TWI520989B - Method for fabricating polymer sphere - Google Patents

Description

Method for preparing polymer spheres

The invention relates to a method for preparing a polymer sphere, in particular to a method for preparing a polymer sphere by thermal annealing treatment.

Polymer spheres are widely used in a wide variety of products, such as polymer spheres, which can be used as coating, sensing, inkjet, and drug release materials. At present, a method of preparing a polymer sphere is usually carried out by a suspension polymerization method or an emulsion polymerization method. However, when these methods are used to prepare a polymer spherical material, only micron-sized polymer spheres can be formed, and there are many problems such as uneven particle size, irregular shape, and long polymerization time. In addition, the conventional preparation method often requires the addition of an additive such as an emulsifier, a dispersant or a surfactant. Therefore, the application of the polymer sphere obtained by the current method is limited.

In view of this, there is a need for a method for preparing a polymer sphere, which does not require the addition of additional additives, and has the advantages of simple and rapid process.

The invention provides a method for preparing a polymer sphere, comprising coating a polymer solution on a substrate to form a polymer film. Next, the polymer The film is placed in a dispersion medium for thermal annealing to form a polymer film into a plurality of polymer balls. The dispersion medium does not dissolve the polymer and has a boiling point higher than the glass transition temperature of the polymer. The thermal annealing treatment is performed at a temperature higher than the glass transition temperature of the polymer and lower than the boiling point of the dispersion medium, and the thermal annealing treatment time is about 1 to 180 minutes.

In one embodiment of the present invention, the method for preparing a polymer sphere further comprises dissolving a polymer in a solvent to form a polymer solution, wherein the solvent is toluene, tetrahydrofuran, acetone, cyclohexane, dimethylformamide, Methyl ethyl ketone, chloroform, acetic acid, pentane or dimethyl hydrazine.

In one embodiment of the present invention, a method of forming a polymer film includes drying a polymer solution coated on a substrate to remove a solvent to form a polymer film.

In one embodiment of the present invention, the polymer is a polyester polymer, a polyamide polymer, a polycarbonate polymer, a polyurethane polymer, or a poly polymer. An alkylene polymer (polyalkylene) or a modified product thereof, a crosslinkable polymer, a copolymer, or any combination thereof.

In one embodiment of the invention, the polyester polymer is polyethylene terephthalate.

In one embodiment of the invention, the polyamine polymer is Nylon-6,6 or polyacrylamide.

In one embodiment of the present invention, the polycarbonate polymer is Lexan® (SABIC Innovative Plastics).

In one embodiment of the present invention, the polyolefin polymer and the modification thereof are polyethylene, polypropylene, polystyrene, poly(methyl methacrylate). ) or polyvinyl chloride.

In one embodiment of the invention, the crosslinkable polymer is an epoxy or a polydimethylsiloxane.

In one embodiment of the invention, the copolymer is an acrylonitrile-butadiene-styrene (ABS) copolymer.

In one embodiment of the invention, the molecular weight of the polymer is from about 10,000 to 1,000,000 Da.

In one embodiment of the present invention, the method of applying the polymer solution onto the substrate is spin coating, blade coating, spray coating, and slit coating ( Slot die coating) or inkjet coating.

In one embodiment of the invention, the thickness of the polymeric film is from about 50 to about 100,000 nm.

In one embodiment of the invention, the dispersion medium is ethylene glycol, 1,2-propylene glycol, glycerol or eucalyptus oil.

In one embodiment of the invention, the temperature of the thermal annealing treatment is about 50 to 250 °C.

In one embodiment of the invention, the polymer spheres have a particle size of from about 50 to about 1000 nm.

100‧‧‧ method

110, 120‧‧‧ steps

210‧‧‧ polymer film

212‧‧‧Polymer sphere

220‧‧‧Substrate

230‧‧‧ container

240‧‧‧Dispersion medium

250‧‧‧ Magnet

To make the features, advantages and embodiments of the present invention more apparent, the description of the drawings is as follows:

FIG. 1 is a schematic flow chart showing the preparation of a polymer sphere according to an embodiment of the present invention.

Fig. 2 is a schematic view showing the operation of preparing a polymer ball according to an embodiment of the present invention.

