CN115559009B - Collagen filament with collagen microfiber structure and preparation method thereof - Google Patents

Abstract

The present invention proposes a collagen filament with a collagen microfiber structure and a preparation method thereof. First, the collagen colloid extracted from cowhide is diluted and stirred with deionized water at room temperature, a water-soluble cross-linking agent is added, and the collagen colloid is removed by centrifugation. Soak treatment, using polyethylene glycol as a coagulation bath, and wet spinning to prepare collagen filaments with excellent performance. Compared with the existing technology, the present invention directly uses collagen colloid as the raw material, only uses deionized water as the diluent of the collagen colloid, and retains the microfiber aggregate structure in natural collagen. It not only has the advantages of being green and environmentally friendly and low cost, but also has the largest It may retain the excellent properties of natural collagen, and the prepared collagen filaments have good mechanical properties and biocompatibility, which provides a basis for the application of collagen filaments in the textile field and medical field and can be industrialized.

Description

Collagen filament with collagen microfiber structure and preparation method thereof

Technical field

The present invention relates to a preparation method of collagen material, in particular to a collagen filament with a collagen microfiber structure and a preparation method thereof, and belongs to the technical field of textile materials.

Background technique

Collagen is a white, opaque, unbranched fibrous protein. It is a biological polymer composed of animal cells. It is widely found in the bones, tendons, muscle sheaths, ligaments, sarcolemma, cartilage and skin of animals. , is an extremely important protein in connective tissue. Collagen tissue is almost the same as human skin tissue and has excellent biocompatibility and biodegradability, which is unmatched by other synthetic polymer materials. The diversity and complexity of collagen structure and function give it a wide range of application prospects in food, cosmetics, nutraceuticals, biofertilizers, textiles and other fields.

The molecular structure of collagen, like other proteins, can be divided into primary, secondary, tertiary and quaternary structures. The primary structure refers to the composition and arrangement of amino acids, which is the most basic structure of a protein; the secondary, tertiary, and quaternary structures are the three-dimensional structures of protein molecules. Different configurations determine the performance and application of proteins. complex and diverse. Secondary structure: The molecular unit of collagen is usually called tropocollagen. Each tropocollagen molecule is a stable triple helix structure composed of three α-peptide chains wound in a parallel, right-handed helix. Tertiary structure: The three peptide chains are firmly connected through acetal cross-linking, aldehyde-amine condensation cross-linking, etc.; Quaternary structure: Procollagen is arranged in parallel bundles according to rules, with head and tail misalignment by 1/4, forming stable collagen microfibers through covalent bonds (microfibril) and further aggregate into bundles to form collagen.

At present, the most commonly used processing method for collagen filaments is to "dissolve" the collagen with a solvent and then wet-spinning to obtain long fiber materials. Commonly used collagen solvents at home and abroad mainly include fluoroalcohols such as hexafluoroisopropanol, acidic systems such as acetic acid and hydrochloric acid, strong alkaline solutions, enzyme solutions and ionic liquids. For example, the invention patent with patent publication number CN107190341A discloses a regeneration method. The preparation method of collagen fibers uses alkali treatment and enzyme treatment to solubilize insoluble collagen; the invention patent application with patent publication number CN111501121A discloses a method of preparing collagen fibers by wet spinning, using sodium acetate/ Acetate buffer solution dissolves collagen. The above methods will cause the aggregated structure of natural collagen, that is, the collagen microfibers are destroyed during the dissolution process, resulting in the loss of the original excellent properties of collagen. The obtained collagen filaments have unsatisfactory mechanical properties, low thermal stability, and stable structure. Shortcomings such as poor sex. Therefore, how to directly use collagen colloids containing collagen microfiber structures for wet spinning to obtain collagen filaments and improve their properties, ensure their application value and expand their application scope are the main directions for future research and development.

Contents of the invention

The purpose of the present invention is to solve the above-mentioned defects existing in the existing collagen fiber production process, and propose a preparation method of collagen filaments that can retain the collagen microfiber structure. The length of the prepared collagen filaments is controllable and retains The microfiber structure maximizes the excellent properties of natural collagen and can be used in the textile and medical fields.

