CN103173893A - Method for producing polymer fiber and polymer fiber thereof - Google Patents

Abstract

The invention provides a method for manufacturing polymer fiber and polymer fiber thereof, the method for manufacturing polymer fiber comprises the following steps: carrying out wet spinning on an aqueous spinning solution containing a natural polymer material and a spinning forming solution to form wet polymer precursor; immersing the wet-type polymer precursor into a softening agent to obtain wet-type polymer precursor treated by the softening agent; immersing the wet polymer protofilament treated by the softening agent into a volatile solvent to remove water in the polymer protofilament to form a polymer fiber. The invention also provides the polymer fiber prepared by the preparation method.

Description

Manufacturing method of polymer fiber and polymer fiber thereof

This application is a divisional application of Chinese Patent Application No. 201010198575.0 with an application date of June 4, 2010, entitled "Manufacturing Method of Polymer Fiber and Wound Dressing and Obtained Wound Dressing".

technical field

The present invention relates to a method for producing polymer fibers and the polymer fibers obtained by the aforementioned method.

Background technique

Most of the currently used wound dressings are based on hydrogel, film or sponge-like structural materials. Although these dressings have been used in the market for a long period of time, the application of these materials is limited due to problems such as mechanical strength, liquid absorption capacity and liquid absorption speed. According to the research of past scholars, the most common three-dimensional configurations are sponge and non-woven fabrics, and the permeability and water absorption of non-woven fabrics are better than those of sponges. Moreover, the non-woven configuration has a better three-dimensional structure, so that cells can have better space adsorption and cell proliferation functions. In addition, the non-woven structure has good flexibility and certain mechanical strength, and the continuous process of textile technology can reduce its manufacturing cost, and produce high-quality and cheap medical-grade dressing materials.

Common wound dressings are made of natural regenerated polymer fibers. Wound dressings are generally made by wet spinning technology, and freeze drying technology is used to dry the fibers. However, the freeze-drying process is time-consuming and energy-intensive; and in the non-woven fabric process, if the hydroforming technology is used, another time-consuming and energy-consuming freeze-drying process is required, while the needle-punching technology requires additional needle-punch machines. Therefore, it is time-consuming and time-consuming to manufacture natural regenerated polymer fibers or non-woven fibers as wound dressings by traditional methods and requires expensive equipment.

Contents of the invention

In order to overcome the problems of fibers or non-woven fabrics used in the manufacture of wound dressings in the prior art, the present invention provides a method for manufacturing wound dressings, which replaces freeze-drying with different drying methods, which not only shortens the process time but also reduces energy consumption.

Therefore, at first the present invention provides a kind of manufacture method of polymer fiber, it is characterized in that comprising the following steps:

(i) Wet spinning the aqueous spinning dope (aqueous dope) containing natural polymer materials and spinning forming solution to form a wet polymer precursor, wherein the natural polymer materials are chitosan, alginate, or a combination of them;

(ii) immersing the wet polymer precursor in a softener to obtain a softener-treated wet polymer precursor;

(iii) immersing the softener-treated wet polymer precursors in a volatile solvent to remove moisture from the polymer precursors to form polymer fibers, wherein the dehydrated wet polymer precursors do not have to pass through Freeze drying to remove water.

In a specific example, the aqueous spinning solution containing natural polymer materials is a chitosan solution with a concentration between 3 and 10% by weight (w/w%), and the spinning forming solution is alkaline , whose concentration is between 3 and 10% by weight.

In a specific example, the aqueous spinning stock solution containing natural polymer materials is a sodium alginate solution with a concentration between 3 and 10% by weight; and the spinning forming solution contains divalent cations, and its concentration is between 3 to 10% by weight.

In a specific example, the softening agent has a concentration of 0.1 to 25% by weight.

In a specific example, the softener is a glycerin solution with a concentration of 0.1 to 25% by weight or a polysorbate solution with a concentration of 0.1 to 10% by weight.

In a specific example, the volatile solvent is a lower alcohol, a lower ketone or a lower ether.

The present invention further provides a polymer fiber prepared by the aforementioned method.

According to the method of the present invention, natural polymer materials such as chitosan, alginate or a combination thereof can be made into polymer fibers without complicated drying steps, and the polymer fibers prepared by this method can be used for wounds Application of dressing.

Description of drawings

Figure 1 is a comparison of the coagulation test results of the commercially available dressing and the dressing of the comparative example.

Fig. 2 is a comparison of the coagulation test results of the dressing obtained by the method of the present invention and the dressing of the comparative example.

