monomer having a functional group capable of reacting with a functional group (mainly a hydroxy group or an amine group) present on the commercialized silica nanoparticle surface to chemically bond the polymer or monomer to the silica nanoparticle. Is a process to disperse nanoscale in various solvents. However, this process is known to have less satisfactory dispersion of silica nanoparticles than complicated processes because of the low degree of grafting efficiency of polymers or monomers bonded to the surface of silica nanoparticles. It is known to be too complicated and expensive to do. Therefore, at present, a process of synthesizing organic alcohols, in particular organic alcohols, in which polymers are combined and using them, to prepare silica nanoparticles that can be dispersed in various solvents is more preferred.

Silica nanoparticles, which are dispersed in nanoscale in various organic solvents, especially in water, are materials that are increasing in demand in biotechnology and cosmetics. In order for the silica nanoparticles to be dispersed in water in nano size, a hydrophilic polymer having sufficient molecular weight must be sufficiently chemically bonded to the silica particle surface. To this end, researches on chemically bonding various hydrophilic polymers to the surface of silica nanoparticles have been actively conducted. That is, various polymer grafting processes and various organoalkoxysilanes have been developed and are still being developed. However, the silica nanoparticles required for biotechnology are silica nanoparticles not only having water dispersibility but also having the ability to support hydrophobic materials. There are very few papers or patent reports on the production of silica nanoparticles having such a function. Therefore, in recent years, research into chemically bonding amphiphilic polymers to silica nanoparticles has been conducted, but there is no such research report in Korea, and the study is still insufficient in foreign countries. The reason is that the amphiphilic polymer must be bonded to the surface of the silica nanoparticles in order to have both water dispersibility and hydrophobic support, but since it is very difficult to synthesize such an amphiphilic polymer itself, It is even more difficult to bond chemically.

Silica nanoparticles of such amphiphilic polymers are expected to be in high demand commercially, particularly in the biotechnology field.

The present invention synthesizes a bridged organosilica precursor having an amphiphilic polymer chain, which is a novel type of organoalkoxysilane, which can produce silica nanoparticles in which amphiphilic polymers are chemically bonded. It is an object of the present invention to provide a method for preparing silica nanoparticles having water dispersibility and hydrophobic material support through a gel process.

In order to achieve the above object, the present invention has a structure of Formula 1,

In Formula 1,

A is a material containing a hydrophobic segment and at least three hydroxyl groups, and reacted with the isocyanate group of B to form a urethane bond;

The B is a material containing two or more isocyanate groups, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other reacts with the C hydroxyl group or amine group to react with a urethane bond or urea bond. Is formed or reacts with the hydroxyl group of D to form a urethane bond;

C is a substance containing a hydroxy group and an alkoxysilane group or an amine group and an alkoxysilane group, wherein the hydroxy group or the amine group reacts with the isocyanate group of B to form a urethane bond or a urea bond;

Wherein D is a substance comprising a hydrophilic segment and two or more hydroxy groups, wherein a urethane bond is formed by reacting with the isocyanate group of B,

It provides a bridged organosilica precursor having an amphiphilic polymer chain.

In addition, the present invention provides a silica / amphiphilic polymer composite nanoparticles that can support a variety of hydrophobic material through a sol-gel reaction using the organosilica precursor.

The present invention synthesizes a bridged organosilica precursor having an amphiphilic polymer chain, which is a novel type of organoalkoxysilane, which can produce silica nanoparticles in which amphiphilic polymers are chemically bonded. The gel process provides silica nanoparticles having water dispersibility and various hydrophobic material loading capabilities.

1 is a diagram of an organosilica precursor including a urethane bond according to the present invention.
2 is a diagram of an organosilica precursor with urea bonds in accordance with the present invention.
3 is a photograph of an organosilica precursor synthesized according to the present invention.
Figure 4 is a photograph of the silica / amphiphilic polymer composite nanoparticles dispersed in water according to the present invention.

The present invention synthesizes a novel alkoxysilane having both a hydrophobic segment and a hydrophilic segment, and uses it as an organosilica precursor to produce a water dispersible silica / amphiphilic polymer composite nanoparticle which can support a hydrophobic material through a typical sol-gel process. It is characterized by manufacturing.

The organosilica precursor according to the present invention is an organoalkoxysilane formed by chemically bonding four materials, A, B, C, and D, as shown in the following Chemical Formula 1.

