TWI615516B - Preparation method of fiber and spinning viscose - Google Patents

Abstract

A method for preparing fibers. In the fiber preparation method, a polymer is first dissolved in a mixed solution of an ionic liquid and a salt to form a spinning mucus. The salt includes KCl, KBr, KOAc, NaBr, ZnCl ₂ or a combination thereof. Then, a spinning process is performed using the spinning slime as a raw material to form fibers.

Description

Preparation method of fiber and spinning slime

The invention relates to a method for preparing a fiber and a spinning slime, and more particularly to a method for preparing a regenerated fiber and a spinning slime.

In recent years, scientists have actively developed to dissolve the existing polymer materials to produce recycled fibers to replace the consumption of natural fibers. Recycled fibers can be widely used in various industries, such as home textiles, optical films, flexible electronic displays, cosmetics, medicines and food additives.

In the process of manufacturing recycled fibers, it is often necessary to dissolve a polymer in a solvent. For example, current commercial cellulose wet spinning typically uses methyl oxymorpholine (NMMO) as a solvent. However, the high process temperature of NMMO (110-130 ° C) causes the solute to degrade and consume energy. In addition, NMMO is a strong oxidant, and additional stabilizers need to be added in the process, resulting in higher recovery costs. Therefore, how to effectively improve fiber strength, reduce process temperature, and save energy are the current research directions.

The invention provides a method for preparing fibers, which can increase the solubility of polymers, improve the strength of fibers, and reduce the process temperature.

The present invention proposes a method for preparing the fiber as follows. First, the polymer is dissolved in a mixed solution of an ionic liquid and a salt to form a spinning mucus. The salt includes KCl, KBr, KOAc, NaBr, ZnCl ₂ or a combination thereof. Then, the spinning viscose is used as a raw material to perform a spinning process to form fibers.

In an embodiment of the present invention, the ionic liquid is composed of a cation and an anion, and the cation is an alkylimidazole type and includes a structure shown in Formula 1:

Wherein R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms. And the anion is Cl ^-, Br ^- or CH ₃ COO ^-.

In one embodiment of the present invention, the ionic liquid is 1-ethyl-3-methylimidazole acetate.

In one embodiment of the present invention, the polymer comprises cellulose or poly (m-xylylenediisophthalamide).

In an embodiment of the present invention, a weight ratio of the salt to the ionic liquid is 10:90 to 0.1: 99.9.

In an embodiment of the present invention, the content of the polymer is 5 wt% to 20 wt% based on the total weight of the spinning mucus.

In one embodiment of the present invention, the polymer is dissolved in an ionic liquid. The mixed solution with salts is performed at a temperature between 60 ° C and 80 ° C.

In an embodiment of the present invention, the spinning process is a wet spinning technology or a dry-jet wet spinning technology.

The present invention further provides a spinning mucus, including a polymer, a salt, and an ionic liquid, wherein the salt includes KCl, KBr, KOAc, NaBr, ZnCl ₂ or a combination thereof.

In an embodiment of the present invention, the ionic liquid is composed of a cation and an anion, and the cation is an alkylimidazole type and includes a structure represented by Formula 1:

Wherein R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms, and the anion is Cl ⁻ , Br ⁻ or CH ₃ COO ⁻ .

In one embodiment of the present invention, the ionic liquid is 1-ethyl-3-methylimidazole acetate.

In one embodiment of the present invention, the polymer comprises cellulose or poly (m-xylylenediisophthalamide).

In an embodiment of the present invention, a weight ratio of the salt to the ionic liquid is 10:90 to 0.1: 99.9.

In an embodiment of the present invention, the content of the polymer is 5 wt% to 20 wt% based on the total weight of the spinning mucus.

Based on the above, the present invention proposes a method for preparing fibers, which can increase the strength of the fibers. In addition, it can reduce the process temperature, improve the phenomenon of process energy consumption, and reduce recycling costs, which has industrial value. In addition, the present invention proposes a spinning adhesive Liquid, good spinnability, using wet spinning technology or dry-jet wet spinning technology can obtain fibers with higher fiber strength.

In order to make the above features and advantages of the present invention more comprehensible, the following specific embodiments are described in detail below.

According to an embodiment of the present invention, a method for preparing a fiber is provided. First, the polymer is dissolved in a mixed solution of an ionic liquid and a salt to form a spinning slime. In this embodiment, the polymer is, for example, cellulose or poly (m-xylylenediisophthalamide). The salts are, for example, KCl, KBr, KOAc, NaBr, ZnCl ₂ or a combination thereof. An ionic liquid is composed of a cation and an anion, for example, and the cation is an alkylimidazole type, and includes a structure represented by Formula 1:

Wherein R ₁ and R ₂ are alkyl groups having 1 to 4 carbon atoms; and the anion is, for example, Cl ⁻ , Br ⁻ or CH ₃ COO ⁻ . In another embodiment, the ionic liquid is, for example, 1-ethyl-3-methylimidazolium acetate ([EMIM] OAc).

