CN101665995B - Sodium alga acid/chitosan composite fluid spinning method - Google Patents
Sodium alga acid/chitosan composite fluid spinning method Download PDFInfo
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- CN101665995B CN101665995B CN200810013113XA CN200810013113A CN101665995B CN 101665995 B CN101665995 B CN 101665995B CN 200810013113X A CN200810013113X A CN 200810013113XA CN 200810013113 A CN200810013113 A CN 200810013113A CN 101665995 B CN101665995 B CN 101665995B
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Abstract
The invention provides a novel method for preparing silk scaffolds for industrial spinning and biomedical tissue engineering. Aiming at a requirement of manufacturing various silk scaffold materials for the industrial spinning and the biomedical tissue engineering, solution of sodium alginate and solution of chitosan capable of generating polyelectrolyte reaction are taken as raw materials, and the solution of chitosan is drawn into silk liquid flow by the solution of sodium alginate by adjusting concentrations and relative movement speeds of the two solution; and the silk liquid flow undergoes the polyelectrolyte reaction with the encountered solution of sodium alginate, and then is cured to from the silk scaffolds with different diameters. Compared with the conventional spinning method, the method has simple and feasible equipment, and can overcome the adverse influence caused by silk breakage phenomenon in the conventional wet spinning process.
Description
Technical field
The present invention relates to biomedical tissue engineering and industrial field of textiles, specifically a kind of spinning process that is suitable for making the thread timbering material of alginate compound.
Background technology
The manufacture method of filamentary material is varied at present, common meltblown (Melt-blown) wet spinning (wetspinning), electrostatic spinning (Electrospinning), phase separation method (Phase separation), self-assembly method (Self-assembly), the template synthetic method (Template synthesis) etc. of mainly containing, but all, in actual production, be subjected to the restriction of different condition because of shortcomings such as manufacturing technique complexity, engineering elapsed time are grown, the raw material scope of application is narrow.Our design and spinning process---the fluid spinning of implementing are compared with said method, have device simple, advantage such as easy and simple to handle, and can overcome the adverse effect that the fracture of wire phenomenon is brought in traditional wet spinning process.(performance and the application of document 1. alginate fibres.Printing and dyeing assistant, the 23rd the 6th phase of volume, in June, 2006.The carbonization technique research of document 2. electrospinning PAN nanofibers.The Chinese science and technology paper is online, http://www.paper.edu.cn.Instability research in the document 3. electrostatic spinning processes.Synthetic fiber industry, in April, 2006, the 29th volume, the 2nd phase.The research of document 4. electrostatic spinning nano fibers and application progress.Synthetic fiber industry, in June, 2006, the 29th volume, the 3rd phase.Document 5.Chitosan-alginate as scaffolding material for cartilage tissueengineering.Journal of Biomedical Materials Research Part A, Volume 75A, Issue 2, Pages 485-493, Published Online:9 Aug 2005.)
Summary of the invention
The present invention proposes a kind of spinning process of the novel thread timbering material of alginate compound, does not have adhesion between the product of its controllable diameter, acquisition mutually; The silk ribbon shape support of preparing can be used for fields such as biomedical tissue engineering rack or industry weaving.
Its principle is: chitosan solution and sodium alginate soln that relative motion meet, and the polyelectrolyte reaction takes place, and make the shitosan filamentous liquid stream that is stretched fixed-type, form solid-state, resilient thread support.With respect to ground, no matter be that chitosan solution keeps static and sodium alginate soln moves with respect to the former, or sodium alginate soln keeps static and shitosan moves with respect to the former, as long as relative motion is arranged between the two, and be in contact with one another, the chitosan solution distortion that can both on contact-making surface, be stretched, and form silk ribbon shape product in the sodium alginate soln reaction.
For achieving the above object, the technical solution used in the present invention is:
Sodium alga acid/chitosan composite fluid spinning method, chitosan solution by with injection, spray or the mode that drips joins in the sodium alginate soln with its relative motion.Under the effect of contact frictional force between two solution, chitosan solution is stretched and forms filamentous liquid stream, because of fixed-type with the reaction of sodium alginate soln generation polyelectrolyte, finally forms silk ribbon shape support simultaneously; Speed of related movement when sodium alginate soln and chitosan solution meet is 20 meter per second to 1500 meter per seconds.
Wherein sodium alginate soln is the solvent preparation with water or the cushioning liquid of pH 5-9, and sodium alginate aqueous solution concentration is that (w/v, g/ml), the sodium alginate molecular weight is 250-600kDa to 0.01-3%.
