A collagen-tamarind gum composite fiber and its preparation method

Abstract

This invention provides a collagen-tamarind gum composite fiber and its preparation method, belonging to the field of composite fiber technology. The invention involves swelling a collagen stock solution to obtain a collagen dispersion, adding tamarind gum and a crosslinking agent to prepare a collagen-tamarind gum dispersion; then degassing the collagen-tamarind gum dispersion to obtain a collagen-tamarind gum spinning solution; finally, the collagen-tamarind gum spinning solution is wet-spun and extruded into a first coagulation bath, followed by traction, a second coagulation bath, and stretching to obtain collagen-tamarind gum composite fibers. In the collagen-tamarind gum composite fiber of this invention, tamarind gum and collagen molecular chains form an interpenetrating network structure and hydrogen bonds, effectively enhancing the mechanical properties of the collagen fiber. The breaking strength of the collagen-tamarind gum composite fiber is greater than 1.5 cN / dtex, meeting the application requirements of many fields.

Description

Technical Field

[0001] This invention relates to the field of composite fiber technology, and in particular to a collagen-tamarind gum composite fiber and its preparation method. Background Technology

[0002] Collagen is a natural protein widely found in connective tissues such as skin, bone, cartilage, teeth, tendons, ligaments, and blood vessels in animals, serving as a major structural protein in these tissues. Based on differences in structure and function, collagen can be classified into several types, with type I collagen being the most common, accounting for approximately 80%–90% of all collagen content. Collagen possesses excellent biocompatibility, biodegradability, and bioactivity, and has broad application prospects.

[0003] Currently, the development of collagen spinning technology faces two major challenges: first, the spinnability of simply formulated collagen spinning solutions is poor, making it difficult to form continuous filaments, which affects the smooth progress of the spinning process and product quality; second, the resulting fibers have low crystallinity, insufficient strength, and are easily brittle, limiting their practicality. To address these issues, researchers have attempted to blend collagen with other materials (such as chitosan, polyvinyl alcohol, and polyacrylonitrile), but these composite fibers have shortcomings in terms of biocompatibility. Meanwhile, the mainstream process for preparing collagen filaments uses solvents (such as fluoroalcohols like hexafluoroisopropanol) to dissolve collagen before wet spinning, but this destroys the aggregated structure of natural collagen, resulting in poor fiber mechanical properties, thermal stability, and structural stability. Therefore, how to improve spinning efficiency and fiber quality while maintaining collagen properties has become a key issue that urgently needs to be addressed in current research. Summary of the Invention

[0004] The purpose of this invention is to provide a collagen-tamarind gum composite fiber and its preparation method, so as to solve the problems of insufficient biocompatibility and poor mechanical properties of collagen composite fibers in the prior art.

[0005] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0006] This invention provides a method for preparing collagen-tamarind gum composite fibers, comprising the following steps:

[0007] S1: Swell the collagen stock solution to obtain a collagen dispersion, add tamarind gum and crosslinking agent to prepare a collagen-tamarind gum dispersion;

[0008] S2: Defoaming treatment is performed on the collagen-tamarind gum dispersion to obtain collagen-tamarind gum spinning solution;

[0009] S3: The collagen-tamarind gum spinning solution is wet-spun and extruded into the first coagulation bath. After traction, second coagulation bath and stretching, collagen-tamarind gum composite fiber is obtained.

[0010] Preferably, in step S1, the concentration of collagen in the collagen dispersion is 1-3 wt%.

[0011] Preferably, in step S1, the swelling is carried out in an acidic solution, wherein the acidic solution contains hydrochloric acid solution or acetic acid solution.

[0012] Preferably, in step S1, after adding tamarind gum and crosslinking agent, the mixture is stirred in an ice-water bath for 3-6 hours to prepare a collagen-tamarind gum dispersion; the amount of tamarind gum added is 5-30% based on the mass of collagen in the collagen dispersion, and the amount of crosslinking agent added is 0.03-0.1%; the crosslinking agent includes glutaraldehyde, genipin, or 1-ethyl-(3-dimethylaminopropyl)carbodiimide / N-hydroxysuccinimide.

