KR102375919B1 - a method for manufacturing nanoparticle using photo-crosslinkable negative charged polymer - Google Patents

Abstract

The present invention relates to a method for producing nanoparticles using a photocrosslinkable negatively charged polymer, and more particularly, to a method for preparing a polymer having an anionic group by mixing and reacting poly(4-vinylphenol) and a basic compound; (b) mixing and reacting the polymer having an anionic group and benzoylbenzoic acid to prepare a copolymer having a photocrosslinkable group; (c) preparing a mixture by mixing the copolymer having the photocrosslinkable group and a solvent; (d) crosslinking the copolymer by irradiating the mixture with ultraviolet rays; And (e) relates to a method for preparing polymer nanoparticles comprising the step of obtaining the cross-linked copolymer, and polymer nanoparticles prepared therefrom.

Description

A method for manufacturing nanoparticles using photo-crosslinkable negatively charged polymer

The present invention relates to a method for producing nanoparticles using a photocrosslinkable negatively charged polymer, and more particularly, to a method for preparing a polymer having an anionic group by mixing and reacting poly(4-vinylphenol) and a basic compound; (b) mixing and reacting the polymer having an anionic group and benzoylbenzoic acid to prepare a copolymer having a photocrosslinkable group; (c) preparing a mixture by mixing the copolymer having the photocrosslinkable group and a solvent; (d) crosslinking the copolymer by irradiating the mixture with ultraviolet rays; And (e) relates to a method for preparing polymer nanoparticles comprising the step of obtaining the cross-linked copolymer, and polymer nanoparticles prepared therefrom.

Polymer electrolytes contain ions within themselves, so they can be applied to various fields.

For example, since the polymer electrolyte has conductivity, efficiency improvement can be expected when applied to electronic devices, and self-assembly characteristics can be expressed through the interaction of charges.

Organic material-based polymer electrolytes have superior solubility in solvents compared to inorganic materials, so they can be prepared in various ways, and are very environmentally friendly materials because they can be dissolved in solvents such as water and alcohol.

However, in other polar solvents, the solubility is very low, so the choice of solvent is extremely limited.

Therefore, it is required to develop a technology capable of controlling the solubility of the polymer electrolyte copolymer and securing morphological stability by introducing an anionic group and a photocrosslinkable functional group.

Korean Patent Registration No. 10-0508365

The present invention is to solve the problems of the prior art, and an object of the present invention is to provide a method for preparing a polymer electrolyte copolymer having excellent solubility in various solvents and improved morphological stability by introducing an anionic group and a photocrosslinkable group there is.

Another object of the present invention is to provide a method for preparing polymer nanoparticles having a uniform particle size and excellent dispersibility from the polymer electrolyte copolymer.

In order to achieve the above object, the present invention comprises the steps of (a) mixing and reacting poly(4-vinylphenol) and a basic compound to prepare a polymer having an anionic group;

(b) mixing and reacting the polymer having an anionic group and benzoylbenzoic acid to prepare a copolymer having a photocrosslinkable group;

(c) preparing a mixture by mixing the copolymer having the photocrosslinkable group and a solvent;

(d) crosslinking the copolymer by irradiating the mixture with ultraviolet rays; and

(e) provides a method for producing polymer nanoparticles comprising the step of obtaining the cross-linked copolymer.

In one embodiment of the present invention, in step (a), 0.05 to 0.5 moles of the basic compound are used per mole of the repeating unit of poly(4-vinylphenol).

In one embodiment of the present invention, the polymer having an anionic group in step (a) is characterized in that it has a structure of the following formula (1).

[Formula 1]

(m and l are integers from 5 to 1,000)

In one embodiment of the present invention, the benzoylbenzoic acid in step (b) is characterized in that at least one selected from 2-benzoylbenzoic acid, 3-benzoylbenzoic acid and 4-benzoylbenzoic acid.

In one embodiment of the present invention, the copolymer having a photocrosslinkable group in step (b) is characterized in that it has a structure of the following formula (2).

[Formula 2]

(o, p and q are integers from 5 to 1,000)

In one embodiment of the present invention, the solvent of step (c) is characterized in that distilled water and ethanol are used.

In addition, the present invention provides polymer nanoparticles prepared by the above manufacturing method.

The present invention can provide a method for preparing a polymer electrolyte copolymer having excellent solubility in various solvents and improved morphological stability by introducing an anionic group and a photocrosslinkable group.

In addition, the present invention can provide a method for producing polymer nanoparticles having a uniform particle size and excellent dispersibility from the polymer electrolyte copolymer.

