TWI673408B - Hygroscopic exothermic agent and method for manufaturing the same - Google Patents

Abstract

A hygroscopic heating agent and a preparation method thereof. The hygroscopic exothermic agent includes 10 parts by weight to 90 parts by weight of a protein, a polymer dispersion liquid, and a remaining carrier that is immiscible with the protein and the polymer dispersion liquid. The polymer dispersion liquid includes 90 to 10 parts by weight of nano cellulose.

Description

Hygroscopic heating agent and preparation method thereof

The invention relates to a hygroscopic heating agent and a preparation method thereof, and in particular to a hygroscopic heating agent having protein and nanocellulose and a preparation method thereof.

Affected by global climate change, extremely cold extreme climates often occur in winter. In order to cope with the extremely cold environment, the textile industry continues to develop various functional materials. Among them, materials with moisture absorption and heat generation properties are regarded as the most potential development targets.

Generally, due to the structure of wool, moisture does not easily come into contact with the proteins in the wool to react, so the moisture absorption and heat generation are not good. In addition, most of the materials commonly used in hygroscopic heating fibers on the market are acrylic fibers, which use the principle of condensed water to generate heat, but the hygroscopic and exothermic properties of acrylic fibers are still insufficient. Therefore, the development of materials with excellent hygroscopic and exothermic properties is still the goal of industry efforts.

The invention provides a hygroscopic heating agent and a preparation method thereof. The hygroscopic heating agent has good hygroscopic heating property, and can be attached to textiles by processing methods such as coating or impregnation, so that the textile has the function of hygroscopic heating.

The hygroscopic exothermic agent of the present invention includes 10 parts by weight to 90 parts by weight of a protein, a polymer dispersion liquid, and a remaining carrier that is immiscible with the protein and the polymer dispersion liquid. The polymer dispersion liquid includes 90 to 10 parts by weight of nano cellulose.

The method for preparing the hygroscopic exothermic agent of the present invention includes the following steps. The protein-containing wool is mixed with the ionic liquid and heated to extract the protein to obtain a mixed solution of the protein and the ionic liquid. The mixed solution is mixed with a non-solvent of the protein and filtered to obtain a regenerated protein. The regenerated protein is mixed with a polymer dispersion.

In an embodiment of the present invention, the protein is, for example, keratin.

In an embodiment of the present invention, the carrier is, for example, water or alcohol.

In an embodiment of the present invention, the protein-containing wool is, for example, wool or feather.

In an embodiment of the present invention, the ionic liquid has a structure represented by Formula (1), for example: Formula (1), wherein R1 and R2 are independently of each other _{-CH 3, -CH 2 CH 3,} -CH 2 CH 2 CH 3 or _{-CH 2 CH 2 CH 2 CH 3} , R3 is F ^-, Cl ^-, Br ^{- _{, HSO 4 -, HCOO -,}} CH 3 COO - or H ₂ PO ₄ ^-.

In an embodiment of the present invention, the polymer dispersion liquid is, for example, nano-cellulose, and the solid content ratio of the regenerated protein to the polymer dispersion liquid is, for example, between 1: 9 and 9: 1.

In an embodiment of the present invention, the method for preparing a hygroscopic exothermic agent further comprises mixing a carrier with a regenerated protein and a polymer dispersion, wherein the carrier and the protein and the polymer dispersion are not mutually soluble.

Based on the above, the nano-cellulose will re-bond and release heat when it comes into contact with protein. Therefore, the hygroscopic heating agent of the present invention can have better hygroscopic heating property, and the hygroscopic heating agent can more effectively absorb water vapor. increase temperature.

In order to make the above features and advantages of the present invention more comprehensible, embodiments are hereinafter described in detail with reference to the accompanying drawings.

Due to the extreme cold environment caused by climate change, the demand for materials with good hygroscopic and exothermic properties is increasing in the market. However, the hygroscopic and exothermic properties of products on the market are still not good enough. Therefore, in response to the extreme cold climate and market demand, The present invention proposes a hygroscopic exothermic agent with good hygroscopic exothermicity and compatible with fabrics through examples. However, the following examples are not intended to limit the present invention.

FIG. 1 is a flowchart of a method for preparing a hygroscopic heating agent according to an embodiment of the present invention. Please refer to FIG. 1, a method for preparing a hygroscopic heating agent according to an embodiment of the present invention is as follows. First, step S100 is performed, and the protein-containing wool is mixed with the ionic liquid and heated to extract the protein to obtain a mixed solution of the protein and the ionic liquid. In one embodiment, the protein-containing wool is mixed with the ionic liquid, for example, through a homogenization process.

In one embodiment, the protein-containing wool may be animal hair or hair, such as wool or feather, and the protein may be keratin. Since the protein has rich hygroscopic heat generating functional groups (for example, -NH ₂ , -COOH, -OH, or a combination thereof), when the protein is combined with water and gas, it emits heat, which increases the temperature.