[0013] Preferably, in step S3, the process parameters for wet spinning are: extrusion pressure of 0.3-0.5 MPa, extrusion speed of 0.3-0.6 mL / min, spinning temperature of 10-30℃, and spinning speed of 0.6-2 m / min.

[0014] Preferably, in step S3, the first coagulation bath is a polyethylene glycol solution with a concentration of 10-25 wt% and a pH value of 9-13; the second coagulation bath is an inorganic salt solution with a concentration of 20-50 wt%.

[0015] Preferably, the polyethylene glycol in the polyethylene glycol solution comprises one or more of PEG4000, PEG8000, PEG10000 and PEG20000; and the inorganic salt in the inorganic salt solution comprises sodium salt, potassium salt or ammonium salt.

[0016] Preferably, in step S3, the stretching ratio is 1.3 to 1.5:1.

[0017] The present invention also provides a collagen-tamarind composite fiber prepared by the above-described method.

[0018] Preferably, the collagen-tamarind composite fiber has a tensile strength of 1.5 to 2.5 cN / dtex.

[0019] The beneficial effects of this invention are:

[0020] (1) The present invention uses collagen and tamarind gum as raw materials to prepare collagen-tamarind gum composite fiber. The added tamarind gum can form an interpenetrating network structure with the collagen molecular chain and form hydrogen bonds, which can effectively enhance the mechanical properties of collagen fiber. The breaking strength of collagen-tamarind gum composite fiber is greater than 1.5 cN / dtex, which meets the application requirements of many fields.

[0021] (2) The preparation method of collagen-tamarind composite fiber provided by the present invention is simple, easy to operate, mild in preparation conditions, and has high production efficiency. It can design collagen fibers of different diameters according to application requirements and can realize large-scale production.

[0022] (3) The present invention avoids the use of organic solvents in the preparation of collagen-tamarind composite fiber, and the production process conforms to the concept of green environmental protection. Attached Figure Description

[0023] Figure 1 This is a schematic diagram of the interpenetrating network structure of the collagen-tamarind composite fiber of the present invention;

[0024] Figure 2 This is a scanning electron microscope image of the collagen-tamarind gum composite fiber from Example 1;

[0025] Figure 3 The diagram shows the mechanical properties of the collagen-tamarind composite fiber from Example 1. Detailed Implementation

[0026] This invention provides a method for preparing collagen-tamarind gum composite fibers, comprising the following steps:

[0027] S1: Swell the collagen stock solution to obtain a collagen dispersion, add tamarind gum and crosslinking agent to prepare a collagen-tamarind gum dispersion;

[0028] S2: Defoaming treatment is performed on the collagen-tamarind gum dispersion to obtain collagen-tamarind gum spinning solution;

[0029] S3: The collagen-tamarind gum spinning solution is wet-spun and extruded into the first coagulation bath. After traction, second coagulation bath and stretching, collagen-tamarind gum composite fiber is obtained.

[0030] In this invention, it is preferred to extract collagen before preparing collagen stock solution. The collagen extraction method is as follows: soak the collagen raw material in an alkaline solution, wash it after soaking, and finally put it in a high-speed blender with ice water and stir evenly to obtain collagen.

[0031] In this invention, the concentration of the alkaline solution is 5-15 wt%; the soaking time is 6-10 h; and the cleaning is preferably performed using deionized water.

[0032] In this invention, the collagen raw material comprises bovine hide, bovine tendon, or bovine ligament.

[0033] In this invention, in step S1, the concentration of collagen in the collagen dispersion is 1-3 wt%, preferably 1.5-2.5 wt%.

[0034] In this invention, in step S1, swelling is carried out in an acidic solution, wherein the acidic solution contains hydrochloric acid solution or acetic acid solution, and the pH value of the acidic solution is 2 to 3.

[0035] In this invention, in step S1, after adding tamarind gum and a crosslinking agent, the mixture is stirred in an ice-water bath for 3-6 hours to prepare a collagen-tamarind gum dispersion; based on the mass of collagen in the collagen dispersion, the amount of tamarind gum added is 5-30%, preferably 10-20%; the amount of crosslinking agent added is 0.03-0.1%, preferably 0.04-0.09%, and more preferably 0.06%.