Fig. 3A is a microscopic image showing a polymer sphere according to an embodiment of the present invention.

Fig. 3B is a microscopic image showing a polymer sphere according to another embodiment of the present invention.

Fig. 4 is a view showing a particle size distribution diagram of a polymer sphere according to an embodiment of the present invention.

Fig. 5A is a microscopic image showing a polymer sphere according to an embodiment of the present invention.

Fig. 5B is a microscopic image showing a polymer sphere according to another embodiment of the present invention.

Fig. 6 is a microscope image showing a polymer sphere according to still another embodiment of the present invention.

In order to make the description of the present invention more detailed and complete, the embodiments of the present invention are described with reference to the accompanying drawings. The embodiments disclosed herein may be combined or substituted with each other in an advantageous manner, and other embodiments may be added to an embodiment without further description or description. In the following description, numerous specific details are set forth However, embodiments of the invention may be practiced without these specific details.

Please refer to FIG. 1 , which is a schematic flow chart of preparing a polymer sphere according to an embodiment of the present invention. The method 100 for preparing a polymer sphere of the present invention first applies a polymer solution onto a substrate to form a polymer film (step 110).

In one embodiment of the present invention, the method for preparing a polymer sphere further comprises dissolving a polymer in a solvent to form a polymer solution, wherein the solvent is toluene, before applying the polymer solution to the substrate. Tetrahydrofuran, acetone, cyclohexane, dimethyl formamide, methyl ethyl ketone, chloroform, acetic acid, pentane (pentane) or dimethyl sulfoxide (DMSO). In this embodiment, the method of forming a polymer film (step 110) further comprises drying the polymer solution coated on the substrate to remove the solvent and form a polymer film.

In one embodiment of the present invention, the polymer is a polyester polymer, a polyamide polymer, a polycarbonate polymer, a polyurethane polymer, or a poly polymer. An alkylene polymer (polyalkylene) or a modified product thereof, a crosslinkable polymer, a copolymer, or any combination thereof.

When the polymer is a polyester polymer, it may be polyethylene terephthalate.

When the polymer is a polyamine polymer, it may be Nylon-6,6 or polyacrylamide.

When the polymer is a polycarbonate polymer, it may be Lexan® (SABIC Innovative Plastics).

When the polymer is a polyolefin polymer or a modified product thereof, it may be a polyolefin polymer, an aromatic polyene polymer, a polyenoic polymer or a halogen-containing polyolefin polymer, for example, poly Polyethylene, polypropylene, polystyrene, poly(methyl methacrylate), and polyvinyl chloride.

When the polymer is a crosslinkable polymer, it may be an epoxy or a polydimethylsiloxane.

When the polymer is a copolymer, it may be a terpolymer such as an acrylonitrile-butadiene-styrene (ABS) copolymer.

In one embodiment of the present invention, the molecular weight of the polymer is about 10,000 to 1,000,000 Da (ie, 10 to 1000 kDa), for example, the molecular weight of the polymer may be 10, 50, 75, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1000 kDa.

The method of applying the polymer solution onto the substrate may be a wet process. The wet process may be spin coating, blade coating, spray coating, slot die coating or inject coating.

Referring to Fig. 1, the method 100 for preparing a polymer sphere of the present invention is followed by subjecting a polymer film to a dispersion medium for thermal annealing treatment to form a polymer film into a plurality of polymer spheres (step 120). Wherein, the dispersion medium does not dissolve the polymer, and the boiling point is higher than the glass transition temperature of the polymer.

It is worth noting that the thermal annealing treatment needs to be carried out at a glass transition temperature higher than that of the polymer to provide polymer energy and change its molecular structure. Change, and then form a sphere state with a stable structure. At the same time, the thermal annealing treatment needs to be below the boiling point of the dispersion medium to avoid boiling of the dispersion medium during the thermal annealing treatment. In an embodiment of the present invention, the temperature of the thermal annealing treatment is about 50 to 250 ° C, for example, the temperature of the thermal annealing treatment may be 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240 or 250 °C.

The thermal annealing treatment time is about 1 to 180 minutes, for example, the thermal annealing treatment time may be 1, 10, 15, 30, 45, 60, 75, 90, 105, 120, 135, 150, 165 or 180 minutes.