In one embodiment, the ionic liquid has a structure represented by Formula (1), for example: Formula (1), wherein R1 and R2 are independently of each other _{-CH 3, -CH 2 CH 3,} -CH 2 CH 2 CH 3 or _{-CH 2 CH 2 CH 2 CH 3} , R3 is F ^-, Cl ^-, Br ^{- _{, HSO 4 -, HCOO -,}} CH 3 COO - or H ₂ PO ₄ ^-. The ionic liquid may be an alkylimidazole-type ionic liquid. In detail, an alkylimidazole-type ionic liquid is composed of a cation and an anion, and the cation is an alkylimidazole-type cation. In this embodiment, the molecular weight of the ionic liquid may be between 100 and 2000 Daltons.

Next, step S200 is performed, and the mixed solution obtained in step S100 is mixed with the non-solvent of the protein and filtered to obtain a regenerated protein. In this embodiment, since the protein is insoluble in the non-solvent and the remaining substances in the mixed solution are dissolved in the non-solvent, the substances other than the protein can be removed by filtering to obtain a solid regenerated protein. The above-mentioned non-solvent is, for example, water, alcohol or acetone, and is preferably water or alcohol.

The regenerated protein formed through step S200 is a protein extracted from wool, which has a higher purity. When the above-mentioned protein is keratin, compared with natural keratin, the regenerated protein (regenerated keratin) of the present invention can effectively increase the temperature by about 4 ° C to 5 ° C or higher after absorbing water vapor, for example, from 28 ° C. Above 33 ° C, it is more suitable for functional fabrics that absorb moisture and generate heat.

After that, step S300 is performed, and the regenerated protein obtained in step S200 is mixed with the polymer dispersion liquid to obtain the hygroscopic heating agent of the present invention. In one embodiment, the polymer dispersion is, for example, a dispersion containing nano cellulose. In addition, in the hygroscopic heating agent of the present invention, the content ratio of the regenerated protein to the nanocellulose is, for example, between 1: 9 and 9: 1. That is, the hygroscopic exothermic agent of the present invention includes 10 to 90 parts by weight of regenerated protein and 90 to 10 parts by weight of nanocellulose. In the range of this content ratio, the hygroscopic heat generating agent of the present invention can more effectively increase the temperature after absorbing water vapor.

Since nanocellulose is rebonded and exothermic when it comes into contact with regenerated protein, the hygroscopic heat generating agent of the present invention uses nanocellulose and regenerated protein as compared to a hygroscopic heat generating agent having only nanocellulose or protein. Re-bonding between them can further increase the temperature. In this embodiment, the hygroscopic heating agent can increase the temperature by about 4 ° C to 5 ° C or more.

In some embodiments, the nanocellulose is, for example, carboxymethyl cellulose (CMC), sodium alginate, oxidized nanocellulose (TOCN), mechanically defibrated nanocellulose (MCN), acid hydrolyzed type Nanocellulose (ACN) or ammonium persulfate modified nanocellulose (APSCN), where oxidized nanocellulose (TOCN) is, for example, 2,2,6,6-tetramethylpiperidine-1- Oxide-oxidized nanocellulose.

In addition, when step S300 is performed, a carrier that is immiscible with the protein and the polymer dispersion can be selectively mixed with the regenerated protein and the polymer dispersion, so that the regenerated protein can be more uniformly dispersed and applied to subsequent coatings. Cloth or infiltration process. The carrier is, for example, water or alcohol.

Because the carrier can more evenly disperse the regenerated protein and the nano-cellulose in the polymer dispersion and apply it to the subsequent coating or impregnation process, the hygroscopic heating agent containing the carrier has high processing and application .

The hygroscopic exothermic agent formed by the preparation method of the embodiment of the present invention has very good hygroscopic exothermicity, and can increase the temperature more effectively after absorbing water vapor. Therefore, it can be used as a coating liquid and can be applied by coating. The coating layer or film is formed on the textile by means of impregnation or the like, so that the treated fabric has the function of absorbing and generating heat. For example, the hygroscopic heating agent in this case can be coated on a non-woven fabric by spraying water mist to make a mask with a warming effect. In addition, the hygroscopic exothermic agent of the present invention can also be added to the spinning dope to further produce a hygroscopic exothermic fiber. Therefore, the hygroscopic heating agent of the present invention has various applications and is not limited to the above.

In the following, the effects of the above examples are confirmed by experimental examples, but the present invention is not limited to the following.

＜ Experimental Example 1 ＞

Wool and 1-butyl-3-methyl-imidazole chloride ([BMIM] Cl) (Ionic liquid represented by formula (1), where R1 is -CH ₂ CH ₂ CH ₂ CH ₃ and R2 is -CH _3, and R3 is Cl ^-) were mixed and heated in order to extract the keratin and keratin mixed solution and the ionic liquid. The mixed solution is mixed with water (non-solvent of keratin) and filtered to obtain regenerated keratin.

After that, the keratin extracted from the wool is mixed with a polymer dispersion containing oxidized nanocellulose (TOCN) to form a hygroscopic heat generating agent. The weight ratio of keratin and oxidized nanocellulose (TOCN) is 2 :1.

