CN109234849B - Chitosan oligosaccharide medical marine fiber and preparation method thereof - Google Patents
Chitosan oligosaccharide medical marine fiber and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/103—Agents inhibiting growth of microorganisms
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Abstract
本发明公开了一种壳寡糖医用海洋纤维及其制备方法，涉及医用纤维领域，纤维由内外双层结构组成，内层组分为金属离子交联海藻酸纤维，外层组分为壳寡糖‑海藻酸金属络合物，纤维中壳聚糖与海藻酸以重量计比例不低于2:100。制备方法通过湿法纺丝与双比拉伸复合工艺稳定合理，且所得纤维具有良好的生物相容性和抑菌性能。The invention discloses a chitosan oligosaccharide medical marine fiber and a preparation method thereof, and relates to the field of medical fibers. The fiber is composed of an inner and outer double-layer structure, the inner layer component is metal ion cross-linked alginate fiber, and the outer layer component is chitosan oligosaccharide fiber. Sugar-alginic acid metal complex, the ratio of chitosan and alginic acid in the fiber is not less than 2:100 by weight. The preparation method is stable and reasonable through the composite process of wet spinning and double-ratio drawing, and the obtained fibers have good biocompatibility and antibacterial properties.
Description
Technical Field
The invention relates to the field of medical fibers, in particular to chitosan oligosaccharide medical marine fiber and a preparation method thereof.
Background
Chitosan was originally prepared from chitin extracted from shells of marine animals such as shrimp and crab shells, and is named as such. Chitosan is a polysaccharide polymer obtained by deacetylation of chitin. However, conventional chitosan is difficult to dissolve in a solvent, and thus is difficult to industrially process. The existing chitosan composite fiber spinning is implemented by adopting a high-voltage electrostatic spinning process, so that the defect of difficult dissolution of chitosan is overcome. However, the electrospinning process often has the inherent defects of high production cost, low efficiency, complex control parameters and poor product consistency. Chitosan oligosaccharide is also called oligochitosan, is an oligosaccharide obtained by degrading chitosan by biological enzyme, and is a cationic basic amino oligosaccharide with positive charge which is few in nature. The fiber has the advantage of regulating high biological activity such as intestinal immunity and is widely concerned, but the low polymer state is difficult to be independently silky and needs to be compounded with other fibers for use. Sodium alginate is a polysaccharide polymer extracted from algal marine plants, and is composed of β -D-mannuronic acid and α -L-guluronic acid as a polysaccharide having a charge structure opposite to that of chitosan, and is an anionic acidic polysaccharide. Therefore, it is difficult to spin both into filaments by the conventional composite method.
Disclosure of Invention
Aiming at the problem that the existing chitosan composite fiber in the prior art is difficult to spin, the invention aims to provide the chitosan oligosaccharide medical marine fiber and the preparation method thereof.
A chitosan oligosaccharide medical marine fiber comprises an inner layer structure and an outer layer structure, wherein the inner layer component is metal ion crosslinked alginic acid fiber, the outer layer component is chitosan oligosaccharide-alginic acid metal complex, and the weight ratio of chitosan to alginic acid in the fiber is not less than 2: 100.
Preferably, the raw material comprises alginate, chitosan oligosaccharide and divalent metal salt, the viscosity of 1wt% of the alginate aqueous solution is (1.05-1.15) Pa.s, the polymerization degree of the chitosan oligosaccharide is 2-15, and the divalent metal salt preferably comprises at least one of calcium chloride, magnesium chloride, zinc chloride, barium chloride and ferric chloride.
The existing chitosan can generate polyion amide reaction with alginic acid and salts thereof in a solution, so that most of spun yarns are short and the controllability is low. Especially in chitosan-alginic acid fibers in which chitosan is a fiber matrix, alginic acid is difficult to attach to and react with chitosan fiber flow due to the acid solubility of chitosan, and it is difficult to truly exert the biocompatibility and antibacterial activity of chitosan.
Therefore, the invention also provides a preparation method of the chitosan oligosaccharide medical marine fiber, wherein the preparation process comprises the following steps:
1) dissolving 1 part by weight of alginate in 20-200 parts by weight of solvent to prepare spinning mother liquor;
2) dissolving 2-7 parts by weight of divalent metal salt in 100 parts by weight of solvent to prepare a coagulating bath solution;
3) dissolving 1 part by weight of chitosan oligosaccharide in 20-200 parts by weight of solvent to prepare a composite bath solution;
4) after the spinning mother liquor is defoamed in vacuum, spinning is carried out by a wet spinning method, the filaments discharged from a spinneret plate are immersed in a coagulating bath solution for coagulation, and traction and primary stretching are carried out simultaneously;
5) and (3) immersing the primary drawn fiber into a composite bath solution for composite reaction, wherein the composite bath temperature is 30-50 ℃, and simultaneously drawing for secondary drawing, wherein the relationship between the secondary drawing and the primary drawing rate is (4-6) to (1-3).
