KR20030067867A - The Manufacturing Method Of Globular Fine Grain Of Polybutylene Succinate - Google Patents

Abstract

The present invention relates to a method for producing polybutylene succinate spherical fine particles, comprising: (a) a first solution comprising a polybutylene succinate and an emulsifying dispersant 2nd step of preparing the respective solutions, (b) a second step of mixing the first solution and the second solution to prepare an emulsion from the mixed solution by the stirring means, and (c) by evaporating the solvent from the prepared emulsion And a third step of precipitating polybutylene succinate spherical fine particles, and the desired particle size and its distribution form can be controlled from the micrometer to the nanometer area by the production method of the present invention.

Description

The manufacturing method of globular fine grain of polybutylene succinate}

The present invention relates to a method for producing polybutylene succinate spherical fine particles, and more particularly, to a method for producing polybutylene succinate spherical fine particles that can control the average particle size and particle size distribution.

Plastics, which are currently used in general, mainly polyethylene terephthalate, polypropylene, polyethylene, and other engineering plastics are already used in various products due to their physical and chemical properties such as corrosion resistance and high strength. However, most of the packaging, living and agricultural plastics are left unused except for the method of recovery and reuse when they are discarded after use. , Soil deterioration and soil pollution. Moreover, in view of the domestic situation in which wastes contain a large amount of plastic and have high landfill dependence, the development and application of degradable polymers are urgently required.

Although the production of high molecular weight polymers by ring-opening polymerization of caprolactone has been known, the production of petrochemicals, films, and molded products using biodegradable aliphatic polyesters has been steadily attempted. Due to the disadvantage of the cost, the use is used only for a limited use such as some medical fibers, but is not widely used in industrial fields, automobile parts, household products, and the like.

Conventional biodegradable resins include degradable resins obtained by copolymerizing aliphatic polyesters with natural polymers from Kolon Co., Ltd. (Korean Patent Publication No. 95-18124), and photodegradable inducing compounds and aliphatic polyesters in Daelim Industries. Degradable resins containing fillers (Korean Patent Publication No. 96-22744), and Samsung General Chemicals has incorporated ketone group-containing polyesters that give photodegradability to biodegradable aliphatic polyesters (Korean Patent Publication No. 95-18116). In Cheil Synthetic Fiber, natural polymers, automatic oxidizers, photosensitizers, plasticizers, colorants, etc. are added based on biodegradable resins containing starch in ethylene and aliphatic polyester (Korean Patent Publication No. 95-18214) and thermoplastic resins. Biodegradable resins (Korean Patent Publication No. 95-10984), and Korea Advanced Institute of Science and Technology A biodegradable polyester (Korean Patent Publication No. 95-23663) to which a chain extender such as a molecular weight polyester heterocyclic compound is added is used. A copolymer of a microbial aliphatic polyester and a chemical synthetic aliphatic polyester (Korean Patent Publication No. 96- 22669), respectively.

MEANS TO SOLVE THE PROBLEM In manufacturing a biodegradable polymer using dicarboxylic acid and glycol as a raw material, 0.1-5 mol% of magnesium salts are added with respect to 100 mol% of dicarboxylic acids as a binder, and a titanium compound is resin as a deglycol reaction catalyst. 0.01 to 1% by weight is added to the whole, and trimethyl phosphate is added as 0.01 to 1.0% by weight with respect to the whole resin as a heat stabilizer. Thus, the obtained polymer is a packaging film or a film for collecting waste that requires a relatively short service life. In order to be used for agricultural films, etc., a biodegradable polymer production method (Korean Patent Publication No. 99-025900) has been developed.

The present invention is to prepare spherical fine particles to be used as a cosmetic filler using the polybutylene succinate prepared according to the Patent Publication No. 99-025900. Particulation by mechanical pulverization is difficult to produce a fine particle powder having a large particle diameter of the obtained powder and excellent in independent monodispersion. In addition, it is also difficult to control the spherical particle shape, particle size distribution, and the like by the above method. For this reason, the development of the manufacturing method of the polybutylene succinate spherical microparticles | fine-particles excellent in monodispersity is urgently desired.

