WO2005108497A1

WO2005108497A1 - Nano-wool emulsion and nano-wool powders, the manufacturing method for them and their uses

Info

Publication number: WO2005108497A1
Application number: PCT/CN2005/000620
Authority: WO
Inventors: Yi Li; Tao Xu; Junyan Hu; Kwokwing Yeung
Original assignee: The Hong Kong Polytechnic University
Priority date: 2004-05-07
Filing date: 2005-05-08
Publication date: 2005-11-17
Also published as: CN100526387C; CN1693371A

Abstract

The present invention relates to nano-wool emulsion and nano-wool powders, the manufacturing method for them and their uses. In order to provide the easy method of manufacturing them in the present invention, the manufacturing process is put forward by the following step: treating the wool by base catalysis hydrolysis, preparing the protein emulsion, dispersing it further and obtaining the nano-protein emulsion and dry powders. The nano-wool emulsion and nano-powders obtained by the method according to the present invention could be used to treat the fabrics, so that the treated fabrics are excellent in several properties such as warm keeping coefficient, UV resistance and infrared thermal protection.

Description

Nano wool emulsion and powder, preparation method and application thereof

The invention relates to a nano-wool emulsion and powder, a preparation method and uses thereof. Background technique

Natural fiber has played an important role in the field of textile materials since ancient times. Because of its unique performance, it has been widely used in modern textile industry as a high-quality textile material. However, due to the limitations and specific requirements of the spinning phase, not all fibers can be used for spinning. Therefore, sometimes natural fibers such as sheep wool, silk, cotton, hemp, etc. are wasted during processing. Due to the excellent inherent characteristics of natural fibers, the development of a new method for recycling these fibers has huge market potential.

At the same time, not only the textile industry, but also other industrial areas also need such technology in the functional design and application of new materials.

In the prior art, there have been some patents related to the recycling of the above-mentioned fibers. For example, US patent us 6,437,050 B1 proposes a polymer nanoparticle composite, which uses poly (alkenybenzene) as the core and polyconjugation. Poly (conjugated diene) is a surface layer, which is prepared by a dispersion polymerization process (a method for preparing a polymer ultrafine powder). Its average particle size is less than 100 m

Chinese patent application CN 94115873.X gives a chemical treatment, crushing, filtering, low-temperature drying method using cotton and hemp fiber to prepare cellulose powder with an average size in the range of 2.5-10 nm.

U.S. Patent No. 5,853,764 proposes a method for preparing ultra-fine silk powder (that is, the material is silk) using an lye, which is a chemical method.

U.S. Patent No. 5,718,954 proposes a method of preparing 4 points of ultrafine filaments (material is silk). Its average particle size is around 10 μm.

U.S. Patent No. 5,763,583 proposes a method for preparing soluble protein by using animal hair as a raw material and denaturing it with thioglycolic acid as an oxidizing agent in a weak alkaline environment to change a water-repellent disulfide bond into a water-soluble group.

U.S. patent US 5,276,138 uses hydrogen peroxide to dissolve in weak alkaline environment 1001C for a long time (> lh)

Confirm this 2 T N2005 / 000620

The animal hair (such as wool) is decomposed, and the precipitate is precipitated below the isoelectric point (pH <3), and then filtered and dried to obtain wool powder with a particle size of 1-10 μm.

Organic materials generally exhibit high strength and ductility, have high fracture strength, and are difficult to pulverize / mill / crush into ultra-fine particle size using traditional steel or iron ball mill machinery. At the same time, traditional metal machinery generates a large amount of thermal energy during the milling process, which changes the inherent structure of organic materials, and the machine itself is prone to wear for long-term working of organic materials. Summary of the invention

Relative to the above-mentioned shortcomings of the prior art, the object of the present invention is to propose a simple chemical method for crushing wool fibers. Using this method, nano-scale emulsions and powders can be prepared from natural wool fibers.

By using the above method of the present invention, environmental protection and utilization of wool fibers can be achieved. Another object of the present invention is to provide a method for pulverizing wool fibers to a nanometer scale and maintaining their inherent structure and characteristics.