Preferably, the primary stretching time in the coagulation bath is (1.0-1.3) min, and the secondary stretching time in the composite bath is (3-5) min. More preferably, the fiber is drawn at a primary draw ratio of (1.2 to 1.6) and at a secondary draw ratio of (1.8 to 2.2).
Preferably, the composite bath solution solvent is water.
Preferably, the solvent of the spinning mother liquor and the coagulation bath solution is water.
Further, in the step 4), the fiber is coagulated with a coagulating bath solution and then immersed in a rinsing bath for rinsing, the rinsing bath is water, absolute ethyl alcohol or an ethanol water solution, and the initial drawing rate in the rinsing bath is the same as that in the coagulating bath.
Preferably, the fiber after the secondary drawing is immersed in absolute ethyl alcohol and rinsed and shaped.
Preferably, the chitosan oligosaccharide is chitosan obtained by chemical degradation, ultrasonic degradation, photo-thermal degradation or enzymatic degradation, more preferably by enzymatic degradation.
The comprehensive effects brought by the invention comprise:
the fiber takes alginate and chitosan oligosaccharide bi-polysaccharide which are both extracted from marine organisms as main raw materials, adopts low molecular weight chitosan oligosaccharide and hydrosolvent as a composite modification system, has high reaction compatibility, fully exposes reaction functional groups chelated by divalent metal ions in the alginate fiber through double-ratio stretching, promotes the fiber to generate polyion complex reaction with chitosan oligosaccharide in aqueous solution in the process of fiber forming reinforcement, has excellent antibacterial property and outstanding biocompatibility, and can be suitable for various medical fields such as surgical sutures, wound dressings, bandages and the like.
Detailed Description
The following examples of the present invention are merely illustrative of specific embodiments for carrying out the present invention and are not to be construed as limiting the invention. Other changes, modifications, substitutions, combinations, and simplifications which may be made without departing from the spirit and principles of the invention are intended to be equivalent substitutions and are within the scope of the invention.
The anionic and cationic polyion reaction of alginic acid and chitosan is one of the main factors influencing the composition of the alginic acid and the chitosan. When two kinds of polysaccharide spinning solutions are simply premixed or one kind of polysaccharide is used as a matrix and the other kind of polysaccharide is used as a coagulating bath for coagulation, the two kinds of polysaccharide spinning solutions usually react instantly in the meeting process due to the requirement of high uniformity of the solutions for wet spinning, so that the spinning solutions are turbid or a spinneret plate of a spinning head in the coagulating bath is blocked, and continuous fibers cannot be obtained.
In the invention, the composite reaction process is delayed to the stretching stage, so that the strength of the fiber matrix is enhanced while normal spinning is not influenced. Then, the primary-setting alginate fiber is stretched twice in a double ratio to ensure that the alginate fiber matrix is subjected to a complex reaction after having a certain strength, and the reaction functional group chelated by the metal ions is fully exposed under the traction action, so that carboxyl in the fiber matrix and the amido of the chitosan oligosaccharide are subjected to polyion reaction to generate an amido group and are continuously complexed with the metal ions. The composite reaction takes water as a basic solvent, so that the condition that the alginate fiber matrix is excessively degraded in the composite reaction process to lose strength is avoided.
Example 1
A chitosan oligosaccharide medical marine fiber comprises an inner layer structure and an outer layer structure, wherein the inner layer component is metal ion crosslinked alginic acid fiber, the outer layer component is chitosan oligosaccharide-alginic acid metal complex, and the weight ratio of chitosan to alginic acid in the fiber is 3: 100.
The raw materials adopted by the embodiment comprise sodium alginate, chitosan oligosaccharide and calcium chloride, the viscosity of a 1wt% aqueous solution of the sodium alginate is 1.10 Pa.s, the average value of the number of repeating units contained in the polymerization degree of the chitosan oligosaccharide is 13, the chitosan oligosaccharide is obtained by chitosan through an enzyme degradation method, and the divalent metal salt is calcium chloride.