The present invention is to provide a method for producing polybutylene succinate spherical fine particles that can control the average particle diameter, particle size distribution and the like. Another object of the present invention is to provide polybutylene succinate spherical fine particles usable for cosmetic fillers.

1 is a scanning electron micrograph of the polybutylene succinate spherical fine particles prepared in Example 1,

2 is a particle size distribution diagram of polybutylene succinate spherical fine particles prepared according to Example 1,

3 is a scanning electron micrograph of the polybutylene succinate spherical fine particles prepared in Example 2,

4 is a particle size distribution diagram of polybutylene succinate spherical fine particles prepared in Example 2,

5 is a particle size distribution diagram of polybutylene succinate spherical fine particles prepared in Example 3,

6 is a particle size distribution diagram of polybutylene succinate spherical fine particles prepared in Example 4,

7 is a particle size distribution diagram of polybutylene succinate spherical fine particles prepared in Comparative Example 1.

The production method of the present invention is a method for producing polybutylene succinate spherical fine particles from a polybutylene succinate polymer,

(a) a first step of preparing a first solution containing a polybutylene succinate polymer and a second solution containing an emulsion dispersant, respectively;

(b) a second step of preparing an emulsion from the mixed solution by mechanical high speed stirring by mixing the first solution and the second solution, and

(c) a third step of depositing polybutylene succinate spherical fine particles by evaporating the solvent from the prepared emulsion.

Hereinafter, the present invention will be described in detail.

(1) First step

In the present invention, polybutylene succinate spherical fine particles are produced using polybutylene succinate polymer as a raw material. Polybutylene succinate is made of dicarboxylic acid and glycol as a raw material, and using such a polybutylene succinate polymer, firstly a first solution and an emulsion dispersant containing the polybutylene succinate polymer as a first step Each 2nd solution containing is prepared. That is, in the present invention, the polybutylene succinate polymer / organic solution and the emulsion dispersion aqueous solution are prepared as separate solutions, respectively.

(a) First solution

The solvent used for the first solution is not particularly limited as long as the polybutylene succinate polymer is substantially dissolved and not mixed with the second solution. For example, a solvent including at least one of methylene chloride, chloroform, formic acid, concentrated sulfuric acid, and concentrated nitric acid can be used.

The ratio of polybutylene succinate and solvent in the first solution may be appropriately set according to the type of polybutylene succinate used, the type of solvent, the concentration of the second solution, and the like. Usually, polybutylene succinate: solvent = 1: 3 to 30, preferably 1: 5 to 15.

(b) second solution

The emulsion dispersant-containing aqueous solution used as the second solution is not particularly limited. For example, polymer-based three-dimensional emulsion dispersants such as gelatin, gum arabic, dextrin, casein, protein, polyvinyl alcohol, sodium alginate, albumin, and sorbitan mono Low molecular type electrostatic emulsifiers such as sorbitan esters such as oleate can be used. These can use 1 type (s) or 2 or more types. Furthermore, in the present invention, a polysaccharide compound may be used in addition to the above-mentioned steric dispersant. The particle size distribution characteristic of the polybutylene succinate microparticles | fine-particles obtained by these can be changed.

The solvent used for the second solution is not particularly limited as long as the emulsion dispersant is substantially dissolved in addition to water, and further, the resulting polybutylene succinate fine particles are not dissolved. Moreover, even if it is a solvent which melt | dissolves in the solvent of a 1st solution, these can also be used if it adjusts so that a polybutylene succinate may precipitate by mixing with the poor solvent of a polymer.