[0036] In this invention, the crosslinking agent comprises glutaraldehyde, genipin, or 1-ethyl-(3-dimethylaminopropyl)carbodiimide (EDC) / N-hydroxysuccinimide (NHS), preferably glutaraldehyde or genipin.

[0037] In this invention, the collagen-tamarind gum dispersion is preferably filtered before degassing treatment to remove insoluble or poorly soluble substances from the dispersion.

[0038] In this invention, the process parameters for wet spinning in step S3 are: extrusion pressure of 0.3-0.5 MPa, extrusion speed of 0.3-0.6 mL / min, spinning temperature of 10-30℃, and spinning speed of 0.6-2 m / min.

[0039] In this invention, in step S3, the first coagulation bath is a polyethylene glycol solution, wherein the concentration of the polyethylene glycol solution is 10-25 wt%, preferably 15-20 wt%, and the pH value is 9-13, preferably 10-12; the second coagulation bath is an inorganic salt solution, wherein the concentration of the inorganic salt solution is 20-50 wt%, preferably 30-40 wt%, and more preferably 30-35 wt%.

[0040] In this invention, the collagen-tamarind gum spinning solution is injected into an alkaline coagulation bath, where it immediately coagulates to form nascent fibers. During the fiber drawing process, a bidirectional diffusion phenomenon occurs between the nascent fibers and the coagulation bath: water inside the fiber diffuses into the solution, while solutes in the solution penetrate into the fiber. This process promotes the gradual coagulation and shaping of the nascent fibers. When using a polyethylene glycol solution, due to its polymer nature and viscosity, it provides appropriate resistance, allowing the nascent fibers to be stretched to a certain extent, which is beneficial for fiber formation. The inorganic salt solution exhibits strong coagulation efficiency, ensuring complete coagulation of the nascent fibers and effectively preventing the possible problems of tangling and adhesion of the collagen-tamarind gum composite fibers during collection. The subsequent multi-stage washing bath ensures that the coagulation bath is thoroughly cleaned from the nascent fibers, while the high-concentration ethanol solution helps remove moisture.

[0041] In this invention, the polyethylene glycol in the polyethylene glycol solution comprises one or more of PEG4000, PEG8000, PEG10000 and PEG20000, preferably one or more of PEG8000, PEG10000 and PEG20000, and more preferably PEG8000; the inorganic salt in the inorganic salt solution comprises sodium salt, potassium salt or ammonium salt.

[0042] In this invention, the sodium salt comprises sodium chloride, sodium sulfate, sodium carbonate, or sodium nitrate; the potassium salt is preferably potassium chloride, potassium sulfate, potassium carbonate, or potassium nitrate; and the ammonium salt is ammonium chloride, ammonium sulfate, ammonium carbonate, or ammonium nitrate.

[0043] In this invention, the stretching process preferably involves a water bath, which comprises four sections: water, 30% ethanol solution, 60% ethanol solution, and 90% ethanol solution.

[0044] In this invention, during step S3, the stretching ratio is 1.3 to 1.5:1, preferably 1.3:1.

[0045] The present invention also provides a collagen-tamarind composite fiber prepared by the above-described method.

[0046] In this invention, the tensile strength of the collagen-tamarind composite fiber is 1.5 to 2.5 cN / dtex.

[0047] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0048] The collagen extraction method used in this embodiment of the invention is as follows: Bovine hide is soaked in a 5wt% NaOH solution to remove fat from the collagen raw material for 6 hours; the collagen raw material after fat removal is taken out, the sodium hydroxide solution is removed with deionized water, and then placed in a blender, ice water is added and stirred evenly to obtain an 8wt% bovine collagen stock solution for later use.