Detailed ways

A kind of manufacture method of polymer fiber is characterized in that comprising the following steps:

(i) wet-spinning the water-based spinning stock solution containing the natural polymer material and the spinning forming solution to form a wet polymer precursor;

(ii) immersing the wet polymer precursor in a softener to obtain a softener-treated wet polymer precursor;

(iii) immersing the softener-treated wet polymer precursors in a volatile solvent to remove moisture from the polymer precursors to form polymer fibers.

According to the present invention, the natural polymer material can be chitosan, alginate, or a combination thereof.

In a preferred example of the present invention, the aqueous spinning stock solution containing natural polymer materials is a chitosan solution with a concentration between 3 and 10% by weight; and the spinning forming solution is alkaline, and its concentration is between Between 3 and 10% by weight.

In another preferred embodiment of the present invention, the aqueous spinning stock solution containing natural polymer materials is a sodium alginate solution with a concentration between 3 and 10% by weight; and the spinning forming solution contains divalent cations at a concentration of Between 3 and 10% by weight.

According to the present invention, the divalent cations include but are not limited to calcium ions.

According to the present invention, the softening agent can maintain a suitable softness of the wet polymer precursor, and the softening agent has a concentration of 0.1 to 25% by weight.

According to the present invention, the softening agent includes but not limited to glycerin, polysorbate and its derivatives, for example, Tween-20 (Tween-20), Tween-60, Tween-80 and Span-80 (Span-80) 80). Preferably, the softening agent is a glycerin solution with a concentration of 0.1 to 25% by weight or a polysorbate solution with a concentration of 0.1 to 10% by weight.

According to the present invention, the wet polymer precursor treated with the softening agent is immersed in a volatile solvent. The volatile solvent is preferably low carbon number alcohols, low carbon number ketones or low carbon number ethers.

The low carbon number alcohols can be methanol, ethanol, propanol, butanol, pentanol, hexanol. The low carbon number ketones can be C ₁ to C ₆ ketones. The lower carbon number ethers can be C ₂ to C ₆ ethers.

The technical means and related experimental results adopted by the present invention to achieve the desired invention goal are further described below by means of the embodiments of the present invention.

Comparative Example: Manufacturing Chitosan Composite Fibers with Prior Art

Prepare an alkaline forming solution containing at least one alkaline compound. Prepare a 5% by weight chitosan solution, and extrude it into the above-mentioned molding solution for wet spinning to form wet chitosan spinning. Wet chitosan spinning was followed by freeze-drying to obtain chitosan fibers. Take a certain amount of chitosan fibers, cut them into 2 to 3 cm lengths, disperse them in water, and disperse them with a high-speed stirring disperser, then form chitosan fiber non-woven fabrics by water scooping, and finally freeze-dry Remove moisture. In this comparative example, two freeze-drying processes were used successively, each of which took 2 to 3 days for freeze-drying, the production time was lengthy, and a large amount of electricity was required for the operation of the freeze-dryer.

Embodiment 1: manufacture chitosan composite fiber with the method of the present invention

A 5% by weight solution of chitosan (molecular weight about 300k Daltons) was prepared. Prepare an alkaline forming liquid containing at least 5% by weight of sodium hydroxide. The chitosan solution is extruded into the above-mentioned forming liquid for molding, and wet spinning is performed to form wet chitosan spinning. Soak the obtained wet chitosan spinning in 2 vol% Tween-20 for 5 minutes, then immerse in 50 vol%, 60 vol%, and 70 vol% ethanol for 5 minutes each for solvent replacement, then replace with The excess solvent was removed by a suction machine, and then dried in an oven at 60° C. for 2 hours to obtain chitosan composite fibers. The total production time is 4 hours.

Embodiment 2: manufacture sodium alginate composite fiber with the inventive method

Prepare a 5% by weight sodium alginate solution. Prepare a molding liquid containing 5% calcium chloride. The sodium alginate solution is extruded into the above-mentioned molding liquid for forming, and wet spinning is performed to form wet sodium alginate spinning. Soak the obtained wet sodium alginate spinning in 2% by volume of Tween-20 for 5 minutes, then soak in 50% by volume, 60% by volume, and 70% by volume of ethanol for 5 minutes each for solvent replacement, then replace with The excess solvent was removed by a suction machine, and then dried in an oven at 60° C. for 2 hours to obtain sodium alginate composite fibers. The total production time is 4 hours.