1 shows a process for preparing a polymer having an anionic group.
2 shows a process for preparing a copolymer having a photocrosslinkable group.
3 shows ¹ H NMR of a copolymer having a photocrosslinkable group.
4 shows a UV-VIS spectrum of a copolymer having a photocrosslinkable group.
5 shows an FT-IR spectrum of a copolymer having a photocrosslinkable group.
6 shows the FT-IR spectrum according to the UV crosslinking time of a copolymer having a photocrosslinkable group.
7 shows the contact angle according to the UV crosslinking time of a copolymer having a photocrosslinkable group.
8 shows the surface charge of polymer nanoparticles prepared by UV crosslinking a copolymer having a photocrosslinkable group.
9 shows an SEM photograph of polymer nanoparticles prepared by UV crosslinking a copolymer having a photocrosslinkable group.

Hereinafter, the present invention will be described in detail based on Examples. Terms, examples, etc. used in the present invention are merely exemplified to explain the present invention in more detail and help those of ordinary skill in the art to understand, and the scope of the present invention should not be construed as being limited thereto.

Technical terms and scientific terms used in the present invention represent meanings commonly understood by those of ordinary skill in the art to which this invention belongs, unless otherwise defined.

In order to achieve the above object, the present invention comprises the steps of (a) mixing and reacting poly(4-vinylphenol) and a basic compound to prepare a polymer having an anionic group;

(b) mixing and reacting the polymer having an anionic group and benzoylbenzoic acid to prepare a copolymer having a photocrosslinkable group;

(c) preparing a mixture by mixing the copolymer having the photocrosslinkable group and a solvent;

(d) crosslinking the copolymer by irradiating the mixture with ultraviolet rays; and

(e) relates to a method for producing polymer nanoparticles comprising the step of obtaining the cross-linked copolymer.

In step (a), a polymer having an anionic group may be prepared by mixing and reacting poly(4-vinylphenol) and a basic compound ( FIG. 1 ). In FIG. 1, n, m, and l are preferably integers of 5 to 1,000.

The basic compound may be used without limitation, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonium hydroxide.

In the present invention, 0.05 to 0.5 moles of the basic compound per mole of the repeating unit of poly(4-vinylphenol) may be used. When the molar ratio satisfies the above numerical range, the particle size distribution and dispersibility of the prepared polymer nanoparticles may be improved.

The polymer having an anionic group is characterized in that it has a structure of the following formula (1).

[Formula 1]

(m and l are integers from 5 to 1,000)

The step (a) comprises the steps of preparing a first mixture by mixing poly(4-vinylphenol) and a solvent; preparing a second mixture by adding and reacting a basic compound to the first mixture; preparing a polymer solution from which residues have been removed by dialysis of the second mixture; and drying the polymer solution to obtain a polymer having an anionic group.

The solvent may be used without limitation, such as ethanol, methanol, acetone.

In step (b), a copolymer having a photocrosslinkable group may be prepared by mixing and reacting the polymer having an anionic group and benzoylbenzoic acid ( FIG. 2 ). In FIG. 2, m, l, o, p and q are preferably integers of 5 to 1,000.

The benzoylbenzoic acid may be one or more selected from 2-benzoylbenzoic acid, 3-benzoylbenzoic acid and 4-benzoylbenzoic acid, and 4-benzoylbenzoic acid is preferable.

In the present invention, 0.1 to 0.5 moles of benzoylbenzoic acid may be used per 1 mole of the repeating unit of the polymer having an anionic group. When the molar ratio satisfies the above numerical range, the particle size distribution and dispersibility of the prepared polymer nanoparticles may be improved.

The copolymer having the photocrosslinkable group is characterized in that it has a structure of the following formula (2).

[Formula 2]

(o, p and q are integers from 5 to 1,000)

The step (b) comprises the steps of preparing a first mixture by mixing the polymer and the solvent having an anionic group; preparing a second mixture by adding N,N'-dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP) and 4-benzoylbenzoic acid to the first mixture and reacting; preparing a polymer solution from which residues have been removed by dialysis of the second mixture; and drying the polymer solution to obtain a copolymer having a photocrosslinkable group.

The solvent may be used without limitation, such as ethanol, methanol, acetone.

The copolymer includes a polar moiety by a phenol group, an ionic moiety by a phenoxide group, and a weakly polar moiety by a benzophenone group. In addition, the benzophenone group may be photocrosslinked by UV irradiation.

The copolymer of the present invention has excellent solubility in various solvents and improved morphological stability by introducing an anionic group and a photocrosslinkable group.

In step (c), a mixture may be prepared by mixing the copolymer having the photocrosslinkable group and a solvent.

The solvent is preferably a mixture of distilled water and ethanol. In addition, distilled water and acetone may be mixed and used.

At this time, it is preferable to use 0.1 to 10 parts by weight of the copolymer with respect to 100 parts by weight of the solvent, more preferably 0.25 to 5 parts by weight.

