CN100457989C - Method for preparing high-strength alginic acid/gelatin cross-blend fiber and its use - Google Patents
Method for preparing high-strength alginic acid/gelatin cross-blend fiber and its use Download PDFInfo
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- CN100457989C CN100457989C CNB2006100699793A CN200610069979A CN100457989C CN 100457989 C CN100457989 C CN 100457989C CN B2006100699793 A CNB2006100699793 A CN B2006100699793A CN 200610069979 A CN200610069979 A CN 200610069979A CN 100457989 C CN100457989 C CN 100457989C
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Abstract
The invention discloses high strength alginic acid/gelatin blended fiber manufacturing method and use. The method includes the following steps: making sodium alginate solution with 3-6% mass percent; making gelatin aqueous solution with 6-12% mass percent and 8.0-9.0 pH; mixing them as 10-50:100 volumetric ratio; stirring to homogeneous phase system; decompress; de-bubbling; using wet spinning method to make fiber under 33 degree centigrade of which total draft is 10-30%. The invention makes cross blend spinning fluid be cross linking with Ca2+ divalent metal ion, and makes the fiber under acidity with polyelectrolyte effect which can further increase fiber cross linking level, breaking tenacity to improve fiber physical mechanical properties. Thus it can be used to make non-woven fabrics such as hospital gauze, dressing etc.
Description
Technical field
The present invention relates to a kind of preparation method of high-strength alginic acid/gelatin cross-blend fiber, belong to the macromolecule chemical material field.
Background technology
Natural polymer is not only given it with synthetic high polymer quite even more performance with their unique texture, and often has premium properties such as nothing (low) poison, good biological histocyte compatibility, biodegradable.Sodium alginate is the natural linear polysaccharide that a class extracts from marine alga, is made up of the beta-D-mannuronic acid (M unit) and the α-L-guluronic acid (G unit) of 1,4 bonding, and nontoxic, biodegradable and tool has high biologically active.With its be feedstock production alginate fibre with its excellent specific property-(as) high moisture absorption becomes colloidality, the whole easily production technology of the property removed, high oxygen permeability, biocompatibility, biodegradation absorbability, macroion adsorptivity and environmental protection to be used widely as hospital gauze, dressing etc. in medical industry.But there is the shortcoming that intensity is low, fiber is more crisp in the alginate fibre by the pure sodium alginate preparation.
Gelatin is through partial hydrolysis and thermal denaturation and the macro-molecular protein that obtains by the collagen in the connective tissues such as the skin of animal, bone.Gelatin and human body do not have foreign matter, inflammation and rejection, have that water-permeable and air permeable is good, activated macrophage, hemostatic good, good biocompatibility, can be absorbed fully in vivo, the premium properties such as nontoxic and easy shaping to human body, especially the biological degradability of gelatin and avirulence, just meeting the requirement of current biomaterial development, is a kind of environment-friendly and bio material that has development prospect.
Chinese invention patent application CN200510018615.8 discloses a kind of employing CaCl
2With the absolute ethyl alcohol mixed liquor as coagulating bath, adopt wet spinning process to prepare the blended fiber of sodium alginate/glutin that a kind of dry strength is 1.18cN/dT, the quality of the blended fiber of sodium alginate/glutin that this patent is produced and characteristic thereof are still waiting further perfect.
Summary of the invention
The present invention is directed to alginic acid fibre elasticity, the desirable shortcoming of insufficient strength, by the simple and effective method of blending and modifying with raising macromolecular material performance, with sodium alginate and gelatin cross-blend with activated macrophage, hemostatic good, good biocompatibility, prepare a kind of high-strength alginic acid/gelatin cross-blend fiber, to improve the physical and mechanical properties and the medicinal properties of alginate fibre, improve the added value of fiber.