Example 3: Preparation of Composite Wound Dressing Using Porous Biomacromolecule Materials

The chitosan composite fiber obtained in Example 1 is cut into short fibers of appropriate length, and fiber processing is carried out with a carding machine, while the chitosan composite fiber cotton web is sprayed with 0.5% seaweed on the take-up roller The sodium alginate solution is sprayed at a rate of 50 milliliters per minute per unit time for fiber bonding and then dried to form a porous biopolymer material containing sodium alginate. When performing this step, the sodium alginate solution can be replaced with various biopolymer solutions, such as collagen, gelatin, hyaluronic acid, etc., to form various porous biopolymer materials.

Then, the obtained porous biopolymer material was removed with a suction machine to remove excess water, and then dried in an oven at 60° C. for 2 hours, and finally a wound dressing with both non-woven and porous composite forms was obtained. This chitosan composite wound dressing was used in the following examples.

Example 4: Basis Weight Test of Composite Wound Dressing Cut the obtained chitosan composite wound dressing into a square with a size of 10cm x 10cm, measure the weight with an electronic balance, record the results of nine samples and take the average, and measure the results As shown in Table 1. After calculation, the average basis weight of the nonwoven fabric is 0.0146g/cm ² , and the basis weight after unit conversion is 146g/m ² .

Table 1 Basis Weight Test Results of Chitosan Composite Wound Dressing (100cm ² )

Embodiment 5: liquid absorption test of composite wound dressing

1. Experimental materials and equipment:

a. The chitosan composite wound dressing obtained by the method of Example 3.

b. Deionized water and different concentrations of physiological saline.

2. Experimental method:

a. Take a composite wound dressing of a certain size and measure the weight on an electronic balance.

b. Soak the weighed composite wound dressing in physiological saline of different concentrations as indicated below for about 8 hours.

c. Take out the composite wound dressing swollen due to soaking in saline, and measure the weight after absorbing liquid with an electronic balance.

d. Calculate the weight difference before and after immersion and the value of the degree of liquid absorption.

The calculation results are shown in Table 2. It can be seen from Table 2 that under the treatment of different concentrations of physiological saline solution, the liquid absorption rate is greater than 100%, and the liquid absorption rate will decrease with the increase of the concentration of the physiological saline solution used.

Table 2 liquid absorption test results

Solution concentration (%) 0 0.25 0.5 1 Liquid absorption rate (%) 707.79 522.03 439.77 402.29

Example 6: Coagulation Test of Composite Wound Dressings

1. Experimental materials and equipment:

a. The chitosan composite wound dressing obtained by the method of Example 3.

b. The chitosan wound dressing obtained by the method of comparative example.

c. Physiological saline.

d. Volunteer whole blood.

e. ELISA (BioAssay Systems QuantiChromTM Hemoglobin Assaykit).

，ConvaTec,USA）作为本实验的控制组。f. Commercially available wound dressings (trade name

, ConvaTec, USA) as the control group in this experiment.

2. Experimental method:

a. Draw whole blood from volunteers, open the lid, shake and oxygenate for 30 minutes.

b. 0.1 g of chitosan wound dressing was mixed with 30 μL of blood, and after mixing for 30, 60, 90 and 120 seconds, the dressing was taken out and shaken in normal saline for 4 minutes.

c. Take out the supernatant and measure the absorbance value at 540nm by ELISA, the reference wavelength is 650nm.

、市售以针轧技术制造的敷料与比较实施例以湿式纺丝制造的创伤敷料的凝血效果比较，比较实施例与市售敷料具有相似的效果。菱形和方形表示市售敷料的结果，三角形表示比较实施例中以湿式纺丝制造的创伤敷料的结果。由图可见，比较实施例使用湿式纺丝获得敷料的凝血效果和市售以针轧技术获得的敷料效果相似。The results of the ELISA experiment are shown in Figure 1 and Figure 2. Figure 1 shows commercially available dressings

1. Comparing the blood coagulation effect of the commercially available dressing made by needle rolling technology and the wound dressing made by wet spinning in the comparative example, the comparative example and the commercially available dressing have similar effects. The diamonds and squares represent the results for commercially available dressings, and the triangles represent the results for the wound dressings produced by wet spinning in Comparative Examples. It can be seen from the figure that the coagulation effect of the dressing obtained by wet spinning in Comparative Example is similar to that of the commercially available dressing obtained by needle rolling technology.

Fig. 2 shows the comparison of the coagulation effect between the dressing of Example 3 of the present invention and the dressing of Comparative Example, the rhombus indicates the result of Comparative Example, and the triangle indicates the result of the wound dressing of Example 3. It can be seen from the figure that compared with the dressing of Comparative Example, the dressing of Example 3 has a better blood coagulation effect.