The existing chitosan can generate polyion amide reaction with alginic acid and salts thereof in a solution, so that most of spun yarns are short and the controllability is low. Especially in chitosan-alginic acid fibers in which chitosan is a fiber matrix, alginic acid is difficult to attach to and react with chitosan fiber flow due to the acid solubility of chitosan, and it is difficult to truly exert the biocompatibility and antibacterial activity of chitosan.
Therefore, the present embodiment also provides a preparation method of the chitosan oligosaccharide medical marine fiber, wherein the preparation process includes the following steps:
1) dissolving 1kg of sodium alginate in 33kg of water to prepare spinning mother liquor of a sodium alginate solution;
2) dissolving 5kg of calcium chloride in 100kg of water to prepare a coagulating bath solution;
3) dissolving 100g of chitosan oligosaccharide in 5kg of water to prepare a composite bath solution;
4) after the spinning mother liquor is defoamed in vacuum, spinning is carried out by a wet spinning method, the filaments discharged from a spinneret plate are immersed in a coagulating bath solution for coagulation, and traction and primary stretching are carried out simultaneously;
the fiber is coagulated with coagulating bath solution and then immersed in rinsing bath for rinsing, the rinsing bath is a v/v 50% ethanol water solution, and the initial drawing speed in the rinsing bath is the same as that in the coagulating bath.
5) And (3) immersing the primary drawn fiber into a composite bath solution for composite reaction, wherein the composite bath temperature is 50 ℃, and simultaneously drawing for secondary drawing, wherein the relationship between the secondary drawing and the primary drawing rate is 5: 2.
The primary stretching time in the coagulation bath is 1min, and the secondary stretching time in the composite bath is 5 min. The primary drawing ratio of the fiber was 1.2, and the secondary drawing ratio was 2.0.
And finally, soaking the fiber after the secondary stretching into absolute ethyl alcohol, and rinsing and shaping.
Example 2
A chitosan oligosaccharide medical marine fiber comprises an inner layer structure and an outer layer structure, wherein the inner layer component is metal ion crosslinked alginic acid fiber, the outer layer component is chitosan oligosaccharide-alginic acid metal complex, and the weight ratio of chitosan to alginic acid in the fiber is 2: 100.
The raw materials adopted by the embodiment comprise sodium alginate, chitosan oligosaccharide and calcium chloride, the viscosity of a 1wt% aqueous solution of the sodium alginate is 1.05 Pa.s, the average value of the number of repeating units contained in the polymerization degree of the chitosan oligosaccharide is 15, the chitosan oligosaccharide is obtained by chitosan through an enzyme degradation method, and the divalent metal salt is zinc chloride.
The existing chitosan can generate polyion amide reaction with alginic acid and salts thereof in a solution, so that most of spun yarns are short and the controllability is low. Especially in chitosan-alginic acid fibers in which chitosan is a fiber matrix, alginic acid is difficult to attach to and react with chitosan fiber flow due to the acid solubility of chitosan, and it is difficult to truly exert the biocompatibility and antibacterial activity of chitosan.
Therefore, the present embodiment also provides a preparation method of the chitosan oligosaccharide medical marine fiber, wherein the preparation process includes the following steps:
1) dissolving 1kg of sodium alginate in 200kg of water to prepare spinning mother liquor of a sodium alginate solution;
2) dissolving 7kg of zinc chloride in 100kg of water to prepare a coagulating bath solution;
3) dissolving 100g of chitosan oligosaccharide in 2kg of water to prepare a composite bath solution;
4) after the spinning mother liquor is defoamed in vacuum, spinning is carried out by a wet spinning method, the filaments discharged from a spinneret plate are immersed in a coagulating bath solution for coagulation, and traction and primary stretching are carried out simultaneously;
and (3) coagulating the fiber and a coagulating bath solution, and then immersing the fiber into a rinsing bath for rinsing, wherein the rinsing bath is sewage ethanol, and the initial drawing and pulling rate in the rinsing bath is the same as that in the coagulating bath.
5) And (3) immersing the primary drawn fiber into a composite bath solution for composite reaction, wherein the composite bath temperature is 40 ℃, and simultaneously drawing for secondary drawing, wherein the relationship between the secondary drawing and the primary drawing rate is 3: 1. Higher compounding temperatures favor the formation of amides by condensation, but too high a temperature tends to cause depolymerization of the alginate fiber egg-box structure.
The primary stretching time in the coagulation bath is 1min, and the secondary stretching time in the composite bath is 5 min. The primary drawing ratio of the fiber was 1.2, and the secondary drawing ratio was 2.0.