The technical solution of the present invention: a collagen filament with a collagen microfiber structure, with a diameter of 30~60 μm, in which the collagen microfibers in the collagen filaments are oriented along the long axis, and the diameter of the collagen microfibers is 80~120 μm. nm.

The specific steps for preparing the collagen filament are as follows:

(1) Disperse the collagen colloid extracted from cowhide in deionized water, add a water-soluble cross-linking agent, and stir continuously at room temperature until uniformly dispersed to obtain a collagen colloid solution with a solution concentration of 10 mg/mL~30 mg/mL; where The water-soluble cross-linking agent is one of glutaraldehyde, genipin or EDC/NHS mass ratio 2:1 compound agent, preferably glutaraldehyde, with a concentration of 0.01% to 0.5%.

(2) Filter and centrifuge the collagen colloid solution prepared in step (1), and let it stand for aging for 1 to 3 days, preferably 3 days, to obtain a uniform collagen colloid spinning solution;

(3) Extrude the collagen colloid spinning solution prepared in step (2) on a wet spinning device, and obtain collagen filaments after drying; the wet spinning device includes a propelling pump, a spinneret, a coagulation Bath and winding device; wherein the propelling pump extrudes the collagen colloid spinning solution from the spinneret to obtain a spinning stream. The spinning stream is solidified in the coagulation bath and collected by the winding device to complete the extrusion molding operation. .

Further, the diameter of the spinneret is 0.36~0.41 mm, preferably 0.41 mm; the extrusion speed of the spinning fine stream extruded from the spinneret is 0.25~0.45 m/min, preferably 0.45 m/min; The winding speed is 0.6~1 m/min.

Further, the coagulation bath is a sodium hydroxide aqueous solution of PEG 8000-20000, preferably PEG-20000; the pH is 10~13.5, preferably 13.5; wherein the mass concentration of PEG is 15%~25%. The coagulation bath temperature is 20~30°C, preferably 25°C.

Compared with the prior art, the advantages of the present invention are:

(1) Collagen filaments containing a collagen microfiber structure were prepared, retaining the excellent properties of natural collagen as much as possible. The collagen microfibers were oriented along the axis of the collagen filaments, improving their mechanical properties;

(2) Deionized water is used as the collagen colloid diluent, no organic solvent is used, it is green, environmentally friendly and low-cost, and has absolute advantages for industrial production;

(3) The preparation method of the present invention has simple equipment, easy operation, and mild conditions. It can quickly prepare fibers of different diameters and different lengths, has high production efficiency, and the prepared fibers have good biocompatibility and mechanical properties, which greatly expands the Application fields of collagen filaments.

(4) The breaking strength of the collagen filament prepared by the present invention can reach 1.52 cN/dtex, and the breaking elongation is 10~17%. It meets the requirements for mechanical properties of textile materials and can be used in the textile field.

Description of the drawings

Figure 1 is a scanning electron microscope image of the surface and cross-sectional microfiber arrangement of the collagen filaments prepared in the present invention.

Figure 2 is a graph showing the mechanical properties of collagen filaments prepared in the present invention.

Figure 3 is a chart of spinning process parameters and fiber properties of each embodiment.

Detailed ways

The technical solution of the present invention will be further described below based on examples. In the description of this specification, the content of each embodiment means that the specific technical features described in conjunction with it are included in at least one embodiment of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific technical features described may be combined in a suitable manner in any one or more embodiments or examples.

Example 1

Disperse the collagen colloid extracted from cowhide in deionized water, add 0.1% glutaraldehyde, and stir continuously at room temperature until uniformly dispersed to obtain a collagen colloid solution, in which the concentration of the collagen colloid solution is 14 mg/mL.