＜ Experimental Example 2 ＞

Keratin was extracted from wool in the same manner as in Experiment 1, and then the keratin was mixed with a polymer dispersion containing carboxymethyl cellulose (CMC) to form a hygroscopic exothermic agent, wherein keratin and carboxymethyl cellulose (CMC) weight ratio is 2: 1.

＜ Experimental Example 3 ＞

Keratin was extracted from wool in the same manner as in Experiment 1, and then mixed with a polymer dispersion containing sodium alginate to form a hygroscopic heat generating agent, wherein the weight ratio of keratin and sodium alginate was 2: 1 .

＜ Experimental Example 4 ＞

Goose feather and 1-ethyl-3-methylimidazole acetate ([EMIM] OAc) (Ionic liquid represented by formula (1), where R1 is -CH ₂ CH ₃ , R2 is -CH ₃ , and R3 is CH ₃ COO ^-) were mixed and heated in order to extract the keratin and keratin mixed solution and the ionic liquid. The mixed solution is mixed with a non-solvent of the protein and filtered to obtain regenerated keratin.

After that, the keratin extracted from the goose feather is mixed with a polymer dispersion containing oxidized nanocellulose to form a hygroscopic heat generating agent, wherein the weight ratio of the keratin and the oxidized nanocellulose is 2: 1.

〈Comparative example 1〉

Comparative example 1 is wool.

〈Comparative example 2〉

Comparative example 2 is a goose feather.

〈Comparative example 3〉

Regenerated keratin was extracted from wool in the same manner as in Experiment 1.

〈Comparative example 4〉

Regenerated keratin was extracted from goose feathers in the same manner as in Experiment 4.

Hygroscopic fever test

Samples of 0.5 g of Experimental Examples 1 to 4 and Comparative Examples 1 to 4 were respectively placed on petri dishes with a diameter of 30 mm. Set the ambient temperature to 24 ° C and the ambient humidity to 50%. Use a humidifier to make the sample absorb water mist. The amount of humidified water is about 0.167 ml / min, and the temperature difference generated by each sample is recorded, as shown in Table 1.

Table 1 Experimental example 1 Experimental example 2 Experimental example 3 Experimental Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Temperature difference (℃) 5.4 4.1 4 5.1 1 0.8 3.3 2.9

According to Table 1, compared to the wool, goose feathers, and regenerated keratin of Comparative Examples 1 to 4, since the hygroscopic heating agent of Experimental Examples 1 to 4 has both keratin and nanocellulose, it can absorb water mist. Cause a large temperature difference. That is, the hygroscopic exothermic agent of the present invention has good hygroscopic exothermic properties.

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 shall be determined by the scope of the attached patent application.

S100, S200, S300: Steps.

FIG. 1 is a flowchart of a method for preparing a hygroscopic heating agent according to an embodiment of the present invention.

Claims (10)

A hygroscopic heating agent includes: 10 parts by weight to 90 parts by weight of protein; a polymer dispersion liquid including 90 parts by weight and 10 parts by weight of nanocellulose; and the balance with the protein and the polymer Dispersions are immiscible carriers. The hygroscopic heat generating agent according to item 1 of the scope of patent application, wherein the protein is keratin. The hygroscopic exothermic agent according to item 1 of the patent application scope, wherein the carrier includes water or alcohol. A method for preparing a hygroscopic exothermic agent comprises: mixing and heating protein-containing wool with an ionic liquid to extract the protein to obtain a mixed solution of the protein and the ionic liquid; and mixing the mixed solution with the ionic liquid; The non-solvent of the protein is mixed and filtered to obtain a regenerated protein; and the regenerated protein is mixed with a polymer dispersion. The method for preparing a hygroscopic exothermic agent according to item 4 of the scope of patent application, wherein the protein is keratin. The method for preparing a hygroscopic exothermic agent according to item 4 of the scope of patent application, wherein the protein-containing wool includes wool or feather. The method for preparing a hygroscopic heat generating agent according to item 4 of the scope of patent application, wherein the ionic liquid includes a structure represented by formula (1): Formula (1), wherein R1 and R2 are independently of each other _{-CH 3, -CH 2 CH 3,} -CH 2 CH 2 CH 3 or _{-CH 2 CH 2 CH 2 CH 3} , R3 is F ^-, Cl ^-, Br ^{- _{, HSO 4 -, HCOO -,}} CH 3 COO - or H ₂ PO ₄ ^-. The method for preparing a hygroscopic exothermic agent according to item 4 of the scope of the patent application, wherein the polymer dispersion liquid includes nano cellulose, and the content ratio of the regenerated protein to the nano cellulose is between 1: 9 to 9: 1. The method for preparing a hygroscopic exothermic agent according to item 4 of the scope of patent application, further comprising mixing a carrier with the regenerated protein and the polymer dispersion, wherein the carrier is dispersed with the protein and the polymer. The liquids are not miscible. The method for preparing a hygroscopic heat generating agent according to item 9 of the scope of application for a patent, wherein the carrier comprises water or alcohol.