And finally, soaking the fiber after the secondary stretching into absolute ethyl alcohol, and rinsing and shaping.
Example 3
A chitosan oligosaccharide medical marine fiber comprises an inner layer structure and an outer layer structure, wherein the inner layer component is metal ion crosslinked alginic acid fiber, the outer layer component is chitosan oligosaccharide-alginic acid metal complex, and the weight ratio of chitosan to alginic acid in the fiber is 2.5: 100.
The raw materials adopted by the embodiment comprise sodium alginate, chitosan oligosaccharide and calcium chloride, the viscosity of a 1wt% aqueous solution of the sodium alginate is 1.15 Pa.s, the average value of the number of repeating units contained in the polymerization degree of the chitosan oligosaccharide is 3, the chitosan oligosaccharide is obtained by chitosan through an enzyme degradation method, and the divalent metal salt is barium chloride.
The existing chitosan can generate polyion amide reaction with alginic acid and salts thereof in a solution, so that most of spun yarns are short and the controllability is low. Especially in chitosan-alginic acid fibers in which chitosan is a fiber matrix, alginic acid is difficult to attach to and react with chitosan fiber flow due to the acid solubility of chitosan, and it is difficult to truly exert the biocompatibility and antibacterial activity of chitosan.
Therefore, the present embodiment also provides a preparation method of the chitosan oligosaccharide medical marine fiber, wherein the preparation process includes the following steps:
1) dissolving 1kg of sodium alginate in 100kg of water to prepare spinning mother liquor of a sodium alginate solution;
2) dissolving 2kg of barium chloride in 100kg of water to prepare a coagulating bath solution;
3) dissolving 100g of chitosan oligosaccharide in 10kg of water to prepare a composite bath solution;
4) after the spinning mother liquor is defoamed in vacuum, spinning is carried out by a wet spinning method, the filaments discharged from a spinneret plate are immersed in a coagulating bath solution for coagulation, and traction and primary stretching are carried out simultaneously;
and (3) coagulating the fiber and the coagulating bath solution, and then soaking the fiber in a rinsing bath for rinsing, wherein the rinsing bath is water, and the initial drawing and pulling rate in the rinsing bath is the same as that in the coagulating bath.
5) And (3) immersing the primary drawn fiber into a composite bath solution for composite reaction, wherein the composite bath temperature is 50 ℃, and simultaneously drawing for secondary drawing, wherein the relation between the secondary drawing and the primary drawing rate is 2: 1.
The primary stretching time in the coagulation bath was 1.3min, and the secondary stretching time in the composite bath was 3 min. The primary drawing ratio of the fiber was 1.6, and the secondary drawing ratio was 2.2.
And finally, soaking the fiber after the secondary stretching into absolute ethyl alcohol, and rinsing and shaping.
Antibacterial proof test
The chitosan oligosaccharide medical marine fiber obtained in examples 1 and 2 was subjected to an example of the antibacterial activity by the agar dilution method:
the alginic acid-chitosan oligosaccharide metal complex marine fibers obtained in example 1 were cut and pulverized, and then added to a culture medium, and the antibacterial activity against gram-negative bacteria was measured by the agar dilution method, and the obtained results are shown in table 1.
The agar dilution method adopted by the invention can be implemented by adopting the conventional antibacterial detection method in the field, and does not generate substantial influence on the antibacterial performance of the sample.
TABLE 1 determination of antibacterial Activity of Chitosan oligosaccharide medical Marine fiber against gram-negative bacteria by agar dilution method
The alginic acid-chitosan oligosaccharide metal complex marine fibers obtained in example 2 were cut and pulverized, and then added to a culture medium, and the antibacterial activity against gram-positive bacteria and candida albicans was measured by the agar dilution method, and the obtained results are shown in table 2.
TABLE 2 determination of the antibacterial Activity of Chitosan oligosaccharide medical Marine fiber against gram-Positive bacteria and Candida albicans by agar dilution method
The fiber obtained by the invention has obvious antibacterial action and good bacteriostatic and bactericidal effects through antibacterial experiments on various clinically separated and purchased pathogenic strains. Has remarkable antibacterial effect on gram-positive bacteria and Candida albicans. Particularly, the chitosan-containing antibacterial agent has better antibacterial and bactericidal effects on gram-negative bacteria with weak effect on chitosan.