[Formula 1]

1 and 2 are diagrams showing the bonding structure between materials of Chemical Formula 1.

Referring to Figure 1 and 2 with reference to Formula 1,

A is a material having a hydrophobic segment and three or more hydroxy groups, and each hydroxy group reacts with an isocyanate group to form a urethane bond. Any material having the above characteristics can be applied to the present invention, but preferably includes polypropylene triol or glycerol.

In the present invention, the polypropylene triol includes an oligomer in a structure in which a propylene ether group is expanded to glycerol. By controlling the molecular weight of the polypropylene triol, it is possible to control various sizes of the composite nanoparticles prepared.

The role of B is a material having two or more isocyanate groups as a role of mediating A and C, A and D. One isocyanate group forms a urethane bond with the hydroxy group of A and the other isocyanate group forms a urethane bond with the hydroxy group of the C or D, or reacts with the amine group of C to form a urea bond. Triisocyanate is also applicable as B, but diisocyanate may be preferably used. The diisocyanate may be any material used for urethane synthesis such as toluene diisocyanate (TDI), isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, tolylidine diisocyanate have.

The C is a material having a hydroxyl group or an amine group as a functional group bonded to the B, and simultaneously having an organoalkoxysilane group to form organosilica nanoparticles according to the sol-gel reaction.

D is characterized by having a hydrophilic segment for water dispersibility, and having two or more hydroxy groups to form a urethane bond with the isocyanate group of B. Preferred materials include polyethylene glycol.

Representative materials of A, B, C, and D that can be applied to the present invention are shown in Table 1 below.

matter constitutional formula Chemical name


A

Glycerol

m = 1-50, n = 0-50, p = 0-50 Polypropylene triol















B

,

2,4-toluene diisocyanate,

2-6-toluene diisocyanate

Isophorone diisocyanate

Methylene diisocyanate

4,4'-methylene diphenyl diisocyanate

Hexamethylene diisocyanate

Xylene diisocyanate

Tolidine diisocyanate



C

Methoxy (polyethyleneoxy) propyltrimethoxysilane

Hydroxymethyltriethoxysilane

Aminopropyltriethoxysilane




C

Bis (trimethoxy) silylpropylamine

(3-glycidoxypropyl) trimethoxysilane

[2- (3,4-epoxycyclohexyl) ethyl] trimethoxysilane
D

Polyethylene glycol

Synthesis of the bridged organosilica precursor having an amphiphilic polymer chain having a structure as shown in Formula 1 is performed through the following process.

Synthesis of Organosilica Precursors

Step 1:

Under a nitrogen atmosphere, a urethane bond is formed between A and B by stirring and reacting a substance A having a hydrophobic segment and at least three hydroxyl groups and a substance B having at least two isocyanate groups at a reaction molar ratio of 1: 3 at 70 ° C. for 4 hours. Form.

Step 2:

A substance C having an amine group, an alkoxysilane group, or a hydroxy group and an alkoxysilane group is added to the compound obtained in the first step and reacted to form a urethane or urea bond between B and C. The reaction molar ratio of the substance C synthesized in the first step is 1 mole ratio.

Step 3:

To the composite obtained in the second step, a hydrophilic segment and a hydroxy group having a substance (D), preferably polyethylene oxide having a molecular weight of 600 to 15,000 in 1 molar ratio and stirred to form a urethane bond between B and D to form silica. Synthesize the precursor.

The present inventor named the bridged organosilica precursor having a novel amphiphilic polymer chain synthesized in the present invention as an abbreviation of Amphiphilic Polymeric Alkoxy Silane.

Amphipathy  With silica / Amity  Preparation of Polymer Composite Nanoparticles

The silica / amphiphilic polymer composite nanoparticles according to the present invention are prepared through a typical sol-gel process using bridged organosilica precursors having the amphiphilic polymer chain.

Silica / amphiphilic polymer composite nanoparticles according to the present invention can carry a hydrophobic material while having water dispersibility.

The size of the composite nanoparticles prepared according to the present invention can be variously controlled by combining the molecular weight of the polypropylene triol used or the molecular weight of polyethylene glycol. Using a bridged organosilica precursor having an amphiphilic polymer chain, a process for preparing silica / amphiphilic polymer composite nanoparticles dispersed in water is as follows.