The volume ratio of the ethanol and distilled water is preferably 1:2-15, and when the volume ratio satisfies the numerical range, the particle size distribution and dispersibility of the prepared polymer nanoparticles can be improved.

In step (d), the copolymer may be cross-linked by irradiating the mixture with ultraviolet rays.

The benzophenone group contained in the copolymer may improve mechanical properties, shape stability, surface properties, etc. of the copolymer by performing a crosslinking reaction by a light source such as ultraviolet rays.

When the copolymer is irradiated with a light source such as ultraviolet rays, radicals are formed in the ketone group of benzophenone contained in the copolymer, and the formed radicals absorb hydrogen from the surrounding hydrocarbon chain to form a hydroxyl group, and coupling between the remaining radicals The reaction is carried out to cause crosslinking.

The crosslinking time is preferably 1 to 20 minutes, and when the crosslinking time satisfies the above numerical range, the particle size distribution and dispersibility of the prepared polymer nanoparticles can be improved.

Step (e) is a step of obtaining the cross-linked copolymer, and polymer nanoparticles can be prepared by removing the solvent contained in the mixture.

The present invention also relates to polymer nanoparticles prepared by the above method.

Since the polymer nanoparticles contain anionic groups on the surface, they have excellent dispersibility and can bind to positively charged metal ions, so that various organic-inorganic composite materials can be prepared.

In addition, the polymer nanoparticles can improve mechanical properties and morphological stability by crosslinking through ultraviolet irradiation.

The polymer nanoparticles have a particle size of 100 to 550 nm, a uniform particle size, and excellent dispersibility.

Hereinafter, the present invention will be described in detail through Examples and Comparative Examples. The following examples are only exemplified for the practice of the present invention, and the content of the present invention is not limited by the following examples.

(Example 1)

A first mixture was prepared by mixing 0.5 g (3.08 mmol) of poly(4-vinylphenol) and 12 ml of ethanol.

12 mg (0.3 mmol) of sodium hydroxide was added to the first mixture and reacted for one day at room temperature under a nitrogen atmosphere to prepare a second mixture.

After the second mixture was concentrated, it was placed in a dialysis tube. Ethanol and water were added in a volume ratio of 1:1 in the dialysis chamber, and then a dialysis tube was put in and the dialysis tube was stirred.

By checking the pH of the solvent in the dialysis chamber once every hour, it was confirmed whether the residual sodium hydroxide came out of the dialysis tube. At this time, the solvent in the dialysis chamber was replaced 5 times or more, once every 2 hours.

The polymer solution from which the residue was removed was dried for one day to obtain 0.47 g of a cloudy brown polymer (polymer having an anionic group; POHX).

A first mixture was prepared by mixing 0.3 g (1.826 mmol) of the anionic polymer (POHX) and 12 ml of ethanol.

N,N'-dicyclohexylcarbodiimide (DCC) 0.11g (0.3eq), 4-dimethylaminopyridine (DMAP) 0.0067g (0.3eq) and 4-benzoylbenzoic acid 0.11g (0.27eq) were added to the first mixture and heated at 40°C A second mixture was prepared by reacting for 12 hours.

After the second mixture was concentrated, it was placed in a dialysis tube. Ethanol was added into the dialysis chamber, and then a dialysis tube was put in and the dialysis tube was stirred.

Once an hour, the solvent in the dialysis chamber was extracted with a capillary tube, and it was checked whether unreacted substances came out of the dialysis tube through ultraviolet irradiation. At this time, the solvent in the dialysis chamber was replaced 5 times or more, once every 2 hours.

The polymer solution from which the residue was removed was dried for one day to obtain 0.41 g of a cloudy ivory polymer (copolymer having a photocrosslinkable group; POHB).

A mixture was prepared by mixing 0.1 g of the copolymer having a photocrosslinkable group (POHB), 1 ml of ethanol, and 9 ml of distilled water.

The copolymer was crosslinked by irradiating the mixture with ultraviolet rays for 3 minutes.

The solvent contained in the mixture was removed to obtain polymer nanoparticles (particle diameter of 220 nm).

3 shows ¹ H NMR of a copolymer (POHB) having a photocrosslinkable group, and a unique peak of benzophenone can be confirmed at 7-8 ppm.

4 shows a UV-VIS spectrum of a copolymer (POHB) having a photocrosslinkable group, and a peak of a phenol group at 225 nm, a peak of a benzophenone at 259 nm, and a peak of a vinyl group at 279 nm can be confirmed.

5 shows the FT-IR spectrum of the copolymer (POHB) having a photocrosslinkable group, and peaks of the carbonyl group of benzophenone can be confirmed at 735 cm ^-1 and 1,650 cm ^-1 .

6 shows the FT-IR spectrum according to the UV crosslinking time of the copolymer having a photocrosslinkable group (POHB). It can be seen that the peak of the carbonyl group at 1,650 cm ^-1 decreases as the crosslinking time increases.