A further object of the present invention is to use the obtained nano-wool emulsion for treating textile fabrics, thereby providing additional functions.

The present invention unexpectedly found that the wool is catalyzed and hydrolyzed by alkaline to prepare nanoemulsions thereof. The obtained product has excellent properties and can be widely used in the textile industry. Technical solution of the present invention ^! Mouth:

1. Preparation of wool protein emulsion using alkaline catalyzed hydrolysis, including:

-Immersing wool fibers in lye to hydrolyze at conventional hydrolysis temperatures and times known in the art;

Then, a nanoemulsion is prepared by using a solution obtained by hydrolysis, wherein the electrolyte (inorganic acid) is slowly added dropwise under stirring (the inorganic acids are well known to those skilled in the art, such as hydrochloric acid, etc., and will not be described here again). a ρΗ value to 5-7, above the isoelectric point, forming an emulsion containing an ordered crystal phase of nanoscale spherical protein crystals; and

■ The resulting emulsion is further dispersed by conventional methods in the art, such as sonication.

2. Steps of preparing dry powder The nano-powder of the emulsion is prepared by a conventional method in the art, such as a spray drying method or a freeze drying method.

3. Application steps: Use nano-protein emulsion to treat the fabric, such as cotton fabric, polyester fiber, etc. · For example, soak the pure cotton fabric in nano-protein emulsion to form a protein coating.

In summary, the present invention provides a nano-scale wool emulsion, which is characterized in that: the emulsion has a particle size distribution as shown in FIG. 3.

Wherein the powder has a particle size of about 73.3 nm on average.

The invention also provides a nano-scale wool powder, characterized in that the wool powder has at least one of the following characteristics:

As shown in Figure 2 (a) and / or Figure 2 (b), (c);

It has a Fourier transform infrared analysis curve as shown in Figure 4;

It has an X-ray diffraction analysis curve as shown in FIG. 5.

The present invention also provides a method for preparing the above-mentioned nano-scale wool emulsion, which is characterized in that: before preparing the nano-wool emulsion, the wool fiber is subjected to alkaline catalytic hydrolysis.

After the wool fiber is immersed in the alkaline solution to be hydrolyzed, a nanoemulsion is prepared by using the solution obtained by the hydrolysis, by: slowly adding the solution obtained by hydrolysis to the inorganic acid electrolyte under stirring, and adjusting the pH value to 5-7, high At the isoelectric point, an emulsion containing an ordered crystal phase of spherical protein crystals on the nanometer scale is formed.

The method further includes the step of further dispersing the obtained emulsion. Wherein said further dispersing said emulsion is performing said further dispersing using sonication.

The invention also provides a method for preparing the above-mentioned nano-scale wool powder, which is characterized by the steps of preparing a nano-wool emulsion after preparing the nano-wool emulsion according to the above steps.

Among them, a spray drying method or a freeze drying method is used to prepare the nano powder. The invention also provides the use of the prepared nano-wool emulsion, wherein the use is to treat textile fabrics, such as pure cotton fabrics, polyester fibers, with the nano-scale wool emulsion.

The above application is to soak a pure cotton fabric in the nano-scale wool emulsion to form a protein ^ coating.

The invention also provides nano-scale wool powder for improving textile fabrics in the textile industry. Uses for surface properties.

In addition, the present invention also provides a method for regenerating and utilizing wool fibers, and a method for crushing wool fibers to a nanometer scale and maintaining its inherent structure and characteristics. The method also includes the above steps for preparing an emulsion or a powder.