The bridged organosilica precursor having an amphiphilic polymer chain of the present invention is mixed with ethanol or tetrahydrofuran at a weight ratio of 1: 4 to 10 at room temperature. The solution is slowly added dropwise to aqueous solutions of ammonia at various concentrations and vigorously stirred to prepare silica / amphiphilic polymer composite nanoparticles.

Example  1 to 9

Under a nitrogen atmosphere, glycerol or polypropylene triol and 2,4-toluene diisocyanate were stirred and reacted at about 70 ° C. for 4 hours in a 1: 3 reaction molar ratio.

To the composite obtained through the above step, methoxy (polyethyleneoxy) propyltrimethoxysilane was added in a 1: 1 reaction molar ratio and stirred.

To the composite obtained in the above step, polyethylene oxide having a molecular weight of 600, 1000, 1500 and 2000, respectively, was added in a 1 molar ratio, followed by stirring to synthesize a bridged organosilica precursor having an amphiphilic polymer chain.

3 is a photograph of an organosilica precursor synthesized according to the present invention.

10 g of the bridged organosilica precursor having the amphiphilic polymer chain was mixed with 40 g of ethanol or tetrahydrofuran at room temperature. The prepared solution was stirred vigorously with 0.32 M aqueous ammonia solution and vigorously stirred to prepare silica / amphiphilic polymer composite nanoparticles.

Figure 4 is a photograph of the silica / amphiphilic polymer composite nanoparticles dispersed in accordance with the present invention.

The characteristics of the silica / amphiphilic polymer composite nanoparticles prepared according to Examples 1 to 9 are shown in Table 2 below.

Example Compound name Polypropylene triol
Molecular Weight (g / mol) Polyethylene glycol
Molecular Weight (g / mol) Particle Size (nm) Example 1   APAS GC-600 92.09 600      189.5 Example 2   APAS GC-1000 92.09 1000      113.7 Example 3   APAS GC-1500 92.09 1500      135.9 Example 4   APAS GC-2000 92.09 2000       78.05 Example 5   APAS 260-1000 260 1000       93.20 Example 6   APAS 260-1500 260 1500       88.45 Example 7   APAS 260-2000 260 2000       80.22 Example 8   APAS 725-1000 725 1000      102.35 Example 9   APAS 725-1500 725 1500      105.2

* In the compound name, GC indicates that glycerol was used in the synthesis of APAS, and when 260, GAS was written after GAS, and when polypropylene triol was used, the molecular weight of polypropylene triol after APAS was expressed in Arabic numerals. Indicated as. Arabic numerals also indicate that the molecular weight of the polypropylene triol used is 260, 725 g / mol. Arabic numerals 1000, 1500 and 2000 refer to the molecular weight of polyethylene glycol used in the synthesis of APAS.

Example  10 to 13: particle size depending on the solvent

In the same manner as in Example 1, the silica / amphiphilic polymer of the present invention through a sol-gel reaction by changing the ratio of the organosilica precursor and the solvent (ethanol, tetrahydrofuran) in the weight ratio of 1: 4 ~ 1:40 Composite nanoparticles were prepared.

The properties of the silica / amphiphilic polymer composite nanoparticles prepared according to Examples 10 to 13 are shown in Table 3 below.

Compound name APAS: Ethanol (weighted) Ammonia Water Concentration Particle Size (nm) Example 6 APAS 260-1500 1: 4 0.32M 88.45 Example 10 APAS 260-1500 1: 5 0.32M 94.33 Example 11 APAS 260-1500 1:10 0.32M 198.5 Example 12 APAS 260-1500 1:20 0.32M coagulation Example 13 APAS 260-1500 1:40 0.32M 54.69

As shown in Table 2 and Table 3, the silica / amphiphilic polymer composite nanoparticles prepared according to the present invention was dispersed very stably in water, the size was in the range of 80-200 nm in nano size. In addition, the particle size was changed depending on the molecular weight of polypropylene triol and polyethylene glycol used in the precursor synthesis, and also changed depending on the ratio of the solvent (ethanol, tetrahydrofuran) and the precursor used.

Example  14 to 22 hydrophobic substances Intelligence

In order to measure the hydrophobic material support of the prepared silica / amphiphilic polymer nanoparticles, the experiment was performed by the following procedure.