7 shows the contact angle according to the UV crosslinking time of a copolymer having a photocrosslinkable group (POHB). It can be seen that the contact angle increases with the crosslinking time, and the maximum contact angle is exhibited at the crosslinking time of 3 minutes, after which the contact angle decreases. Therefore, in consideration of the surface characteristics and the contact angle, the UV crosslinking time of the copolymer is preferably 1 to 20 minutes.

8 shows the surface charge of polymer nanoparticles prepared by UV crosslinking a copolymer having a photocrosslinkable group. It can be confirmed that the surface charge of the nanoparticles represents a negative charge.

9 shows an SEM photograph of polymer nanoparticles prepared by UV crosslinking a copolymer having a photocrosslinkable group. The polymer nanoparticles have a particle size (particle diameter) of 100 to 550 nm, and it can be confirmed that the particle size is uniform and the dispersibility is excellent.

(Example 2)

Polymer nanoparticles were obtained in the same manner as in Example 1, except that 0.5 g (3.08 mmol) of poly(4-vinyl phenol) and 4 mg (0.1 mmol) of sodium hydroxide were used.

(Example 3)

Polymer nanoparticles were obtained in the same manner as in Example 1, except that 0.5 g (3.08 mmol) of poly(4-vinyl phenol) and 72 mg (1.8 mmol) of sodium hydroxide were used.

(Example 4)

Polymer nanoparticles were obtained in the same manner as in Example 1, except that 5 ml of ethanol and 5 ml of distilled water were mixed and used.

(Example 5)

Polymer nanoparticles were obtained in the same manner as in Example 1, except that 0.5 ml of ethanol and 9.5 ml of distilled water were mixed and used.

(Comparative Example 1)

Polymer nanoparticles were obtained in the same manner as in Example 1, except that the copolymer (POHB) having a photocrosslinkable group was not prepared, and polymer nanoparticles were prepared from a polymer (POHX) having an anionic group.

The size, uniformity and dispersibility of the polymer nanoparticles prepared in Examples and Comparative Examples were measured, and the results are shown in Table 1 below.

The size and uniformity of polymer nanoparticles were measured using SdFFF.

The uniformity of the polymer nanoparticles was marked as excellent if the standard deviation of the average nanoparticle size was 5% or less of the average nanoparticle size, excellent if 10% or less, normal if 15% or less, and bad if it exceeded 15%.

The dispersibility of polymer nanoparticles was confirmed after the nanoparticle composition was placed in a container and allowed to stand at 25° C. for 12 hours.

Visually, the dispersibility was marked as excellent, excellent, average, and poor.

division Example comparative example One 2 3 4 5 One size of nanoparticles
(nm) 220 370 310 280 330 580 Nanoparticle uniformity eminence commonly commonly Great commonly error dispersibility eminence commonly Great commonly commonly error

From the results of Table 1, it can be seen that the polymer nanoparticles of Examples 1 to 5 have a uniform particle size and excellent dispersibility. In particular, Example 1 has the most excellent properties.

On the other hand, it can be seen that Comparative Example 1 is inferior to that of Example.

Claims (7)

(a) preparing a polymer having an anionic group by mixing and reacting poly(4-vinylphenol) and a basic compound;
(b) mixing and reacting the polymer having an anionic group and benzoylbenzoic acid to prepare a copolymer having a photocrosslinkable group;
(c) preparing a mixture by mixing the copolymer having the photocrosslinkable group and a solvent;
(d) crosslinking the copolymer by irradiating the mixture with ultraviolet rays; and
(e) a method for producing polymer nanoparticles comprising the step of obtaining the cross-linked copolymer.
According to claim 1,
The step (a) is
A method for producing polymer nanoparticles, characterized in that 0.05 to 0.5 moles of the basic compound are used per mole of the repeating unit of poly(4-vinylphenol).
3. The method of claim 2,
The polymer having an anionic group in step (a) is
Method for producing polymer nanoparticles, characterized in that having the structure of the following formula (1).

[Formula 1]

(m and l are integers from 5 to 1,000)
4. The method of claim 3,
The benzoylbenzoic acid of step (b) is
2-benzoylbenzoic acid, 3-benzoylbenzoic acid and 4-benzoylbenzoic acid production method, characterized in that at least one selected from the polymer nanoparticles.
5. The method of claim 4,
The copolymer having a photocrosslinkable group of step (b) is
Method for producing polymer nanoparticles, characterized in that having the structure of the following formula (2).

[Formula 2]

(o, p and q are integers from 5 to 1,000)
6. The method of claim 5,
The solvent of step (c) is
Method for producing polymer nanoparticles, characterized in that using distilled water and ethanol.
Polymer nanoparticles prepared by the method of claim 1.

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