The concentration of the emulsifying dispersant in the second solution may be appropriately set depending on the type of polybutylene succinate used, the concentration of the first solution, and the like, but is usually about 0.05 to 10% (w / L), preferably 0.2 to 5% (w / L). If the concentration of the emulsion dispersant is 0.05% or less, the spherical particles are aggregated and coalesced, and if the concentration of the emulsion dispersant is 10% or more, the economic efficiency is lowered, and there is a hassle of removal in the subsequent process.

(2) second process

In the second step, the first solution and the second solution are mixed to form a polymer emulsion solution from the mixed solution by the stirring means. The mixing ratio of the first solution and the second solution can be appropriately changed depending on the type of polybutylene succinate, the concentration of each solution, etc., but usually it is mixed in a range of about 1: 1 to 20, preferably 1: 2 to 10. Do it.

If the mixing ratio of the first solution and the second solution is 1: 1 or less, it is impossible to form the emulsified particles. If the mixing ratio of the first solution and the second solution is 1:20 or more, the size of the reaction tank becomes large and the yield decreases.

The stirring means of the second step is mechanical stirring by a stirrer, it is possible to refine the average particle diameter by adjusting the stirring speed by a homomixer. A homomixer can employ | adopt a well-known stirring apparatus and operation conditions as it is. The rotational speed of the stirrer may be appropriately set in accordance with the desired particle size and the like, and is usually about 1,000 to 20,000 rpm, preferably 2,000 to 10,000 rpm. If the rotational speed of the stirrer is less than 1,000rpm, the size of the emulsion particles formed is too large to obtain the desired particle size, if the rotational speed of the stirrer is more than 20,000rpm overloading the stirrer is inferior in economic efficiency.

Another embodiment of the stirring means of the second process is the ultrasonic stirring by the ultrasonic generator, it is possible to refine the average particle diameter by adjusting the stirring speed by ultrasonic stirring. Ultrasonic stirring can employ | adopt a well-known stirring apparatus and operation conditions as it is. The frequency of the ultrasonic generator may be appropriately set in accordance with the desired particle size and the like, and may usually be about 20 to 130 KHz, preferably 30 to 80 KHz. Ultrasonic agitation can perform finer agitation than mechanical agitation, and other various agitation means can be used in addition to the ultrasonic agitation and mechanical agitation.

The temperature in the second step is not particularly limited and may be usually about 10 to 30 ° C, preferably 15 to 25 ° C. In addition, the stirring time may be performed until the precipitation of the polybutylene succinate fine particles is substantially completed. Usually, it is about 30 to 240 minutes, but there is no problem even if it is outside this range, but if the stirring time is 30 minutes or less, the solvent of the first solution If it is not completely volatilized and stirring time is 240 minutes or more, there exists a possibility that the possibility of particle coagulation may increase.

In the second step, the present invention can further add a poor solvent of polybutylene succinate to the mixed solution. The solvent used for the first solution or the second solution may not be precipitated (or difficult to precipitate) depending on the type of solvent. In this case, by adding a poor solvent of polybutylene succinate, Polybutylene succinate microparticles | fine-particles can be precipitated more efficiently. The poor solvent added to the mixed solution is not particularly limited and may be appropriately selected depending on the kind of polybutylene succinate produced, the solvent used for the first solution, the second solution, and the like.

(3) Third process

In the third step, polybutylene succinate spherical fine particles are precipitated while removing the organic solvent of the first liquid from the emulsion by heating and evaporating it out of the reaction system. The heating temperature for the emulsion varies depending on the type of solvent used in the first solution, but usually 30 to 100 ° C. is preferred, and the second solution needs to be replenished in consideration of the evaporation amount of the second solution as the high temperature is heated. .

If the heating temperature is 30 ° C or less, the solvent of the first solution is difficult to evaporate. If the heating temperature is 100 ° C or more, the solvent of the second solution is evaporated, and coagulation between the produced particles occurs easily. The heating time is about 10 seconds to 30 minutes, preferably 1 to 15 minutes when the emulsion is formed. The heating for solvent evaporation may be performed until the precipitation of the polybutylene succinate fine particles is completed.

