KR102207129B1 - A method for preparing resin fiber based polyalkylene carbonate - Google Patents

Abstract

The present invention relates to a method of manufacturing a polyalkylene carbonate-based resin fiber.According to the present invention, since the equipment configuration is simple, energy consumption is low, and it is manufactured in the form of a nonwoven fabric using centrifugal spinning, the process can be simplified. In addition, since it is possible to manufacture polyalkylene carbonate-based resin fibers having various advantages of fibers that cannot be realized in a film form, there is an advantage that its use can be expanded to new fields of use.

Description

Manufacturing method of polyalkylene carbonate resin fiber {A METHOD FOR PREPARING RESIN FIBER BASED POLYALKYLENE CARBONATE}

The present invention relates to a method for producing a polyalkylene carbonate-based resin fiber.

Polyethylene carbonate (Poly Ethylene Carbonate) is a kind of eco-friendly polymer, and is mainly used for biodegradable composites, packaging films, protective films, and tubes.

Currently, polyethylene carbonate polymers are mainly processed and used in film form due to their characteristics such as biodegradability and high gas barrier properties, so the main field of use is limited to the film field, and thus, it has limitations in grafting into various application fields. There is a need to implement a furnace.

In this regard, Korean Laid-Open Patent Publication No. 2014-0018099 discloses a polyalkylene carbonate-based resin film and a method of manufacturing the same, but the application field of the polyalkylene carbonate-based resin is limited to the film field, and thus the application field is limited. There is a problem with this.

Republic of Korea Patent Publication No. 2014-0018099

Accordingly, the present invention is to provide a method of manufacturing a polyethylene carbonate-based resin fiber having various advantages of fibers that cannot be implemented in a film form by centrifugal spinning.

In addition, the present invention is to provide a resin fiber manufactured by the above manufacturing method.

The present invention comprises the steps of (1) copolymerizing carbon dioxide and alkylene oxide to prepare a polyalkylene carbonate; (2) preparing a spinning solution by dissolving the polyalkylene carbonate in an organic solvent; And (3) placing the spinning solution in a spinneret and centrifugal spinning to prepare a polyalkylene carbonate resin fiber. As a method for producing a polyalkylene carbonate-based resin fiber containing,

It provides a method for producing a polyalkylene carbonate-based resin fiber, characterized in that the polyalkylene carbonate is mixed in an amount of 35 to 55% by weight with respect to the organic solvent.

In addition, the present invention provides a polyalkylene carbonate-based resin fiber prepared by the above production method.

The manufacturing method of the polyalkylene carbonate-based resin fiber according to the present invention has the advantage of simplifying the process because the equipment configuration is simple, energy consumption is low, and it is manufactured in the form of a nonwoven fabric using centrifugal spinning. Since it is possible to manufacture polyalkylene carbonate-based resin fibers having various advantages of fibers that cannot be implemented, there is an advantage that its use can be expanded to new fields of use.

1 is a photograph of a part of a polyethylene carbonate-based resin fiber (nonwoven fabric) prepared under the conditions of Example 2.
2 is a scanning electron microscope (SEM) photograph of a polyethylene carbonate-based resin fiber (nonwoven fabric) prepared under the conditions of Example 2.
3 is a photograph of a polyethylene carbonate-based resin fiber (nonwoven fabric) prepared under the conditions of Comparative Example 5.
4 is a photograph of a polyethylene carbonate-based resin fiber (nonwoven fabric) prepared under the conditions of Comparative Example 6.
5 is a photograph of a polyethylene carbonate-based resin fiber (nonwoven fabric) prepared under the conditions of Comparative Example 7.
6 is a photograph of a polyethylene carbonate-based resin fiber (nonwoven fabric) prepared under the conditions of Example 4.
7 is a photograph of a polyethylene carbonate-based resin fiber (nonwoven fabric) prepared under the conditions of Example 1.
FIG. 8 is a photograph of a spinning solution remaining in the detention chamber due to the high viscosity of the spinning solution under the conditions of Comparative Example 8.
9 is a photograph showing the appearance of the spinning solution according to the content of polyalkylene carbonate contained in the spinning solution.

The present invention relates to a method for producing a polyalkylene carbonate-based resin fiber.

It will be described in steps of the manufacturing method below.