The above-mentioned collagen colloid solution is filtered and centrifugally defoamed, and then left to stand for aging for 3 days to obtain a uniform collagen colloid spinning solution;

The above-mentioned spinning stock solution is extruded on the wet spinning device, and the spinning stock solution is extruded from the needle through a syringe pump at a speed of 0.45 m/min, and enters the pH of 20% PEG-20000 solution as the coagulant. After solidification in a coagulation bath at a temperature of about 13.5, the formed fibers are wound and collected at a speed of 1 m/min and dried naturally to obtain collagen filaments. The needle diameter is 0.41mm, and the coagulation bath temperature is 25°C.

Field emission scanning electron microscopy was used to characterize the surface and internal microfibers of collagen filaments, and it was found that the internal microfibril structure of collagen filaments was relatively intact and oriented uniformly along the long axis; a monofilament yarn strength meter was used to test the obtained collagen filaments. Mechanical properties were tested and the breaking strength of collagen filament was 1.52 cN/dtex and the elongation at break was 12%. The scanning electron micrograph of the surface and cross-sectional microfiber arrangement of the prepared collagen filaments is shown in Figure 1, and the mechanical properties diagram is shown in Figure 2.

Example 2

Disperse the collagen colloid extracted from cowhide in deionized water, add 0.1% glutaraldehyde, and stir continuously at room temperature until uniformly dispersed to obtain a collagen colloid solution, in which the concentration of the collagen colloid solution is 14 mg/mL.

The above-mentioned collagen colloid solution is filtered and centrifugally defoamed, and then left to stand for aging for 3 days to obtain a uniform collagen colloid spinning solution;

The above-mentioned spinning stock solution is extruded on the wet spinning device, and the spinning stock solution is extruded from the needle through a syringe pump at a speed of 0.45 m/min, and enters the pH of 20% PEG-20000 solution as the coagulant. After solidification in a coagulation bath at a temperature of about 13.5, the formed fibers are wound, collected, and naturally dried at a speed of 0.8 m/min to obtain collagen filaments. The needle diameter is 0.41 mm, and the coagulation bath temperature is 25°C. The collagen filaments obtained by the above method were characterized and tested, and it was found that the filaments had a relatively complete microfiber structure and good mechanical properties.

Example 3

Disperse the collagen colloid extracted from cowhide in deionized water, add 0.25% glutaraldehyde, and stir continuously at room temperature until uniformly dispersed to obtain a collagen colloid solution, in which the concentration of the collagen colloid solution is 14 mg/mL.

The above-mentioned collagen colloid solution is filtered and centrifugally defoamed, and then left to stand for aging for 3 days to obtain a uniform collagen colloid spinning solution;

The above-mentioned spinning stock solution is extruded on the wet spinning device, and the spinning stock solution is extruded from the needle through a syringe pump at a speed of 0.45 m/min, and enters a pH of 20% PEG-20000 solution as the coagulant. The fibers are coagulated in a coagulation bath at a temperature of about 13.5 m/min, and the formed fibers are wound and collected at a speed of 0.6 m/min and dried naturally to obtain collagen filaments. The needle diameter is 0.41 mm, and the coagulation bath temperature is 25°C. The collagen filaments obtained by the above method were characterized and tested, and it was found that the filaments had a relatively complete microfiber structure and good mechanical properties.

Example 4

Disperse the collagen colloid extracted from cowhide in deionized water, add 0.1% glutaraldehyde, and stir continuously at room temperature until uniformly dispersed to obtain a collagen colloid solution, in which the concentration of the collagen colloid solution is 16 mg/mL.

The above-mentioned collagen colloid solution is filtered and centrifugally defoamed, and then left to stand for aging for 3 days to obtain a uniform collagen colloid spinning solution;

The above-mentioned spinning stock solution is extruded on the wet spinning device, and the spinning stock solution is extruded from the needle through a syringe pump at a speed of 0.45 m/min, and enters the pH of 15% PEG-20000 solution as the coagulant. After solidification in a coagulation bath at a temperature of about 13.5, the formed fibers are wound and collected at a speed of 1 m/min and dried naturally to obtain collagen filaments. The needle diameter is 0.41 mm, and the coagulation bath temperature is 25°C. The collagen filaments obtained by the above method were characterized and tested, and it was found that the filaments had a relatively complete microfiber structure and good mechanical properties.