Although the present invention has been described in detail, modifications within the spirit and scope of the invention will be apparent to those skilled in the art. Further, it should be understood that the various aspects recited herein, portions of different embodiments, and various features recited may be combined or interchanged either in whole or in part. In the various embodiments described above, those embodiments that refer to another embodiment may be combined with other embodiments as appropriate, as will be appreciated by those skilled in the art. Furthermore, those skilled in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention.
Claims (6)
1. A method for preparing chitosan oligosaccharide medical marine fiber is characterized in that,
the fiber consists of an inner layer and an outer layer, wherein the inner layer is composed of metal ion crosslinked alginic acid fiber, the outer layer is composed of chitosan oligosaccharide-alginic acid metal complex, and the weight ratio of chitosan to alginic acid in the fiber is not less than 2:100;
the raw materials comprise alginate, chitosan oligosaccharide and divalent metal salt, wherein the viscosity of 1wt% of water solution of the alginate is 1.05-1.15 Pa.s, the polymerization degree of the chitosan oligosaccharide is 2-15, and the divalent metal salt comprises at least one of calcium chloride, magnesium chloride, zinc chloride, barium chloride and ferrous chloride;
the preparation process comprises the following steps:
1) dissolving 1 part by weight of alginate in 20-200 parts by weight of solvent to prepare spinning mother liquor;
2) dissolving 2-7 parts by weight of divalent metal salt in 100 parts by weight of solvent to prepare a coagulating bath solution;
3) dissolving 1 part by weight of chitosan oligosaccharide in 20-200 parts by weight of solvent to prepare a composite bath solution;
4) after the spinning mother liquor is defoamed in vacuum, spinning is carried out by a wet spinning method, the filaments discharged from a spinneret plate are immersed in a coagulating bath solution for coagulation, and traction and primary stretching are carried out simultaneously;
5) immersing the primary drawn fiber into a composite bath solution for composite reaction, wherein the composite bath temperature is 30-50 ℃, and simultaneously carrying out traction secondary drawing, wherein the relationship between the secondary drawing and the primary drawing rate is 4-6:1-3;
the primary stretching time in the coagulation bath is (1.0-1.3) min, and the secondary stretching time in the composite bath is (3-5) min.
2. The method according to claim 1, wherein the fiber is drawn at a primary draw ratio of 1.2 to 1.6 and a secondary draw ratio of 1.8 to 2.2.
3. The method of claim 1, wherein the composite bath solution solvent is water.
4. The process according to claim 1, wherein in step 4), the fiber is coagulated with a coagulation bath solution and then rinsed by immersing in a rinsing bath of water, absolute ethanol or an aqueous ethanol solution, and the initial drawing rate in the rinsing bath is the same as that in the coagulation bath.
5. The method according to claim 4, wherein the fiber after the secondary drawing is immersed in absolute ethanol and rinsed and set.
6. The method for preparing according to claim 1, wherein the chitosan oligosaccharide is chitosan obtained by chemical degradation, sonication, photothermal degradation or enzymatic degradation.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1174243A1 (en) * | 2000-07-22 | 2002-01-23 | Kalle GmbH & Co. KG | Process and apparatus for manufacturing a seamless tubular film and seamless tubular film |
| CN1940153A (en) * | 2006-09-21 | 2007-04-04 | 青岛大学 | Chitose graft alginate fibre, its production and use |
| CN107029272A (en) * | 2017-04-10 | 2017-08-11 | 河南汇博医疗股份有限公司 | A kind of alginate medical dressing and preparation method thereof |
| CN107469128A (en) * | 2017-08-02 | 2017-12-15 | 武汉医佳宝生物材料有限公司 | A kind of antimicrobial form alginates complex function dressing and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1174243A1 (en) * | 2000-07-22 | 2002-01-23 | Kalle GmbH & Co. KG | Process and apparatus for manufacturing a seamless tubular film and seamless tubular film |
| CN1940153A (en) * | 2006-09-21 | 2007-04-04 | 青岛大学 | Chitose graft alginate fibre, its production and use |
| CN107029272A (en) * | 2017-04-10 | 2017-08-11 | 河南汇博医疗股份有限公司 | A kind of alginate medical dressing and preparation method thereof |
| CN107469128A (en) * | 2017-08-02 | 2017-12-15 | 武汉医佳宝生物材料有限公司 | A kind of antimicrobial form alginates complex function dressing and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 海藻酸钙/壳聚糖复合纤维的制备及性能研究;黄亚飞等;《合成纤维工业》;20171231;第40卷(第1期);6-10 * |
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