In one embodiment of the present invention, the polymer film has a thickness of about 50 to 100,000 nm, for example, a thickness of 50, 100, 200, 300, 400, 500, 1000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70000, 80000, 90000 or 100000 nm. The thickness of the polymer film affects the particle size of the formed polymer sphere. If the thickness of the polymer film is less than 100 nm, it may have a small size effect, and the particle diameter of the formed polymer sphere may be 100 nm or less. In one embodiment of the present invention, the polymer sphere obtained by the preparation method of the present invention has a particle diameter of about 50 to 1000 nm, for example, the particle diameter may be 50, 100, 150, 200, 250, 300, 350, 400. , 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950 or 1000 nm.

The preparation method of the present invention uses a dispersion medium which does not dissolve the polymer as a uniform medium, and the polymer film can be uniformly heated therein by the dispersion medium. In addition, the boiling point of the dispersion medium needs to be higher than the glass transition temperature of the polymer to avoid boiling of the dispersion medium during thermal annealing. In the invention In one embodiment, the dispersion medium is ethylene glycol, 1,2-propanediol, glycerol or eucalyptus oil.

The thermal annealing treatment refers to placing a polymer film in a container containing a dispersion medium, and heating the polymer film by providing a uniform heating environment by a heating device. In an embodiment of the present invention, during the thermal annealing treatment, the dispersion medium is continuously stirred to uniformly heat the polymer film, and the polymer film and the generated polymer ball are prevented from being deposited on the bottom of the container, thereby causing the polymer film. Re-aggregate and fuse with the polymer sphere. For example, a magnet may be added to a dispersion medium and heated by a heating device capable of generating a magnetic force to rotate the magnet to agitate the dispersion medium.

In the process of thermal annealing, due to the interfacial tension between the polymer film and the dispersion medium, the surface of the polymer film will fluctuate and bulge after heating, and when the degree of fluctuation increases, the protrusion gradually becomes spherical. After the heating time increases, it leaves the film body and enters a uniform dispersion medium to form an energy-stable polymer sphere.

Please refer to FIG. 2 , which is a schematic view showing the operation of preparing the polymer ball 212 according to an embodiment of the present invention. First, the polymer film 210 is formed on the substrate 220. Next, the polymer film 210 is placed in a container 230 containing the dispersion medium 240 to be thermally annealed, and the dispersion medium 240 is stirred by the magnet 250. After the polymer film 210 is subjected to thermal annealing for a period of time, the morphology changes to the polymer ball 212.

In one embodiment, the substrate 220 is a solid planar substrate such as a glass substrate or a tantalum substrate.

It should be noted that the method for preparing the polymer sphere of the present invention can be as shown in FIG. 2, after the polymer film 210 is stripped from the substrate 220, and then the polymer film 210 is placed in the container 230 containing the dispersion medium 240. For thermal annealing treatment. In another embodiment of the present invention, the method for preparing a polymer sphere of the present invention can also directly place a polymer film together with a substrate in a container containing a dispersion medium, followed by thermal annealing.

In one embodiment, the container 230 is a heat resistant glass bottle such as a round bottom bottle.

In one embodiment, the heating device (not shown) is an electromagnetic hot plate. When the heating device is an electromagnetic heating mixer, the magnet 250 can be added to the dispersion medium 240 to stir the dispersion medium, so that the polymer film 210 can be uniformly heated, and the polymer film and the polymer ball can be prevented from re-aggregating and fusing.

It is worth noting that if the polymer film is placed in the air for heat treatment, the polymer film cannot be deformed to produce a polymer ball. The method for preparing a polymer sphere of the present invention provides an environment in which the polymer film 210 can be uniformly heated by the dispersion medium 240, and the polymer film 210 is thermally annealed by means of an oil bath. The thermal annealing treatment changes the morphology of the polymer film 210, and the polymer ball 212 is released in the oil bath.