A uniform solution was prepared by mixing 10 g of the bridged organosilica precursor having an amphiphilic polymer chain with 40 g of ethanol. 1-5 g of tocopherol, which is a representative hydrophobic substance, was added to the prepared solution and mixed at room temperature. Stirring for about 10 minutes gave a uniform solution. The solution was dripped vigorously while being dropped into ammonia water, and it was confirmed that the silica / amphiphilic polymer composite nanoparticles having the tocopherol formed in the water were formed very stably at nano size.

The particle size and the supporting ability of the prepared nano composite nanoparticles are shown in Table 4 below.

Compound name Support amount (wt%) Intelligence (%) Particle Size (nm) Example 14  APAS GC-1500 10 98 209.5 Example 15  APAS GC-1500 30 85 183.7 Example 16  APAS GC-1500 50 78 195.9 Example 17  APAS 260-1500 10 99 108.05 Example 18  APAS 260-1500 30 92 193.20 Example 19  APAS 260-1500 50 90 188.45 Example 20  APAS 725-1500 10 100 100.22 Example 21  APAS 725-1500 30 100  111.35 Example 22  APAS 725-1500 50 100 115.2

Claims (9)

Has a structure of Formula 1,
[Formula 1]

In Chemical Formula 1,
A is a material containing a hydrophobic segment and at least three hydroxyl groups, and reacted with the isocyanate group of B to form a urethane bond;
The B is a material containing two or more isocyanate groups, one isocyanate group reacts with the hydroxyl group of A to form a urethane bond, and the other reacts with the C hydroxyl group or amine group to react with a urethane bond or urea bond. Is formed or reacts with the hydroxyl group of D to form a urethane bond;
C is a substance containing a hydroxy group and an alkoxysilane group or an amine group and an alkoxysilane group, wherein the hydroxy group or the amine group reacts with the isocyanate group of B to form a urethane bond or a urea bond;
D is a material containing a hydrophilic segment and two or more hydroxy groups, and reacted with an isocyanate group of B to form a urethane bond,
Bridged organosilica precursors having an amphiphilic polymer chain.
The method of claim 1,
A is a polypropylene triol or glycerol, bridged organosilica precursor having an amphiphilic polymer chain.
The method of claim 1,
Wherein B is diisocyanate, bridged organosilica precursor having an amphiphilic polymer chain.
The method of claim 3,
The diisocyanate is one or two or more amphiphilic polymers selected from the group consisting of toluene diisocyanate, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, tolidine diisocyanate Bridged organosilica precursors with chains.
The method of claim 1,
C is methoxy (polyethyleneoxy) propyltrimethoxysilane, hydroxymethyltriethoxysilane, aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (3-glycidoxypropyl) trimeth A bridged organosilica precursor having an amphiphilic polymer chain, which is one or two or more selected from the group consisting of oxysilane, [2- (3,4-epoxycyclohexyl) ethyl] trimethoxysilane.
The method of claim 1,
Wherein D is polyethylene glycol, bridged organosilica precursor having an amphiphilic polymer chain.
The method according to claim 6,
The molecular weight of the polyethylene glycol is 600 to 15,000, bridged organosilica precursor having an amphiphilic polymer chain.
Under nitrogen atmosphere, polypropylene triol or glycerol
1: 3 reaction molar ratio with at least one selected from diisocyanate group consisting of toluene diisocyanate, isophorone diisocyanate, methylene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, tolidine diisocyanate A first step of stirring reaction;
To the material obtained in the first step, methoxy (polyethyleneoxy) propyltrimethoxysilane, hydroxymethyltriethoxysilane, aminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, (3-glycidyl) Doxypropyl) trimethoxysilane, [2- (3,4-epoxycyclohexyl) ethyl] trimethoxysilane, and one or more selected from the group consisting of a second reaction molar ratio by further adding a second reaction step;
And a third step of adding a polyethylene oxide having a molecular weight of 600 to 15,000 to a material obtained in the second step in a 1: 1 reaction molar ratio to stir reaction.
A method for producing a bridged organosilica precursor having an amphiphilic polymer chain.
Dissolving the bridged organosilica precursor having an amphiphilic polymer chain according to claim 1 in an organic solvent;
Adding and mixing hydrophobic substances to be supported in the solution;
It includes a sol-gel reaction step of reacting by dropping ammonia water to the mixed solution,
Method for producing silica / amphiphilic polymer composite nanoparticles loaded with a hydrophobic material.

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