Wherein chitosan solution is the solvent preparation in order to water or the cushioning liquid of pH 3-6, and chitosan solution concentration is that (w/v, g/ml), the chitosan molecule amount is 15-250kDa to 0.01-3%, deacetylating degree of chitosan 80-98%.
Wherein chitosan solution is in the mode of continuous fluid, and injection enters sodium alginate (spinning of injecting type fluid); Or, drip or spraying enters sodium alginate soln (spinning of spray-type fluid) in the mode of discontinuous drop.
The entrance port unit are flow that chitosan solution injection, sprinkling or dropping enter sodium alginate soln is 10-3000L/hrm
2
Specifically can be, 1. prepare certain density sodium alginate soln and chitosan solution, wherein the sodium alginate molecular weight is 250-600kDa; The chitosan molecule amount is 15-250kDa, deacetylating degree of chitosan 80-98%;
2. make the speed of related movement of sodium alginate soln and chitosan solution on average reach 20 meter per second to 1500 meter per seconds in modes such as stirring or rotations;
3. the gageable injection device (or sprayer unit) of an amount of chitosan solution being packed into enters (or spray into, splash into) sodium alginate soln with the certain flow injection.Chitosan solution is stretched and forms filamentous liquid stream, and is fixed-type with the reaction of sodium alginate soln generation polyelectrolyte simultaneously, finally forms silk ribbon shape support; (for the output that guarantees last spinning product and the homogeneity of spinning diameter, the chitosan solution volumetric usage should be the 2-30% of sodium alginate soln volume);
4. centrifugal with 2500-3500g, collect thread support.
This characteristic feature of an invention possesses following advantage:
1. raw material is simple: main raw material is shitosan and sodium alginate;
2. equipment is simple: only need solution device for formulating, filter, agitating device, injection or flusher and common devices such as centrifugal device and drying device;
3. technological operation is easy: no high temperature, high pressure, risky operation such as poisonous;
4. by selection of process parameters, can prepare at the controlled silk ribbon shape support of 0.5 micron-2 millimeters scope interior diameters (the diameter here is meant the long axis length of silk ribbon cross section);
The product of Huo Deing be do not have each other adhesion, the thread support of alginate compound polyelectrolyte, present flocculence on the whole, excellent biological compatibility is arranged, be easy to the cell growth metabolism, good viscoplasticity is arranged, be easy to further machine-shaping;
6. product is of many uses, can be used for fields such as biomedical tissue engineering rack or industrial wool spinning;
7. this spinning technique with respect to the advantage of industrial wet spinning is, can ignore the fracture of wire phenomenon in the spinning process, avoids owing to be broken into influencing each other between piece and single spinning in the spinning that the fracture of wire phenomenon causes.
Description of drawings
Fig. 1 is a principle schematic of the present invention.Wherein left hand view is an injecting type fluid device for spinning schematic diagram, and right part of flg is an atomizing fluid device for spinning schematic diagram, and a is a sodium alginate soln, and b is a chitosan solution, and c is an agitating device, and d is the injection sprayer unit.
The ribbon spinning product of Fig. 2 for obtaining according to embodiment 1.
The ribbon spinning product of Fig. 3 for obtaining according to embodiment 2.
The ribbon spinning product of Fig. 4 after for the freeze drying that obtains according to embodiment 3.
The ribbon spinning product of Fig. 5 for obtaining according to embodiment 4.
The ribbon spinning product of Fig. 6 for obtaining according to embodiment 5.
The ribbon spinning product of Fig. 7 for obtaining according to embodiment 6.
The ribbon spinning product of Fig. 8 for obtaining according to embodiment 7.
The specific embodiment
Embodiment 1
1. prepare acetate buffer solution (solution composition: 0.2M acetic acid and 0.1M sodium acetate, pH3-6);
2. with the acetate buffer solution solvent, preparation chitosan-containing 0.01% (w/v, solution g/ml);
3. preparation contains sodium alginate 0.01% (w/v, aqueous solution g/ml);
4. with the flow of 4ml/hr chitosan solution being injected the sodium alginate soln that flow velocity is 20 meter per seconds with the syringe of medical No. 5 syringe needles, obtain thread support, its diameter distributes between 40-60 μ m, and average diameter is about 50 μ m, as Fig. 2;
5. thread support 3000g is centrifugal, collect sediment, the product of acquisition be do not have each other adhesion, the thread support of alginate compound polyelectrolyte.