The method for preparing a polymer sphere of the present invention uses a polymer film as a raw material, and provides polymer energy by an oil bath and through a thermal annealing technique, and converts the morphology of the polymer film into a sphere having a stable energy state. A spherical ball formed of a polymer film having a uniform particle size and a regular shape, which can be applied to various applications, such as: paint, sensor, drug carrier, inkjet Print ink and 3D printing ink. The method for preparing a polymer sphere of the invention has the advantages of low cost, simple and rapid process, and easy implementation, and can rapidly and mass-produce polymer spheres. According to the prior art, the method for preparing a polymer sphere of the present invention requires only a heating medium (ie, a dispersion medium) and a heating device, and only requires a polymer film as a raw material, without adding an additional initiator, a surfactant, or The remaining templates form a polymer sphere.

The following examples are given to illustrate the method of the present invention in more detail, and are intended to be illustrative only and not to limit the invention, and the scope of the invention is defined by the scope of the appended claims.

Preparation of polymer spheres

The method for preparing a polymer sphere according to an embodiment of the present invention comprises the following steps:

1. Dissolving poly(methyl methacrylate (PMMA) in a solvent to form a polymer solution. PMMA is an acrylic resin. In this embodiment, the solvent is toluene.

2. The polymer solution of the step 1 is applied to the glass substrate by spin coating, and after drying, the solvent is removed to form a PMMA polymer film. In this embodiment, the spin coating speed is 800 rpm and the drying temperature is 200 °C.

3. The PMMA polymer film of the step 2 is removed from the glass substrate, placed in a container containing the dispersion medium, and subjected to thermal annealing treatment at 150 ° C for 1 hour to obtain a PMMA polymer sphere. In this embodiment, the dispersion medium is ethylene glycol and the container is a round bottom bottle having a capacity of 10 mL.

In this embodiment, after the polymer film is thermally annealed for about 10 minutes, the polymer film starts to form a polymer ball. After thermal annealing for about 1 hour, a plurality of polymer spheres having a uniform particle size can be formed.

In the following Examples 1 and 2, polymer spheres were produced using different experimental parameters in the above-described method for preparing polymer spheres.

The first embodiment is prepared by the above method for preparing a polymer ball, wherein the baked PMMA polymer film has a thickness of about 14 μm, is removed from the glass substrate, and then placed in a round bottom bottle containing ethylene glycol for heat. Annealing treatment experiment.

Referring to Fig. 3A, there is shown a microscope image of the polymer sphere of Example 1 of the present invention. After the polymer film is thermally annealed, the PMMA polymer ball of Example 1 can be obtained. As can be seen from the figure, the PMMA polymer sphere of Example 1 obtained by using a PMMA polymer film having a thickness of 14 μm has a particle diameter of about 160 to 180 nm.

The second embodiment was also prepared by the above method for preparing a polymer ball. The difference between the first embodiment and the second embodiment is that the PMMA polymer film used in the preparation of the second embodiment has a thickness of about 11 μm.

Referring to Fig. 3B, there is shown a microscope image of the polymer sphere of Example 2 of the present invention. As can be seen from the figure, the PMMA polymer sphere of Example 2 obtained by using a PMMA polymer film having a thickness of 11 μm has a particle diameter of about 180 to 210 nm.

Please refer to FIG. 4, which is a graph showing the particle size distribution of the polymer sphere according to an embodiment of the present invention, which is obtained by each of the high scores of the statistical example 1 and the embodiment 2. The number of occurrences of the particle size of the sub-ball. As can be seen from the figure, the particle diameters of the PMMA polymer spheres of Examples 1 and 2 are mostly in the range of 170 to 220 nm.

The preparation method of the invention can directly remove the polymer film from the substrate, and directly place the polymer film together with the substrate in a container containing the dispersion medium, and then perform thermal annealing treatment.

The preparation method of the PMMA polymer spheres of the third embodiment and the fourth embodiment is substantially the same as that of the first embodiment and the second embodiment, except that the PMMA polymer film is placed in a round bottom bottle containing ethylene glycol together with a glass substrate for heat annealing. Processing. Both Example 3 and Example 4 were prepared from a PMMA polymer film having a thickness of 17 μm, and the two were PMMA polymer spheres obtained in different experiments.

Referring to Fig. 5A, there is shown a microscopic image of a polymer sphere according to a third embodiment of the present invention. The PMMA polymer sphere of Example 3 was obtained by subjecting a PMMA polymer film having a thickness of 17 μm to a substrate and thermally annealing the dispersion medium. As can be seen from the figure, the PMMA polymer sphere of Example 3 has a particle diameter of about 160 to 180 nm.