The polybutylene succinate fine particles precipitated in the third step may be recovered by solid-liquid separation according to a known method such as centrifugation. When polybutylene succinate fine particles (powder) obtained in the third step are produced as spherical particles, the polybutylene succinate fine particles (powder) are generally excellent in monodispersity with an average particle diameter of 0.05 to 80 m (preferably 0.1 to 20 m). According to the present invention, the irregular shape with respect to the spherical shape can be made less than 0.1% to have the maximum surface area.

Examples will be shown below to further clarify the features of the present invention. In the present invention, the average particle size and the particle size distribution were measured using a particle size analyzer (Malvern Instruments, UK), and the particle surface was observed by scanning electron microscopy (SEM).

Example 1

10 ml (polybutylene succinate: methylene chloride = 1: 3) dissolved in methylene chloride as a first solution and 20 ml of an aqueous solution containing 0.5% polyvinyl alcohol as a second solution were prepared. Both solutions were then mixed at 25 ° C. to prepare an emulsion with a homomixer (2,500 rpm). The prepared emulsion liquid precipitated polybutylene succinate fine particles by stirring at 40 degreeC for 60 minutes. Then, the precipitate was collect | recovered by the centrifugal method and the fine particle (powder) was obtained by drying under reduced pressure.

By observing the precipitated fine particles with a scanning electron microscope (SEM), it was confirmed that the polybutylene succinate fine particles were composed of spherical particles having excellent monodisperse phase. The observation result is shown in FIG. In addition, the average particle diameter of the polybutylene succinate microparticles | fine-particles was 1.2 micrometers as a result of the measurement by the particle size analyzer. The measurement result is shown in FIG.

Example 2

10 ml (polybutylene succinate: methylene chloride = 1: 3) dissolved in methylene chloride as a first solution and 20 ml of a 0.25% polyvinyl alcohol-containing aqueous solution were prepared as a second solution. Both solutions were then mixed at 25 ° C. to prepare an emulsion with a homomixer (3,000 rpm). The prepared emulsion liquid precipitated polybutylene succinate fine particles by stirring at 40 degreeC for 60 minutes. Then, the precipitate was collect | recovered by the centrifugal method and the microparticles | fine-particles (powder) were obtained by drying under reduced pressure.

By observing the precipitated fine particles with a scanning electron microscope (SEM), it was confirmed that the polybutylene succinate fine particles were composed of spherical particles having excellent monodisperse phase. The observation result is shown in FIG. Moreover, the average particle diameter of the polybutylene succinate microparticles | fine-particles was 3.6 micrometers as a result of the measurement by the particle size analyzer. The measurement results are shown in FIG. 4.

Example 3

10 ml (polybutylene succinate: methylene chloride = 1: 3) dissolved in methylene chloride as a first solution and 20 ml of an aqueous solution containing 0.5% polyvinyl alcohol as a second solution were prepared. Both solutions were then mixed at 25 ° C. to prepare an emulsion by ultrasonic stirring (30 KHz). The prepared emulsion liquid precipitated polybutylene succinate fine particles by stirring at 40 degreeC for 60 minutes. Then, the precipitate was collect | recovered by the centrifugal method and the fine particle (powder) was obtained by drying under reduced pressure.

By observing the precipitated fine particles with a scanning electron microscope (SEM), it was confirmed that the polybutylene succinate fine particles were composed of spherical particles having excellent monodisperse phase. In addition, the average particle diameter of the polybutylene succinate microparticles | fine-particles was 1.45 micrometers as a result of the measurement by the particle size analyzer. The measurement results are shown in FIG. 5.

Example 4

10 ml (polybutylene succinate: methylene chloride = 1: 1) dissolved in methylene chloride as a first solution and 20 ml of a 0.25% polyvinyl alcohol-containing aqueous solution were prepared as a second solution. Both solutions were then mixed at 25 ° C. to prepare an emulsion by ultrasonic stirring (30 KHz). The prepared emulsion liquid precipitated polybutylene succinate fine particles by stirring at 40 degreeC for 60 minutes. Then, the precipitate was collect | recovered by the centrifugal method and the fine particle (powder) was obtained by drying under reduced pressure.