First, (1) carbon dioxide and alkylene oxide were copolymerized to prepare polyalkylene carbonate.

The alkylene oxide is, for example, ethylene oxide, propylene oxide, 1-butene oxide, 2-butene oxide, isobutyrene oxide, 1-pentene oxide, 2-pentene oxide, 1-hexene oxide, 1-octene oxide , Cyclopentene oxide, cyclohexene oxide, styrene oxide or butadiene monooxide may be, and may be two or more selected from among them, and ethylene oxide is preferred.

Next, (2) a spinning solution was prepared by dissolving the polyalkylene carbonate in an organic solvent.

In the step (2), the polyalkylene carbonate is mixed in an amount of 35 to 55% by weight based on the organic solvent.

The concentration of the polyalkylene carbonate in the organic solvent is suitable for maintaining the fibrous shape during spinning. When the polyalkylene carbonate is mixed in an amount of less than 35% by weight, fiber formation is poor during spinning and a drop due to a low concentration is formed, making it impossible to form a fibrous shape. In addition, when the mixture exceeds 55% by weight, the content of polyalkylene carbonate is too high, so the viscosity of the spinning solution is high, so that fibers cannot be formed due to poor spinning.

Accordingly, the polyalkylene carbonate is preferably included in the range of 35 to 55% by weight, and more preferably included in the range of 40 to 50% by weight with respect to the organic solvent.

If the volatility of the solvent is too high during the preparation of the spinning solution, the viscosity of the spinning solution increases instantaneously due to the volatilization of the solvent, causing a problem in which spinning is impossible.

Accordingly, the organic solvent used in the preparation of the spinning solution of the present invention may be one or more selected from the group consisting of dimethyl formamide, methyl chloride, chloroform, dimethyl sulfoxide and N-methylpyrrolidine,

It is preferably one or more selected from the group consisting of dimethyl sulfoxide and N-methylpyrrolidine, but is not limited thereto.

In the next step, (3) the spinning solution was placed in a spinneret and centrifuged to produce polyalkylene carbonate resin fibers.

For the centrifugal spinning, the centrifugal spinning equipment of Fiberio in the United States was used, but there is no restriction on its use as long as it is a centrifugal spinning equipment capable of exhibiting the same effect, and a spinning solution obtained by dissolving a polyalkylene carbonate resin in a solvent of a specific content This is a method of manufacturing a nonwoven fabric by placing it in a spinneret with holes and rotating at high speed, and then using the centrifugal force applied at this time to stretch the non-solidified polymer, thereby laminating the fine and solidified fibers on the collection body. The advantage of centrifugal spinning is that the equipment configuration is simple, energy consumption is low, the limit of the polymer that can be used is small, and the process can be simplified because it is manufactured in the form of a nonwoven fabric.

Regarding the rotational speed of the spinneret, if the rotational speed is too slow, the centrifugal force is small, making it impossible to discharge the spinning solution to the outside of the spinneret. There is a problem in that the manufacturing fibers are cut or sprayed on the collecting surface in the form of beads by the action of.

Accordingly, in the present invention, the rotation speed during centrifugal spinning is preferably 5,000 rpm to 8,000 rpm, and more preferably 7,000 rpm to 8,000 rpm, but is not limited thereto.

In the present invention, the polyalkylene carbonate is a kind of polycarbonate-based polymer, and is made of a single polymer composed of a repeating unit represented by the following formula (1) so as to maintain unique physical properties according to the repeating unit represented by the following formula (1), or It may be defined as a single polymer or a copolymer including the repeating unit of Formula 1.

[Formula 1]

In Formula 1, n is an integer of 10 to 1000, and R1 and R2 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms. Is a cycloalkyl group, and R1 and R2 may be linked to each other to form a cycloalkyl group having 3 to 10 carbon atoms.

However, the polyalkylene carbonate resin contains at least one of the repeating units of Formula 1 in order to maintain the unique physical properties due to the repeating unit of Formula 1, for example, biodegradability or low glass transition temperature. It may be a copolymer comprising 40 mol% or more, preferably about 60 mol% or more, and more preferably about 80 mol% or more.

In addition, the repeating unit of Formula 1 may be substituted with various functional groups such as hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms. , In consideration of the mechanical properties or biodegradability of the polyalkylene carbonate resin to be finally obtained, an appropriate functional device may be selected among them.