The effects of the present invention are:

-With this method, nano-scale ultra-fine powder of wool can be easily obtained;

■ And this kind of wool nano-scale powder can be easily used to treat fabrics, that is, this method is very convenient for industrial batch production of nano-protein ^ functional powders, and no complicated process is required;

■ The treated fabric has excellent performance in various properties such as the coefficient of warmth, UV resistance, and infrared thermal protection;

-The nano-wool powder obtained by using the preparation process conditions of the present invention shows a higher degree of crystallinity (see Fig. 5);

■ The nano wool powder of the present invention has almost no structural difference from the original wool material; ■ The preparation method has a wide range of uses: The wool hydrolysis method of the present invention can be widely used to prepare nano functional powders or emulsions of organic materials and is easy to realize industrial production The product has a wide range of uses: The product of the present invention can be widely used in many industrial fields, such as textiles, medicine and so on. For example, wool powder can be widely used in the textile industry and as a new coating agent. These products can improve the surface properties of textile fabrics after treatment, for example, the surface of synthetic fiber fabrics can be treated to have both natural and artificial fiber properties. BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1 shows a photomicrograph of wool fibers. The illustrated wool is about 60-120 mm long and 25 μm in diameter.

Figures 2 (a) to (c) show transmission micrographs of the prepared nano-scale wool protein particles. The number of scales in the lower right corner of Figure 2 (a) is 100 nm; Figures 2 (b) and (c) are 400 nm.

Figure 3 shows the particle size and distribution results of the protein emulsion measured by the LS 13320 laser particle size analyzer. The results show that the average particle size is about 73.3mn. Figure 4 compares the Fourier transform infrared analysis curve of the original wool powder with the nano wool protein powder prepared by the above method.

Figure 5 compares the X-ray diffraction analysis curves of the original wool powder and the nano-wool protein powder prepared by the method of the present invention.

In terms of defining the nanowool emulsion or powder of the present invention, generally it can only be defined by its size, that is, the "nano" grade, or by its map (such as those listed in the drawings), or by the method of preparation definition. detailed description

The present invention uses wool as a treatment object.

The size of a material is generally its naturally-occurring size. The present invention exemplifies the wool shown in FIG. 1 with a length of 60-120 mm and a diameter of 25 μm. However, the size of the raw material of the present invention is not limited by the size of this example.

The following is a demonstration of the preparation of wool protein emulsion:

Examples

Wool fibers (5g) were immersed in 100ml, 5% sodium hydroxide solution, and the temperature was controlled at 100 V. After 15 minutes, almost all wool fibers were dissolved.

A 3.7% hydrochloric acid solution was added dropwise to the obtained solution under low-speed stirring, and the pH value of the wool hydrolyzate was adjusted to 6.92 to form a wool protein emulsion.

Thereafter, using methods well known in the art:

The emulsion is further dispersed by sonication;

Spray drying method or freeze drying method are used to prepare nano wool protein powder; nano wool protein emulsion is used to treat pure cotton fabric.

The effect of the present invention is confirmed as follows:

2 (a) to (c) show transmission micrographs of the prepared nano-scale wool protein particles. The particle size and distribution of the protein emulsion measured by the LS 13320 laser particle size analyzer (shown in Figure 3) showed that the average particle size was 73.3 nm.

Comparing the original wool powder with the nano wool protein powder prepared by the method of the present invention, The respective Fourier transform infrared analysis curves are shown in FIG. 4.

The results of Fourier infrared spectroscopy in Fig. 4 show several characteristic absorption peaks. The 1653 cm " ¹ absorption peak shows the stretching vibration of the C = 0 group of the polypeptide chain; 1548 cm- ¹ shows that the NH in the peptide bond is trans- The configurational form exists; 1401cm- ¹ shows that the NH in the peptide bond exists as a cis configuration relative to C = 0. There is almost no structural difference between the nano wool protein powder and the original wool material.

X-ray diffraction analysis curves of the original wool powder and the nano wool protein powder prepared by the method of the present invention are shown in FIG. 5. The X-ray diffraction analysis results in Fig. 5 show that under this preparation process condition, the nano wool protein powder shows a higher degree of crystallinity.