By observing the precipitated fine particles with a scanning electron microscope (SEM), it was confirmed that the polybutylene succinate fine particles were composed of spherical particles having excellent monodisperse phase. In addition, the average particle diameter of the polybutylene succinate microparticles | fine-particles was 2.23 micrometers as a result of the measurement by the particle size analyzer. The measurement results are shown in FIG. 6.

Comparative Example 1

It was prepared in the same manner as in Example 1 except that 10 ml (polybutylene succinate: methylene chloride = 1: 1) dissolved in methylene chloride was used as the first solution.

By observing the precipitated fine particles with a scanning electron microscope (SEM), it was confirmed that the polybutylene succinate fine particles were composed of agglomerated nonuniform particles, and the average particle diameter of the polybutylene succinate fine particles was 27.2 by particle size analysis. It was μm, and the measurement result is shown in FIG.

According to the production method of the present invention, polybutylene succinate spherical fine particles can be reliably produced. In addition, the production method of the present invention can control the desired particle size and its distribution form from the micrometer to the nanometer region by appropriately adjusting the conditions between the respective processes.

The polybutylene succinate spherical fine particles obtained by the present invention can be used as a polymer additive for cosmetics, and can be widely used for various other applications. For example, it is also useful for electrical / electronic materials, medical materials, various filter materials, chromatography materials, spacer agents, film additives, composite material additives, polybutylene succinate varnish additives, and the like.

Claims (7)

In the method for producing polybutylene succinate spherical fine particles from a polybutylene succinate polymer, (a) a first step of preparing a first solution containing a polybutylene succinate polymer and a second solution containing an emulsion dispersant, respectively; (b) a second step of preparing an emulsion from the mixed solution by stirring means by mixing the first solution and the second solution, and (c) A method for producing polybutylene succinate spherical fine particles comprising a third step of depositing polybutylene succinate spherical fine particles by evaporating the solvent from the prepared emulsion. The method of claim 1, wherein the polybutylene succinate polymer of the first solution of the first step is a polymer prepared from dicarboxylic acid and glycol. The solvent of claim 1, wherein the solvent of the first solution includes at least one of methylene chloride, chloroform, formic acid, concentrated sulfuric acid, and concentrated nitric acid, and the ratio of polybutylene succinate and the solvent is 1: 3 to 30. The manufacturing method of the polybutylene succinate spherical microparticles | fine-particles which are used. The method of claim 1, wherein the solvent of the second solution is gelatin, gum arabic, dextrin, casein, protein, polyvinyl alcohol, soda alginate, albumin, etc., polymer-based three-dimensional emulsion dispersant and sorbitan such as sorbitan monooleate A method for producing polybutylene succinate spherical fine particles comprising at least one kind of ester-based low molecular weight electrostatic emulsifying dispersant, wherein the concentration of the dispersant in the solution is 0.05 to 10% (w / L). The method according to any one of claims 1 to 4, wherein the stirring means is mechanical stirring by a stirrer, the mixing ratio of the first solution and the second solution is 1: 1-20, and the rotation speed of the stirrer is 1,000. A process for producing polybutylene succinate spherical fine particles, characterized in that the stirring time is 30 to 240 minutes at -20,000 rpm. The method according to any one of claims 1 to 4, wherein the stirring means is ultrasonic stirring by an ultrasonic generator, the mixing ratio of the first solution and the second solution is 1: 1-20, and the stirring time is 30- Method for producing polybutylene succinate spherical fine particles, characterized in that 240 minutes. The polybutylene succinate spherical fine particles according to claim 1, wherein the polybutylene succinate spherical fine particles are precipitated by heating and evaporating the organic solvent of the first solution at 30 to 100 ° C from the emulsion of the third step. Manufacturing method.