Embodiment 7: animal healing test of compound wound dressing

1. Experimental materials and equipment:

a. The chitosan composite wound dressing obtained by the method of Example 3.

b. The chitosan wound dressing obtained by the method of comparative example.

c. Rats (wistar rats).

d.Microscope.

2. Experimental method:

a. Anesthesia (0.001mL/g) was administered to the rats by intramuscular injection, and the experiment was carried out after they entered deep anesthesia.

b. Use an electric shaver to shave the hair on both sides of the rat, and then use a hair removal cream to remove the hair completely.

c. Disinfect the experimental site with iodine, and perform two 2cm x 2cm wounds on the back of the rat.

d. The composite wound dressing obtained by the method of the present invention and the dressing of the comparative example were respectively covered on the back wound of the rat.

e. Continuously observe the wound healing situation, measure and record it. The skin and wound healing process were observed, and digital cameras were used to take pictures to record the adhesion between the dressing and the tissue, the amount of wound fluid secretion, the infection of the tissue around the wound, and the size of the wound.

3. Results:

Table 3 shows the results of macroscopic observation of the wound site and measurement of the wound area using the chitosan composite wound dressing obtained by the method of Example 3 and the chitosan wound dressing obtained by the method of Comparative Example.

Table 3 compares the wound healing situation that obtains dressing with embodiment 3 and comparative example

The dressing test results obtained by using Example 3 and Comparative Example are all considered to be good in terms of area restoration. The wound using the dressing of the comparative example has almost recovered to a long scab shape in the third week; the wound using the dressing of the embodiment 3 has recovered to a round wound in the third week. The dressing is easy to remove and does not stick to the wound.

Example 8: Cytotoxicity test of composite wound dressing

1. Experimental materials and equipment:

a. The chitosan composite wound dressing obtained by the method of Example 3.

b. L929 mouse connective tissue cells.

c. Fluorescent electron microscope (The Olympus FSX100Bio Imaging Navigator all-in-one microscope).

2. Experimental method:

This test is based on ANSI/AAMI/ISO10993-5:1999 (named "in vitro toxicity test of medical materials") to evaluate the cytotoxicity (cyctotxicity) of composite wound dressings. The L929 cells cultured in the culture dish were used as the negative control group, the L929 mouse cells were treated with known cytotoxic phenol as the positive control group, and only the PE film was used as the blank control group to compare with the wound dressing of the present invention. experimental group for comparison.

The cells of the negative control group, the blank control group, the positive control group and the experimental group (the chitosan composite wound dressing obtained in Example 3) were collected and stained with trypan blue (trypan blue) to count the number of late-stage cells. The results showed in Table 4. The results in Table 4 show that the number of cells obtained by using the chitosan composite wound dressing of Example 3 is close to the number of the negative control group and the reagent control group, and it will hardly cause the normal mouse fibroblasts to die, so it does not have any Cytotoxicity.

Table 4 Cytotoxicity test results of composite wound dressings

group Average number of cells (cells/mL) negative control group 1.27x10 ⁶ Reagent control group 1.3x10 ⁶ positive control group 1.67x10 ⁴ test group 1.11x10 ⁶

Embodiment 9: Composite wound dressing intradermal irritation test

1. Experimental materials and equipment:

a. The chitosan composite wound dressing obtained by the method of Example 3.

b. Physiological saline.

c. Male New Zealand white rabbits.

2. Experimental method:

a. Prepare samples according to ANSI/AAMI/ISO10993-12:2007 (named "Biological Evaluation of Medical Devices - Part 12: Sample Preparation and Reference Materials"). Physiological saline and cottonseed oil are used as the extraction solution, and the extraction ratio is 6cm ² /mL. The test substances were soaked in the extraction solvent in proportion, placed on a shaker with a rotation speed of 100 rpm, and extracted at a temperature of 37°C for 72 hours. In addition, the extraction solvent was treated under the same conditions without the test substance as a blank control.

b. In this experiment, 2 rabbits were used for the test. 18-24 hours before the test, the hair on the back of the rabbit was removed with an electric clipper, with an area of about 15cm x 10cm. Before the test, the test rabbit's back skin was visually inspected to ensure that there was no damage.

c. During the test, the test substance physiological saline extract was injected intradermally into 5 parts on the left front side of the back of 2 rabbits. At the same time, the blank control solution was intradermally injected into 5 sites on the left rear side of the test rabbit's back as a control. In the same way, the test substance cottonseed oil extract and the blank control solution were intradermally injected on the right side of the back of the test rabbit. The injection volume for each site is 0.2 mL.

d. 24, 48 and 72 hours after the injection, observe and record the erythema and edema at each injection point of the test site and the control site according to the intradermal reaction scoring system (Table 5). Table 6.