In this embodiment, salts are added to the ionic liquid, and the salts and the ionic liquid The ratio of the weight ratio of the body is, for example, 10:90 to 0.1: 99.9, preferably, the ratio of the weight ratio of the salt to the ionic liquid is, for example, 3:97 to 1:99, and more preferably, the salt and the ion The ratio of the weight ratio of the liquid is, for example, 3:97. Adding salts to the ionic liquid can increase the polarity of the ionic liquid to further increase the solubility of the polymer.

In this embodiment, the content of the polymer is, for example, 5 wt% to 20 wt% based on the total weight of the spinning mucus. In another embodiment, the content of the polymer is, for example, 10 wt% to 15 wt% based on the total weight of the spinning mucus. In another embodiment, the content of the polymer is, for example, 10% by weight based on the total weight of the spinning mucus.

It is worth noting that the polymer is dissolved in the mixed solution of ionic liquid and salt at a temperature between 60 ° C and 80 ° C. The process temperature of the conventional technology using NMMO is 110 ° C ~ 130 ° C, which is relatively energy-consuming. In contrast, the use of the ionic liquid of the present invention can effectively reduce the overall process temperature, therefore, it can improve the degradation of the polymer and have energy saving effects. In addition, ionic liquids also have the advantages of no volatility, high chemical stability and high stability.

Thereafter, the spinning viscose is used as a raw material to perform a spinning process to form fibers. In this embodiment, the spinning process is, for example, spinning the spinning viscose through Dry-jet Wet Spinning, and dropping the spun silk into a molding solution (for example, ethanol, water or Combination), and then moved to water for washing to complete the preparation of the fiber. In other embodiments, the spinning process may also be performed by, for example, wet spinning technology.

In the following, the experimental examples are used to explain in detail the preparation and characteristics of the fibers proposed in the above examples. However, the following experimental examples are not intended to limit the present invention.

Experimental example

In order to prove that the fiber prepared by the fiber preparation method provided by the present invention has excellent fiber strength, and the overall process temperature is low, and it has energy saving effects, this experimental example is specifically made below.

Preparation of fibers Example 1

48.5 g of ionic liquid 1-ethyl-3-methylimidazole acetate (hereinafter referred to as [EMIM] OAc) and 1.5 g (3 wt%) of KOAc were heated and dissolved at 60 ° C. until dissolved to form a mixed solution. Next, 5 g of cellulose was added and dissolved at 60 ° C. with stirring and heating to form a spinning slime. A spinning process is performed using the spinning slime as a raw material, and a cellulose fiber is formed by a dry-jet wet spinning technology.

Example 2

48.5g of ionic liquid [EMIM] OAc, 1g (2wt%) of KOAc and 0.5g (1wt%) of KBr were heated and dissolved at 60 ° C until dissolved to form a mixed solution. Next, 5 g of cellulose was added and dissolved at 60 ° C. with stirring and heating to form a spinning slime. A spinning process is performed using the spinning slime as a raw material, and a cellulose fiber is formed by a dry-jet wet spinning technology.

Example 3

48.5 g of ionic liquid [EMIM] OAc and 1.5 g (3.wt%) of KBr were heated and stirred at 60 ° C. until dissolved to form a mixed solution. Next, 5 g of cellulose was added and dissolved at 60 ° C. with stirring and heating to form a spinning slime. A spinning process is performed using the spinning slime as a raw material, and a cellulose fiber is formed by a dry-jet wet spinning technology.

Example 4

48.25 g of ionic liquid [EMIM] OAc and 1.75 g (3.5 wt%) of KBr were heated and stirred at 60 ° C. until dissolved to form a mixed solution. Next, 5 g of cellulose was added and dissolved at 60 ° C. with stirring and heating to form a spinning slime. A spinning process is performed using the spinning slime as a raw material, and a cellulose fiber is formed by a dry-jet wet spinning technology.

Example 5

48.5 g of ionic liquid [EMIM] OAc and 1.5 g (3 wt%) of KCl were heated and stirred at 80 ° C. until dissolved to form a mixed solution. Next, 5 g of cellulose was added and dissolved at 80 ° C. with stirring and heating to form a spinning slime. The spinning viscose is used as a raw material to perform a spinning process, and a dry jet wet spinning technology is used to form fibers.

Example 6

48.5 g of ionic liquid [EMIM] OAc and 1.5 g (3 wt%) of KBr were heated and stirred at 80 ° C. until dissolved to form a mixed solution. Next, add 10g of Poly-m-xylylene-m-phenylenediamine is dissolved and stirred at 80 ° C to form a spinning slime.

Comparative example

5g of wood pulp cellulose was added to 50g of ionic liquid [EMIM] OAc, and after being dissolved by stirring and heating at 60 ° C, a spinning process was performed, and fibers were formed by a dry-jet wet spinning technology.