Referring to Fig. 5B, there is shown a microscope image of the polymer sphere of Example 4 of the present invention. As can be seen from the figure, the PMMA polymer sphere of Example 4 has a particle diameter of about 160 to 190 nm.

A method for preparing a polymer sphere according to another embodiment of the present invention comprises the following steps:

1. An acrylonitrile-butadiene-styrene (ABS) copolymer is dissolved in a solvent to form a polymer solution. In this embodiment, the solvent is dimethyl sulfoxide (DMSO).

2. The polymer solution of the step 1 is applied to the glass substrate by spin coating, and after drying, the solvent is removed to form an ABS polymer film. In this embodiment, the spin coating speed was 800 rpm and the drying temperature was 150 °C. In this embodiment, the ABS polymer film has a thickness of about 32 μm.

3. The ABS polymer film of the second embodiment is obtained by placing the ABS polymer film of the step 2 together with the glass substrate in a container containing a dispersion medium and subjecting it to thermal annealing at 150 ° C for 1 hour. In this embodiment, the dispersion medium is ethylene glycol and the container is a round bottom bottle.

Please refer to Fig. 6, which is a microscope image showing the polymer sphere of Example 5 of the present invention. After the ABS polymer film is thermally annealed, the ABS polymer ball of Example 5 can be obtained. As can be seen from the figure, the ABS polymer sphere of Example 5 obtained by using an ABS polymer film having a thickness of about 32 μm has a particle diameter of about 290 to 320 nm.

From the above results, it is known that the method for preparing a polymer sphere of the present invention is indeed reproducible, and a polymer ball having a uniform particle size, a regular shape, and a nanometer size can be formed in a large amount and rapidly by a simple operation step. .

In summary, the method for preparing a polymer sphere of the present invention uses a polymer film as a raw material, through a thermal annealing technique, and by means of a heating device capable of providing a uniform heating environment, the morphology of the polymer film can be converted into A polymer sphere with uniform particle size and regular shape. The preparation method of the invention is low in cost, simple in process, and easy to implement. Compared with the prior art, the present invention The method for preparing the polymer sphere requires only a heating medium and a heating device, and the polymer sphere can be formed rapidly and in a large amount without additionally adding an initiator, a surfactant or the rest of the template.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.

100‧‧‧ method

110, 120‧‧‧ steps

Claims (5)

A method for preparing a polymer sphere, comprising: coating a polymer solution on a substrate to form a polymer film; and placing the polymer film in a dispersion medium for thermal annealing to form the polymer film Forming into a plurality of polymer spheres, wherein the dispersion medium does not dissolve the polymer and has a boiling point higher than a glass transition temperature of the polymer, the thermal annealing treatment being higher than the glass transition temperature and lower than the boiling point of the dispersion medium The time of the thermal annealing treatment is about 1 to 180 minutes, and the temperature of the thermal annealing treatment is about 50 to 250 ° C, wherein the molecular weight of the polymer is about 10,000 to 1,000,000 Da, and the polymer spheres are The particle size is about 50 to 1000 nm, and the polymer is a polyester polymer, a polyamine polymer, a polycarbonate polymer, a polyurethane polymer, a polyolefin polymer or a modification thereof, and crosslinkability. A polymer, a copolymer or any combination of the above, and wherein the dispersion medium is ethylene glycol, 1,2-propylene glycol, glycerol or eucalyptus oil. The method of claim 1, further comprising dissolving the polymer in a solvent to form the polymer solution, wherein the solvent is toluene, tetrahydrofuran, acetone, cyclohexane, dimethylformamide , methyl ethyl ketone, chloroform, acetic acid, pentane or dimethyl hydrazine. The method of claim 2, wherein the method of forming the polymer film comprises drying the polymer solution coated on the substrate to remove the solvent and form the polymer film. The method of claim 1, wherein the method of applying the polymer solution to the substrate is spin coating, doctor blade coating, spray coating, slit coating or inkjet coating. The method of claim 1, wherein the polymer film has a thickness of about 50 to 100,000 nm.