Table 5 Scoring system for intradermal reactions

Table 6 Rabbit skin irritation reaction scoring table

From the results in Table 6, it can be seen that the chitosan composite wound dressing obtained according to the method of the present invention has no irritating reaction on animal skin.

Embodiment 10: Composite wound dressing allergy test

1. Experimental materials and equipment:

a. The chitosan composite wound dressing obtained by the method of Example 3.

b. Physiological saline.

c. Male guinea pigs.

2. Experimental method:

a. Prepare samples according to ANSI/AAMI/ISO10993-12:2007. Physiological saline was used as the extraction liquid, and the extraction ratio was 3 cm ² /mL. Extraction process The test substance was soaked in the extraction solvent in proportion, placed on a shaker with a rotation speed of 100rpm, and extracted at 37°C for 72 hours. In addition, the extraction solvent was treated under the same conditions without the test substance as a blank control.

b. Before the test, 15 guinea pigs were randomly assigned to the test group and the control group. Ten guinea pigs and five guinea pigs were used in the test group and the control group respectively.

c. 18 to 24 hours before the test, shave off the coat of all test animals with an electric clipper, with an area of about 5cm x 7cm. Before the test, the test rabbit's back skin was visually inspected to ensure that there was no damage.

d. The day before the test, the prepared extract was intradermally injected in a volume of 0.1 mL to the shaved site on both sides of the shoulder blade of each animal.

e. On the sixth day of the test, the hair of the test site was shaved again, and vaseline containing 10% sodium dodecylsulfonate was applied.

f. On the seventh day of the test, drop 0.5mL of the test substance extract or the blank control solution on gauze about 2cm x 4cm in size, and after making it fully absorbed, apply it to the scapula shaved area of the test group or the control group in a local way. hairy area, and remove the skin patch after 48 hours.

g. After removing the skin patch, observe and score any allergic reactions that may occur at the test site of each animal according to the evaluation criteria in Table 7.

Table 7 Allergy Test (Magnusson-Kligman) Rating Criteria

In the test of 24 hours, 48 hours, and 72 hours after the skin patch was taken off, there was no subcutaneous irritation in guinea pigs. That is to say, the chitosan composite wound dressing obtained according to the present invention has no irritation reaction on animal skin after an allergy test.

The above description is only a preferred embodiment of the present invention, and does not limit the present invention in any form. Although the invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this field , without departing from the scope of the present invention, when the technical content disclosed above can be used to make some changes or modifications to equivalent embodiments of equivalent changes, but all the content that does not depart from the technical solution of the present invention, according to the technical essence of the present invention Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solution of the present invention.

Claims (8)

1. the manufacture method of a macromolecular fibre is characterized in that comprising the following step:

Water-based spinning solution and the spinning moulding liquid that i) will contain natural macromolecular material carry out wet spinning formation one wet type macromolecule precursor, and wherein this natural macromolecular material is spherical chitosan, alginate or their combination;

Ii) this wet type macromolecule precursor is immersed the wet type macromolecule precursor that obtains in softener once the softener processing;

Iii) will be somebody's turn to do to immerse in solvent flashing through the wet type macromolecule precursor that softener is processed and form macromolecular fibre to remove the moisture in this macromolecule spinning, wherein said wet type macromolecule precursor through dewatering needn't be removed moisture through freeze drying.

2. method according to claim 1, wherein this water-based spinning solution that contains natural macromolecular material is the spherical chitosan solution of concentration between 3 to 10 % by weight, and this spinning moulding liquid is alkalescence, its concentration is between 3 to 10 % by weight.

3. method according to claim 1, wherein this water-based spinning solution that contains natural macromolecular material is the sodium alginate soln of concentration between 3 to 10 % by weight; And this spinning moulding liquid contains bivalent cation, and its concentration is between 3 to 10 % by weight.

4. method according to claim 1 and 2, wherein this softer consistency is between 0.1 to 25 % by weight.

5. method according to claim 1 and 2, wherein this softener be concentration between the glycerite between 0.1 to 25 % by weight or concentration the polysorbate ester solution between 0.1 to 10 % by weight.

6. method according to claim 1 and 2, wherein this solvent flashing is low carbon number alcohol, low carbon number ketone or low carbon number ether.

7. method according to claim 5, wherein this solvent flashing is low carbon number alcohol, low carbon number ketone or low carbon number ether.

8. a macromolecular fibre, is characterized in that utilizing the described method of claim 1 to 7 any one to make gained.

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