[0049] Example 1

[0050] Bovine collagen stock solution was fully swollen in hydrochloric acid solution (pH 2) to prepare a collagen dispersion with a concentration of 1.5 wt% and pH 2. Tamarind gum (10%) and glutaraldehyde crosslinking agent (0.03%) were added, and the mixture was stirred in an ice-water bath for 6 hours to obtain a collagen-tamarind gum dispersion. The dispersion was then filtered and centrifuged at 8000 rpm for 10 minutes to obtain a collagen-tamarind gum spinning solution.

[0051] Collagen-tamarind gum spinning solution was extruded through a wet spinning device (with a spinneret orifice diameter of 0.2 mm, an aspect ratio of 60, an extrusion pressure of 0.4 MPa, an extrusion speed of 0.5 mL / min, a spinning temperature of 20 °C, and a spinning speed of 1.0 m / min) into a PEG8000 solution (concentration of 20 wt%, pH = 12). After being drawn into a 30 wt% ammonium sulfate solution, the solution was washed sequentially with deionized water, 30% ethanol solution, 60% ethanol solution, and 90% ethanol solution. Finally, the solution was stretched at a stretch ratio of 1.3:1 and dried at 40 °C to obtain collagen-tamarind gum composite fibers.

[0052] Example 2

[0053] The difference from Example 1 is that the amount of tamarind gum added is 20%, while all other conditions are the same.

[0054] Example 3

[0055] Bovine collagen stock solution was fully swollen in hydrochloric acid solution (pH 2) to prepare a collagen dispersion with a concentration of 2.0 wt% and pH 2. Tamarind gum (20%) and glutaraldehyde crosslinking agent (0.06%) were added, and the mixture was stirred in an ice-water bath for 6 hours to obtain a collagen-tamarind gum dispersion. The dispersion was then filtered and centrifuged at 8000 rpm for 10 minutes to obtain a collagen-tamarind gum spinning solution.

[0056] Collagen-tamarind gum spinning solution was extruded through a wet spinning device (with a spinneret orifice diameter of 0.2 mm, an aspect ratio of 60, an extrusion pressure of 0.4 MPa, an extrusion speed of 0.5 mL / min, a spinning temperature of 20 °C, and a spinning speed of 1.0 m / min) into a PEG8000 solution (concentration of 20 wt%, pH = 12). After being drawn into a 30 wt% ammonium sulfate solution, the solution was washed sequentially with deionized water, 30% ethanol solution, 60% ethanol solution, and 90% ethanol solution. Finally, the solution was stretched at a stretch ratio of 1.3:1 and dried at 40 °C to obtain collagen-tamarind gum composite fibers.

[0057] Example 4

[0058] The difference from Example 3 is that the collagen concentration in the collagen dispersion is 2.5 wt%, the amount of crosslinking agent glutaraldehyde added is 0.09%, and all other conditions are the same.

[0059] Example 5

[0060] The difference from Example 3 is that the crosslinking agent is genipin, and the amount of genipin added is 0.06%, while all other conditions are the same.

[0061] Example 6

[0062] The difference from Example 3 is that the concentration of the PEG8000 solution is 15 wt%, while all other conditions are the same.

[0063] Example 7

[0064] The difference from Example 3 is that the concentration of the ammonium sulfate solution is 35 wt%, while all other conditions are the same.

[0065] Example 8

[0066] The difference from Example 3 is that the stretching ratio is 1.5:1, while all other conditions are the same.

[0067] Comparative Example 1

[0068] Bovine collagen stock solution was placed in hydrochloric acid solution (pH 2) for full swelling to prepare a collagen dispersion with a concentration of 1.5 wt% and pH 2. Glutaraldehyde crosslinking agent (addition amount of 0.03%) was added, and the mixture was stirred for 6 hours under ice-water bath conditions to obtain the collagen dispersion. The dispersion was then filtered through a filtration device and centrifuged at 8000 rpm for 10 minutes to obtain the collagen spinning solution.