Measurement of fiber strength

Next, the cellulose fibers of Examples 1 to 5 and the cellulose fibers of Comparative Examples were measured for fiber strength by the detection method of ASTM D3822, and the results of each measurement are shown in Table 1 below.

As can be seen from Table 1 above, the comparative example dissolves cellulose only with an ionic liquid, and the fiber strength of the prepared cellulose fiber is 3.2 gf / den. In contrast, Examples 1 to 5 are celluloses prepared according to the fiber preparation method of the present invention. Preparation of fibers, where the ionic liquid used is [EMIM] OAc, and 3wt% KOAc, 2wt% KOAc / 1wt% KBr, 3wt% KBr, 3.5wt% KBr, or 3wt% KCl and other salts are added to the ionic liquid. . The cellulose is then dissolved in the mixed solution of the aforementioned ionic liquid and salt, and the fibers are formed by the dry-jet wet spinning technology. As can be seen from Table 1, the cellulose fibers formed in Examples 1 to 5 had fiber strengths of 4.6 gf / den, 3.8 gf / den, 4.1 gf / den, 4.9 gf / den, and 3.5 gf / den, respectively. Therefore, the fiber strength of the fibers prepared in Examples 1 to 5 is significantly higher than that of the cellulose fibers prepared in Comparative Examples. That is, the fiber preparation method proposed by the present invention can significantly improve the fiber strength.

In summary, the present invention provides a method for preparing fibers, which can increase the solubility of the fibers and increase the fiber strength. The ionic liquid itself is non-volatile, has high chemical stability and high thermal stability, and can also be recycled. Adding salts to ionic liquids can increase polarity, improve solubility in polymers, and effectively increase fiber strength. In addition, the process temperature can be lowered to improve the phenomenon of process energy consumption. In addition, compared with the conventional technology using NMMO, the fiber preparation method provided by the present invention does not require additional stabilizers or solvents (such as DMSO), so it can reduce the cost of recycling and has industrial value. In addition, the present invention proposes a spinning slime, which has good spinnability. Fibers with high fiber strength can be obtained by using wet spinning technology or dry-jet wet spinning technology.

Although the present invention has been disclosed as above with the examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some modifications and retouching without departing from the spirit and scope of the present invention. The protection scope of the present invention Subject to the scope of the attached patent application.

Claims (14)

A fiber preparation method includes: dissolving a polymer in a mixed solution of an ionic liquid and a salt to form a spinning slime, wherein the salt includes KCl, KBr, KOAc, NaBr, ZnCl ₂ or A combination thereof; and a spinning process using the spinning slime as a raw material to form the fiber. The method for preparing a fiber according to item 1 of the scope of the patent application, wherein the ionic liquid is composed of a cation and an anion, and the cation is an alkylimidazole type and includes a structure shown in Formula 1:

Wherein R ₁ and R ₂ are alkyl groups having 1-4 carbon atoms; the anion is Cl ⁻ , Br ⁻ or CH ₃ COO ⁻ . The method for preparing a fiber according to item 1 of the application, wherein the ionic liquid includes 1-ethyl-3-methylimidazole acetate. The method for preparing a fiber according to item 1 of the scope of patent application, wherein the polymer comprises cellulose or poly (m-xylylenediisophthalamide). The method for preparing a fiber according to item 1 of the scope of the patent application, wherein a weight ratio of the salt to the ionic liquid is 10:90 to 0.1: 99.9. The method for preparing a fiber according to item 1 of the scope of the patent application, wherein the content of the polymer is 5 wt% to 20 wt% based on the total weight of the spinning slime. The method for preparing a fiber according to item 1 of the scope of patent application, wherein the The polymer is dissolved in the mixed solution at a temperature between 60 ° C and 80 ° C. The method for preparing a fiber according to item 1 of the scope of patent application, wherein the spinning process is a wet spinning technology or a dry-jet wet spinning technology. A spinning slime includes: a polymer; an ionic liquid; and a salt, wherein the salt includes KCl, KBr, KOAc, NaBr, ZnCl ₂ or a combination thereof. The spinning slime according to item 9 of the scope of the patent application, wherein the ionic liquid is composed of a cation and an anion, and the cation is an alkylimidazole type, including a structure shown in Formula 1:

Wherein R ₁ and R ₂ are alkyl groups having 1-4 carbon atoms; the anion is Cl ⁻ , Br ⁻ or CH ₃ COO ⁻ . The spinning slime according to item 9 of the scope of the patent application, wherein the ionic liquid includes 1-ethyl-3-methylimidazole acetate. The spinning slime according to item 9 of the scope of the patent application, wherein the polymer comprises cellulose or poly (m-xylylenediisophthalamide). The spinning slime according to item 9 of the scope of the patent application, wherein the ratio of the salt to the ionic liquid is from 10:90 to 0.1: 99.9 by weight. The spinning slime as described in item 9 of the patent application scope, wherein the spinning The content of the polymer is 5 wt% to 20 wt% based on the total weight of the mucus.