For example, when hydrogen or a functional group having a smaller carbon number (for example, an alkyl group having a small carbon number or a cycloalkyl group, etc.) is substituted, the polyalkylene carbonate resin including the repeating unit of Formula 1 is more biodegradable in terms of biodegradability. It may be advantageous, and when a functional group having a relatively large carbon number is substituted, it may be advantageous in terms of mechanical properties such as strength of the resin.

The polyalkylene carbonate produced by the production method of the present invention is, for example, polyethylene carbonate, polypropylene carbonate, poly(1-butene carbonate), poly(2-butene carbonate), poly(isobutene) carbonate, Poly(1-pentene carbonate), poly(2-pentene carbonate), poly(1-hexene carbonate), poly(1-octene carbonate), poly(cyclopentene carbonate), poly(cyclohexene) carbonate, poly(styrene) It may be carbonate or poly(butadiene) carbonate, but among them, it is preferable that it is a polyethylene carbonate that is excellent in biodegradability and can be manufactured inexpensively, thereby reducing manufacturing cost.

And, in the polyalkylene carbonate resin, the degree of polymerization n of the repeating unit of Formula 1 may be 10-1000, preferably 50-500, and the polyalkylene carbonate resin including the same may be about 10,000 to about 1,000,000, Preferably, it may have a weight average molecular weight of about 50,000 to about 500,000.

As the repeating unit and the polyalkylene carbonate resin have a degree of polymerization and a weight average molecular weight in such a range, a resin layer or a disposable resin molded article obtained therefrom may exhibit biodegradability along with mechanical properties such as appropriate strength.

The fiber produced by the manufacturing method of the present invention is preferably a nonwoven fabric, but is not limited thereto.

The polyalkylene carbonate-based resin fiber according to the present invention may be suitably used for a resin molded article. Here, the resin molded article may include the resin fiber of the embodiment, or may be formed of only such resin fiber. As an example of such a molded article, there is no limitation if it is a molded article belonging to a product group requiring biodegradability and elasticity.

The use of the disposable resin molded article is not particularly limited, and may encompass molded articles used in various fields such as medicine, chemistry, chemicals, food, or cosmetics.

In addition, the present invention relates to a polyalkylene carbonate-based resin fiber prepared by the above production method.

Hereinafter, the present invention will be described in more detail by non-limiting examples. Embodiments of the present invention disclosed below are illustrative to the last, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and furthermore, it contains the meanings equivalent to the claims recorded and all modifications within the scope. In addition, "%" and "parts" indicating content in the following examples and comparative examples are based on mass unless otherwise noted.

Example

Manufacturing example 1. Polyethylene Carbonate Produce

Carbon dioxide and alkylene oxide were copolymerized to prepare a polyalkylene carbonate having a repeating unit represented by the above formula. In the above formula, n is an integer from 10 to 1000.

Polyethylene Carbonate system Production of resin fibers

[Example 1]

Polyethylene carbonate was heated at 100° C. for about 12 hours at a content of 45% by weight using dimethyl sulfoxide as a solvent to prepare a spinning solution. 5 g of the spinning solution was quantified, put into a spinneret having a size of 600 µm, heated at 100°C, and spun at a rotational speed of 7,000 per minute to prepare a polyethylene carbonate nonwoven fabric.

[Example 2]

A polyethylene carbonate nonwoven fabric was prepared in the same manner as in Example 1, except that polyethylene carbonate was used in an amount of 50% by weight using dimethyl sulfoxide as a solvent, and was spun at a rotational speed of 7,500 per minute.

[Example 3]

Polyethylene carbonate was heated at 100° C. for about 12 hours at 40% by weight using N-Methyl Pyrrolidone as a solvent to prepare a spinning solution. 5 g of the spinning solution was quantified, put into a spinneret having a holding size of 600 µm at room temperature, and spun at a rotational speed of 7,000 per minute to prepare a polyethylene carbonate nonwoven fabric.

[Example 4]

A polyethylene carbonate nonwoven fabric was prepared in the same manner as in Example 1, except that polyethylene carbonate was included in an amount of 40% by weight using dimethyl sulfoxide as a solvent.