[0069] Collagen spinning solution was extruded through a wet spinning device (with a spinneret orifice diameter of 0.2 mm, an aspect ratio of 60, an extrusion pressure of 0.4 MPa, an extrusion speed of 0.5 mL / min, a spinning temperature of 20 °C, and a spinning speed of 1.0 m / min) into a PEG8000 solution (concentration of 20 wt%, pH = 12). After being drawn into a 30 wt% ammonium sulfate solution, it was washed sequentially with deionized water, 30% ethanol solution, 60% ethanol solution, and 90% ethanol solution. Finally, it was stretched at a stretch ratio of 1.3:1 and dried at 40 °C to obtain collagen fibers.

[0070] Performance testing: The mechanical properties of the collagen-tamarind composite fibers prepared in Examples 1-8 and the collagen fiber of Comparative Example 1 were tested using a multifilament yarn strength tester. The test method was as follows: the mechanical properties of the fibers were tested using a multifilament strength tester (multifilament A0-3000cN), with a clamping distance of 200mm, a tensile speed of 250mm / min, and a pre-tension of 5cN. Ten sets of valid data were obtained and the average value was taken. The test results are shown in Table 1.

[0071] Table 1. Spinning process parameters and composite fiber performance test results of Examples 1-8 and Comparative Example 1

[0072]

[0073] As can be seen from Table 1, the addition of tamarind gum can effectively enhance the mechanical properties of collagen fibers, and the breaking strength of collagen-tamarind gum composite fibers is greater than 1.5 cN / dtex.

[0074] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing collagen-tamarind gum composite fibers, characterized in that, Includes the following steps: S1: Swell the collagen stock solution to obtain a collagen dispersion, add tamarind gum and crosslinking agent to prepare a collagen-tamarind gum dispersion; S2: Defoaming treatment is performed on the collagen-tamarind gum dispersion to obtain collagen-tamarind gum spinning solution; S3: The collagen-tamarind gum spinning solution is wet-spun and extruded into the first coagulation bath. After traction, second coagulation bath and stretching, collagen-tamarind gum composite fiber is obtained. The amount of tamarind gum added is 5-30% based on the mass of collagen in the collagen dispersion, and the amount of crosslinking agent added is 0.03-0.1%. In step S3, the first coagulation bath is a polyethylene glycol solution with a concentration of 10-25 wt% and a pH value of 9-13; the second coagulation bath is an inorganic salt solution with a concentration of 20-50 wt%.

2. The method for preparing collagen-tamarind gum composite fiber according to claim 1, characterized in that, In step S1, the concentration of collagen in the collagen dispersion is 1-3 wt%.

3. The method for preparing collagen-tamarind gum composite fiber according to claim 1 or 2, characterized in that, In step S1, swelling is carried out in an acidic solution, wherein the acidic solution contains hydrochloric acid solution or acetic acid solution.

4. The method for preparing collagen-tamarind gum composite fiber according to claim 3, characterized in that, In step S1, after adding tamarind gum and crosslinking agent, a collagen-tamarind gum dispersion is prepared by stirring in an ice-water bath for 3-6 hours; the crosslinking agent includes glutaraldehyde, genipin or 1-ethyl-(3-dimethylaminopropyl)carbodiimide / N-hydroxysuccinimide.

5. The method for preparing collagen-tamarind gum composite fiber according to claim 1, 2, or 4, characterized in that, In step S3, the process parameters for wet spinning are: extrusion pressure of 0.3-0.5 MPa, extrusion speed of 0.3-0.6 mL / min, spinning temperature of 10-30℃, and spinning speed of 0.6-2 m / min.

6. The method for preparing collagen-tamarind gum composite fiber according to claim 5, characterized in that, The polyethylene glycol in the polyethylene glycol solution contains one or more of PEG4000, PEG8000, PEG10000, and PEG20000; the inorganic salt in the inorganic salt solution contains sodium salt, potassium salt, or ammonium salt.

7. The method for preparing collagen-tamarind gum composite fiber according to claim 4 or 6, characterized in that, In step S3, the stretching ratio is 1.3 to 1.5:

1.

8. Collagen-tamarind composite fiber prepared by the method of any one of claims 1 to 7.

9. The collagen-tamarind composite fiber according to claim 8, characterized in that, The tensile strength of the collagen-tamarind composite fiber is 1.5 to 2.5 cN / dtex.

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