Example 5

Disperse the collagen colloid extracted from cowhide in deionized water, add 0.05% glutaraldehyde, and stir continuously at room temperature until uniformly dispersed to obtain a collagen colloid solution, in which the concentration of the collagen colloid solution is 16 mg/mL.

The above-mentioned collagen colloid solution is filtered and centrifugally defoamed, and then left to stand for aging for 3 days to obtain a uniform collagen colloid spinning solution;

The above-mentioned spinning stock solution is extruded on the wet spinning device, and the spinning stock solution is extruded from the needle through a syringe pump at a speed of 0.45 m/min, and enters the pH of 15% PEG-20000 solution as the coagulant. After coagulation in a coagulation bath for about 12 seconds, the formed fibers are wound and collected at a speed of 1 m/min and dried naturally to obtain collagen filaments. The needle diameter is 0.41 mm, and the coagulation bath temperature is 25°C. The collagen filaments obtained by the above method were characterized and tested, and it was found that the filaments had a relatively complete microfiber structure and good mechanical properties. The spinning process parameters and fiber properties of each of the above embodiments are shown in Figure 3.

It is obvious to those skilled in the art that the present invention is not limited to the details of the above-described exemplary embodiments, and that the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, the embodiments should be regarded as illustrative and non-restrictive from any point of view, and the scope of the present invention is defined by the appended claims rather than the above description, and it is therefore intended that all claims falling within the claims All changes within the meaning and scope of equivalent elements are included in the present invention. Any reference signs in a claim shall not be construed as limiting the claim in question.

In addition, it should be understood that although this specification is described in terms of implementations, not each implementation only contains an independent technical solution. This description of the specification is only for the sake of clarity, and those skilled in the art should take the specification as a whole. , the technical solutions in each embodiment can also be appropriately combined to form other implementations that can be understood by those skilled in the art.

Claims (2)

1. A method for preparing collagen filaments with a collagen microfiber structure, characterized in that the method specifically includes the following steps: (1) Disperse the collagen colloid extracted from cowhide in deionized water, add a water-soluble cross-linking agent, and stir continuously at room temperature until uniformly dispersed to obtain a collagen colloid solution; (2) Filter and centrifuge the collagen colloid solution prepared in step (1), and then let it stand for aging to obtain a uniform collagen colloid spinning solution; (3) Extrude the collagen colloid spinning solution prepared in step (2) on a wet spinning device, and obtain collagen filaments after drying; The concentration of the collagen colloid solution in step (1) is 10 mg/mL~30 mg/mL; The water-soluble cross-linking agent in step (1) is one of glutaraldehyde, genipin or EDC/NHS mass ratio 2:1 compound agent; the mass concentration of the water-soluble cross-linking agent is 0.01%~0.5% ; The standing aging time in step (2) is 1 to 3 days; The wet spinning device in step (3) includes a propelling pump, a spinneret, a coagulation bath and a winding device; wherein the propelling pump extrudes the collagen colloid spinning solution from the spinneret to obtain a spinning stream. The filament flow is solidified in the coagulation bath and collected by the winding device to complete the extrusion molding operation; The diameter of the spinneret is 0.36~0.41 mm; The coagulation bath is a sodium hydroxide aqueous solution of PEG 8000-20000, with a pH of 10-13.5; the mass concentration of PEG is 15%-25%; The coagulation bath temperature is 20~30°C; The extrusion speed of the spinning fine stream extruded from the spinneret is 0.25~0.45 m/min, and the winding speed is 0.6~1 m/min. 2. A collagen filament with a collagen microfiber structure prepared by the preparation method as claimed in claim 1, characterized in that: the diameter of the collagen filament is 30~60 μm, and the collagen filament has a diameter of 30 to 60 μm. The collagen microfibers are oriented along the long axis, and the diameter of the collagen microfibers is 80~120 nm.