The specific performance of the pure cotton fabric treated with the nano wool protein emulsion of the present invention is as follows:

Sample index

Cotton fabric 01: Untreated cotton fabric

Cotton Fabric 02: Cotton Fabric Treated with Nano Wool Protein Emulsion

2. A value of warmth coefficient

Standard deviation Standard error Mean weight (g) Cotton fabric 1 4.52 9.04 6.72 2.26 1.31 6.76 2.69 Cotton fabric 2 46.61 49.32 49.32 1.57 0.91 48,42. 3.19

3.UPF value determination

4. Infrared analysis of cotton 101 cotton willow 2

0.0188

0.0067

0.3021

0.0942

The above 3.854 results show:

Thermal analysis, after the ooo ¹ ^ "protein emulsion of the present invention is treated, the thermal insulation coefficient (α value) increases, and

Inch *

Cotton fabrics are 8 times warmer than untreated cotton fabrics.

UPF analysis. After the cotton fabric is treated with protein, the UPF value is more than 3 times that of the untreated cotton fabric, and the UV resistance of the fabric is greatly improved.

Analysis of infrared characteristics. After the pure cotton fabric is treated with the protein emulsion of the present invention, the K value (slope) is increased and the integral between 2s-9s is also increased at the same time, indicating that the ability to absorb and emit infrared is increased and decreased.了 Transmission. Therefore, the pure cotton fabric has an infrared thermal protection function after being processed by the protein emulsion of the present invention.

Claims

Claim

A nano-scale wool emulsion, characterized in that: the emulsion has a particle size distribution as shown in FIG. 3.

2. The nano-scale wool emulsion according to claim 1, wherein the powder has a particle size of about 73.3 nm on average.

3. A nano-scale wool powder, characterized in that the wool powder has at least one of the following characteristics:

As shown in Figure 2 (a) and / or Figure 2 (b), (c);

It has a Fourier transform infrared analysis curve as shown in Figure 4;

It has an X-ray diffraction analysis curve as shown in FIG. 5.

4. A method for preparing a nano-scale wool emulsion according to claim 1 or 2, characterized in that: before preparing the nano-wool emulsion, the wool fibers are subjected to alkaline catalytic hydrolysis.

5. The method according to claim 4, which is characterized by:

After the wool fiber is immersed in the alkaline solution to be hydrolyzed, a nanoemulsion is prepared by using the solution obtained by the hydrolysis, by the method: slowly adding the solution obtained by the hydrolysis to the inorganic acid electrolyte under stirring, and adjusting the pH to 5-7, which is higher than The isoelectric point forms an emulsion containing an ordered crystal phase of spherical protein crystals on the nanometer scale.

6. The method according to claim 5, further comprising the step of further dispersing the obtained emulsion.

7. The method according to claim 6, wherein said further dispersing said emulsion is performing said further dispersing using ultrasonication.

8. A method for preparing a nano-scale wool powder according to claim 3, which is characterized in that:

The step of preparing the nanoemulsion obtained by claim 6 or 7 into a nano powder.

9. The method according to claim 8, wherein the nano powder is prepared by a spray drying method or a freeze drying method.

10. The use of a nano-scale wool emulsion according to claim 1 or 2, wherein the use is A textile fabric is treated with the nano-scale wool emulsion.

11. The use according to claim 10, wherein the fabric is a pure cotton fabric or a polyester fiber.

12. The use according to claim 11, wherein a pure cotton fabric is soaked in said nano-scale wool emulsion to form a protein coating.

13. The use of the nano-scale wool powder according to claim 3 in the textile industry to improve the surface properties of textile fabrics.

14. A method for regenerating and utilizing wool fibers, said method having the steps of any one of claims 4-7.

15. A method for pulverizing wool fibers to a nanometer scale and maintaining its inherent structure and characteristics, said method having the steps according to any one of claims 4-7.

16. A method for regenerating and utilizing wool fibers, said method having the steps of claim 8.

17. The method according to claim 16, wherein said method has the steps according to claim 9.

18. A method of pulverizing wool fibers to a nanometer scale and maintaining its inherent structure and characteristics, said method having the steps of claim 8.

19. The method according to claim 18, wherein said method has the steps according to claim 9.