Embodiment 2
1. prepare acetate buffer solution (solution composition: 0.2M acetic acid and 0.1M sodium acetate, pH3-6);
2. with the acetate buffer solution solvent, preparation chitosan-containing 1.5% (w/v, solution g/ml);
3. preparation contains sodium alginate 1.5% (w/v, aqueous solution g/ml);
4. with the flow of 4ml/hr chitosan solution being injected the sodium alginate soln that flow velocity is 750 meter per seconds with the syringe of medical No. 5 syringe needles, obtain the ribbon polymer, its diameter distributes between 17.5-22.5 μ m, and average diameter is about 20 μ m, as Fig. 3;
5. polymer 3000g is centrifugal, collect sediment, the product of acquisition be do not have each other adhesion, the thread support of alginate compound polyelectrolyte.
Embodiment 3
1. prepare acetate buffer solution (solution composition: 0.2M acetic acid and 0.1M sodium acetate, pH3-6);
2. with the acetate buffer solution solvent, preparation chitosan-containing 3% (w/v, solution g/ml);
3. preparation contains sodium alginate 3% (w/v, aqueous solution g/ml);
4. with the flow of 4ml/hr chitosan solution being injected the sodium alginate soln that flow velocity is 1500 meter per seconds, obtain the ribbon polymer, as Fig. 4 with the syringe of medical No. 5 syringe needles;
5. polymer 3000g is centrifugal, collect sediment, freeze drying, the product of acquisition be do not have each other adhesion, the thread support of alginate compound polyelectrolyte.
Embodiment 4
1. prepare acetate buffer solution (solution composition: 0.2M acetic acid and 0.1M sodium acetate, pH3-6);
2. with the acetate buffer solution solvent, preparation chitosan-containing 0.01% (w/v, solution g/ml);
3. preparation contains sodium alginate 0.01% (w/v, aqueous solution g/ml);
4. with common agricultural agroatomizer chitosan solution is sprayed in the sodium alginate soln that flow velocity is 20 meter per seconds, obtain the ribbon polymer, its diameter distributes between 27.5-32.5 μ m, and average diameter is about 30 μ m, as Fig. 5;
5. polymer 3000g is centrifugal, collecting precipitation thing, the product of acquisition be do not have each other adhesion, the thread support of alginate compound polyelectrolyte.
Embodiment 5
1. prepare acetate buffer solution (solution composition: 0.2M acetic acid and 0.1M sodium acetate, pH3-6);
2. with the acetate buffer solution solvent, preparation chitosan-containing 1.5% (w/v, solution g/ml);
3. preparation contains sodium alginate 1.5% (w/v, aqueous solution g/ml);
4. with common agricultural agroatomizer chitosan solution is sprayed in the sodium alginate soln that flow velocity is 750 meter per seconds, obtain the ribbon polymer, its diameter distributes between 17.5-22.5 μ m, and average diameter is about 20 μ m, as Fig. 6;
5. polymer 3000g is centrifugal, collect sediment, the product of acquisition be do not have each other adhesion, the thread support of alginate compound polyelectrolyte.
Embodiment 6
1. prepare acetate buffer solution (solution composition: 0.2M acetic acid and 0.1M sodium acetate, pH3-6);
2. with the acetate buffer solution solvent, preparation chitosan-containing 3% (w/v, solution g/ml);
3. preparation contains sodium alginate 3% (w/v, aqueous solution g/ml);
4. with common agricultural agroatomizer chitosan solution is sprayed in the sodium alginate soln that flow velocity is 1500 meter per seconds, obtain the ribbon polymer, its diameter distributes between 12.5-17.5 μ m, and average diameter is about 15 μ m, as Fig. 7;
5. polymer 3000g is centrifugal, collect sediment, the product of acquisition be do not have each other adhesion, the thread support of alginate compound polyelectrolyte.
Embodiment 7
1. prepare acetate buffer solution (solution composition: 0.2M acetic acid and 0.1M sodium acetate, pH3-6);
2. with the acetate buffer solution solvent, preparation chitosan-containing 0.03% (w/v, solution g/ml);
3. preparation contains sodium alginate 3% (w/v, aqueous solution g/ml);
4. the syringe that will have medical No. 5 syringe needles is filled chitosan solution, is fixed on the stirrer paddle tip, and syringe needle only allows syringe needle be immersed in the sodium alginate soln down, and paddle rotates, and the radius of turn of needle point is 2cm, and rotary speed is 1500 rev/mins.Syringe flows out chitosan solution with the flow of 4ml/hr in the trend sodium alginate soln, obtain the ribbon polymer, and its diameter distributes between 1-2 μ m, and average diameter is about 1.5 μ m, as Fig. 8;
5. polymer 3000g is centrifugal, collect sediment, the product of acquisition be do not have each other adhesion, the thread support of alginate compound polyelectrolyte.