[Comparative Example 1]

A spinning solution was prepared in an amount of 10% by weight by using polyethylene carbonate as a solvent and methylene chloride. 5 g of the prepared spinning solution was quantified and injected into a spinneret having a holding size of 150 µm, 300 µm, and 600 µm, respectively, and spinning at a rotation speed of 5,000 to 14,000 per minute at a rate of 1,000 units difference. In this test, the viscosity of the spinning solution was low, so the spinning solution was sporadic under all conditions, and it was impossible to prepare a fibrous sample.

[Comparative Example 2]

It was prepared in the same manner as in Comparative Example 1, except that a spinning solution prepared in 20% by weight was used. In this test, the viscosity of the spinning solution was low, so the spinning solution was sporadic under all conditions, and it was impossible to prepare a fibrous sample.

[Comparative Example 3]

5 g of polyethylene carbonate pellets were quantified and put into a spinneret having a confinement size of 600 μm, and the conditions were changed at a rate of 1,000 units at a rotational speed of 8,000-12,000 per minute at a temperature of 180° C. and spun. In this test, when the spinning temperature was 180°C, the polymer could not be discharged out of the spinneret because the polyethylene carbonate was not sufficiently melted, and the sample production failed.

[Comparative Example 4]

It was prepared in the same manner as in Comparative Example 3, except that the spinning temperature was set to 240°C. In this test, some fibrous phases were formed at a rotational speed of 12,000 per minute, but as the temperature of the spinneret decreased due to high-speed rotation, the polymer could not be discharged out of the spinneret, and the sample production failed.

[Comparative Example 5]

A polyethylene carbonate nonwoven fabric was prepared in the same manner as in Example 1, except that polyethylene carbonate was included in an amount of 10% by weight using dimethyl sulfoxide as a solvent.

[Comparative Example 6]

A polyethylene carbonate nonwoven fabric was prepared in the same manner as in Example 1, except that polyethylene carbonate was included in an amount of 20% by weight using dimethyl sulfoxide as a solvent.

[Comparative Example 7]

A polyethylene carbonate nonwoven fabric was prepared in the same manner as in Example 1, except that polyethylene carbonate was included in an amount of 30% by weight using dimethyl sulfoxide as a solvent.

[Comparative Example 8]

A polyethylene carbonate nonwoven fabric was prepared in the same manner as in Example 1, except that polyethylene carbonate was included in an amount of 60% by weight using dimethyl sulfoxide as a solvent.

Experimental example

Experimental example 1. Scanning electron microscope ( SEM ) analysis

SEM analysis was performed in order to observe the state of the polyethylene carbonate-based resin fiber prepared in Example 2, and is shown in FIG. 2.

Experimental example 2. Confirmation of fiber formation according to the solvent and spinning conditions used

It is shown in Table 1 below whether the variables of Examples 1 to 3 and Comparative Examples 1 to 4 were adjusted and fiber formation.

radiation
Condition use
menstruum radiation
Solution content Detention
size Per minute
Rotation speed radiation
Temperature fiber
formation Specifics when forming fibers Example 1 menstruum
DMSO
(Dimethyl
sulfoxide) 45% by weight 600 μm 7,000RPM 100℃ O Good fibrous formation
Sample preparation available Example 2 50% by weight 600 μm 7,500RPM 100℃ O Example 3 NMP
(N-methyl
Pyrrolidone) 40% by weight
600 μm 7,000RPM Room temperature
(25℃) O Comparative Example 1 MC
(methylene
Chloride) 10% by weight 150-
600 μm 5,000-
14,000
RPM Room temperature
(25℃) X The viscosity of the spinning solution is low
It is impossible to form fibrous,
As a spinning solution due to high volatility
Not suitable (solution spatter) Comparative Example 2 20% by weight 150-
600 μm 5,000-
14,000
RPM Room temperature
(25℃) X Comparative Example 3 Melting - 100% by weight 600 μm 8,000-
12,000
RPM 180℃ X Unable to radiate due to low discharge temperature Comparative Example 4 100% by weight 600 μm 8,000-
12,000
RPM 240℃ △ Some fibers are formed at the beginning of spinning.
Or by lowering the temperature by rotation
Discharge and fibrous manufacturing impossible

As shown in Table 1, Examples 1 to 3 using dimethyl sulfoxide or N-methylpyrrolidine as an organic solvent showed good fiber formation.