Claims (5)
1. alginate is collaborated fluid spinning method, it is characterized in that: chitosan solution is joined in the sodium alginate soln by the mode with injection, sprinkling or dropping; Speed of related movement when sodium alginate soln and chitosan solution meet is 20 meter per second to 1500 meter per seconds; When two kinds of above-mentioned solution meet with certain relative velocity motion, chitosan solution is under the effect of contact frictional force between two solution, being stretched forms filamentous liquid stream, because of fixed-type with the reaction of sodium alginate soln generation polyelectrolyte, finally forms silk ribbon shape support simultaneously;
Described sodium alginate soln is the solvent preparation with water or the cushioning liquid of pH 5-9, and sodium alginate aqueous solution concentration is 0.01-3%w/v, and the sodium alginate molecular weight is 250-600kDa;
Described chitosan solution is the solvent preparation with water or the cushioning liquid of pH 3-6, and chitosan solution concentration is 0.01-3%w/v, and the chitosan molecule amount is 15-250kDa, deacetylating degree of chitosan 80-98%.
2. in accordance with the method for claim 1, it is characterized in that: chitosan solution is in the mode of continuous fluid, and injection enters sodium alginate; Or, drip or spraying enters sodium alginate soln in the mode of discontinuous drop.
3. it is characterized in that in accordance with the method for claim 1: the entrance port unit are flow that chitosan solution injection, sprinkling or dropping enter sodium alginate soln is 10-3000L/hrm
2
4. in accordance with the method for claim 1, it is characterized in that: in order to keep the homogeneity of last spinning product diameter, the chitosan solution volumetric usage is the 2-30% of sodium alginate soln volume.
5. in accordance with the method for claim 1, it is characterized in that: the reaction solution that has silk ribbon shape support that is obtained is centrifugal with 2500-3500g, collect thread support.
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| CN108601860A (en) * | 2016-02-12 | 2018-09-28 | 金珂生物医疗公司 | Chitosan ultrafine fiber system |
| CN106267340A (en) * | 2016-08-12 | 2017-01-04 | 上海交通大学医学院附属第九人民医院 | A kind of foam stand and preparation method thereof |
| CN107219194B (en) * | 2017-05-03 | 2019-07-02 | 哈尔滨工业大学 | The preparation method and application for having the compound polyelectrolyte of the patterning micro nano structure of response |
| CN107237005B (en) * | 2017-06-19 | 2020-06-09 | 山东大学 | Alginic acid and chitosan double-component fiber and preparation method thereof |
| CN109208112B (en) * | 2018-07-19 | 2021-03-02 | 恒天纤维集团有限公司 | Polyelectrolyte-containing fiber and method for producing same |
| CN109943899A (en) * | 2019-03-27 | 2019-06-28 | 西宝生物科技（上海）股份有限公司 | A kind of Biodegradable anti-biotic material and preparation method thereof |
| CN110804773B (en) * | 2019-10-22 | 2021-04-02 | 东华大学 | Anionic-cationic polyelectrolyte composite material and salt inhibition preparation process thereof |
| CN115400257A (en) * | 2022-08-31 | 2022-11-29 | 皖南医学院 | Preparation method and application of degradable suture line based on polyelectrolyte method |
| CN116065262B (en) * | 2023-01-07 | 2024-04-05 | 华南理工大学 | Method for preparing environment-friendly nanofiber through high-pressure treatment |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997039170A1 (en) * | 1996-04-12 | 1997-10-23 | Bristol-Myers Squibb Company | Composite fibres, wound dressings incorporating such fibres and a method for making same |
| CN1919352A (en) * | 2006-09-15 | 2007-02-28 | 东华大学 | Preparing method and use of chitosan-containing nano fibrous tissue recovery support |
| CN1940153A (en) * | 2006-09-21 | 2007-04-04 | 青岛大学 | Chitose graft alginate fibre, its production and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997039170A1 (en) * | 1996-04-12 | 1997-10-23 | Bristol-Myers Squibb Company | Composite fibres, wound dressings incorporating such fibres and a method for making same |
| CN1919352A (en) * | 2006-09-15 | 2007-02-28 | 东华大学 | Preparing method and use of chitosan-containing nano fibrous tissue recovery support |
| CN1940153A (en) * | 2006-09-21 | 2007-04-04 | 青岛大学 | Chitose graft alginate fibre, its production and use |
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