Experimental example 3. Confirmation of fiber formation according to the content of spinning solution

Examples 1 to 2 and 4 and Comparative Examples 5 to 8 of the variable adjustment and fiber formation are shown in Table 2 and Figs. 2 to 9 below.

radiation
Condition use
menstruum radiation
Solution content Detention
size Per minute
Rotation speed radiation
Temperature fiber
formation SEM analysis Specifics when forming fibers Comparative Example 5 solution
radiation DMSO
(Dimethyl
sulfoxide) 10% by weight 600 μm 7,000RPM Room temperature
(25℃) X Figure 3 Due to the low viscosity of the spinning solution, it is impossible to form a fibrous shape, and it is not suitable as a spinning solution due to the high volatility of the solvent. Comparative Example 6 20% by weight 600 μm 7,000RPM Room temperature
(25℃) X Fig. 4 Comparative Example 7 30% by weight 600 μm 7,000RPM Room temperature
(25℃) X Figure 5 Example 4 40% by weight 600 μm 7,000RPM Room temperature
(25℃) O Fig. 6 Good fibrous formation and sample preparation possible Example 1 45% by weight 600 μm 7,000RPM Room temperature
(25℃) O Fig. 7 Example 2 50% by weight 600 μm 7,500RPM Room temperature
(25℃) O Figure 2 Comparative Example 8 60% by weight 600 μm 7,000RPM Room temperature
(25℃) X Fig. 8 Sample production is impossible due to the impossibility of detention and discharge of polymer due to high viscosity

Looking at Table 2, it was found that Examples 1 to 3 having a spinning solution content of 35 to 55% by weight showed good fiber formation, and Comparative Examples 5 to 8, which did not have good fiber formation.

9 shows the appearance of the spinning solutions of Comparative Examples 3 to 5, Examples 4, 1 and 2, and Comparative Example 8, which change as the amount of polyalkylene carbonate contained in the spinning solution increases.

In addition, referring to FIGS. 3 to 5, when prepared according to Comparative Examples 5 to 7, it is shown that the solution is scattered and thus fibers are not formed. In addition, looking at Figures 6 to 7 and 2, it is shown that the fibers are well manufactured when manufactured according to Examples 1 to 2 and 4. In addition, referring to FIG. 8, it is shown that in the case of manufacturing according to Comparative Example 8, the solution is not discharged from within the detention, so that the fiber cannot be manufactured.

Claims (8)

(1) preparing polyalkylene carbonate by copolymerizing carbon dioxide and alkylene oxide;
(2) preparing a spinning solution by dissolving the polyalkylene carbonate in an organic solvent; And
(3) placing the spinning solution in a spinneret and centrifugal spinning to prepare a polyalkylene carbonate resin fiber;
As a method for producing a polyalkylene carbonate-based resin fiber containing,
In the step (2), the polyalkylene carbonate is mixed in an amount of 40 to 50% by weight based on the organic solvent. The method according to claim 1,
The polyalkylene carbonate is a method for producing a polyalkylene carbonate-based resin fiber, characterized in that the polyethylene carbonate. The method according to claim 1,
The method for producing a polyalkylene carbonate-based resin fiber, characterized in that the rotation speed during the centrifugal spinning is 5,000 rpm to 8,000 rpm. The method according to claim 1,
The organic solvent is a method of producing a polyalkylene carbonate-based resin fiber, characterized in that at least one selected from the group consisting of dimethyl sulfoxide and N-methylpyrrolidine. The method according to claim 1,
The method for producing a polyalkylene carbonate-based resin fiber, characterized in that the fiber is a non-woven fabric. The method according to claim 1,
The polyalkylene carbonate resin is a method of producing a polyalkylene carbonate-based resin fiber, characterized in that it comprises a repeating unit represented by the following formula (1):
[Formula 1]

In Formula 1,
n is an integer from 10 to 1000,
R1 and R2 are each independently hydrogen, a C1-C20 alkyl group, a C6-C20 aryl group, a C1-C20 alkenyl group, or a C3-C20 cycloalkyl group, and R1 and R2 are connected to each other to have 3 Can form a cycloalkyl group of to 10. The method according to claim 1,
The polyalkylene carbonate resin is a method of producing a polyalkylene carbonate-based resin fiber, characterized in that it has a weight average molecular weight of 10,000 to 1,000,000. delete

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