Its technical solution is:
A kind of preparation method of high-strength alginic acid/gelatin cross-blend fiber comprises the steps:
1. produce mass percent and be 3%～6% sodium alginate soln;
2. produce mass percent and be 6%～12%, the pH value is 8.0～9.0 aqueous gelatin solution;
3. with above-mentioned sodium alginate soln and aqueous gelatin solution by volume 10～50: 100 mix, the mixed solution brute force is stirred to homogeneous system, vacuum deaerator, under 33 ± 1 ℃, adopt wet spinning process to make fibre forming through metal freezing bath and sour coagulating bath successively, the total extensibility of fiber is 10%～30%.
Above-mentioned steps 3. in, mixed solution at first forms primary filament in metal freezing is bathed, the primary filament extensibility is 10%～20%, then with primary filament stretched further one-tenths thread in sour coagulating bath.
Above-mentionedly produce the sodium alginate that sodium alginate soln selects for use and be preferably the food-grade sodium alginate; Produce gelatin that aqueous gelatin solution selects for use and be preferably and analyze pure level gelatin, adopt dissolved in distilled water, the temperature of distilled water is preferably 30 ℃～70 ℃.
Above-mentioned steps 2. in, select NaOH, triethanolamine or Na for use
2HPO
4The aqueous solution is regulated alkaline agent as the pH value of aqueous gelatin solution.The pH value of above-mentioned aqueous gelatin solution is preferably 8.2～8.3.
Preferred mass percentage is the pH value that 1% the triethanolamine aqueous solution is regulated aqueous gelatin solution.
Above-mentioned metal freezing is bathed the CaCl that can be 2%～6% (mass percent)
2, Al
2(SO
4)
3Or ZnCl
2The mixed liquor that solution and absolute ethyl alcohol form, absolute ethyl alcohol and metal salt solution volume ratio are 30～100: 100.
Above-mentioned mixed liquor is preferably 1: 1 4%CaCl of volume ratio
2Mixed liquor with absolute ethyl alcohol.
Above-mentioned sour coagulating bath can be hydrochloric acid, phosphoric acid, acetate, DL-malic acid or the BTCA aqueous solution, and the pH value is 3.2～4.2.
It is 4.0 the BTCA aqueous solution that above-mentioned sour coagulating bath is preferably the pH value.
The present invention mainly be with the co-blended spinning liquid of sodium alginate and gelatin by with Ca
2+Deng bivalent metal ion crosslinked and under acid condition the two polyelectrolyte effect prepare alginic acid/gelatin cross-blend fiber.Easy and some the bivalent cation complexing formation aquogel of sodium alginate, it is typical ionomer aquogel.As in sodium alginate aqueous solution, adding Cu
2+, Zn
2-, Ca
2+, Sr
2+, Ba
2+After CATION, the Na on the G unit
+With bivalent metal ion generation ion-exchange reactions.Contain Ca in employing
2+The aqueous solution be metal freezing when bathing the preparation alginate fibre, the G unit and the Ca of sodium alginate
2+Generate " egg-box " structure, form three-dimensional space net structure, separate out thereby be transformed into aquagel fibre.Gelatin-NH
3 +With sodium alginate-COO
-Under acid condition, produce the polyelectrolyte effect, can further improve the degree of cross linking of fiber, improve the fracture strength of fiber, thereby improve the alginic acid/gelatin cross-blend fiber physical and mechanical properties.
Because high-strength alginic acid/gelatin cross-blend fiber has the advantage of sodium alginate and gelatin concurrently, mechanical property and water imbibition greatly improve, and can make nonwoven fabric such as medical materials such as hospital gauze, dressing.
The specific embodiment
Embodiment 1: get the 30g sodium alginate powder under the normal temperature and be dissolved in 970g distilled water, stirring and dissolving gets sodium alginate soln; Under 50C the 30g gelatin is dissolved in 470g distilled water, stirring and dissolving gets aqueous gelatin solution; Select NaOH, triethanolamine or Na for use
2HPO
4In any pH value adjusting alkaline agent that waits the aqueous solution as aqueous gelatin solution, the pH value of regulating aqueous gelatin solution is 8.0,8.2,8.25,8.3,8.5 or 9.0, with above-mentioned two kinds of solution blendings, the mixed proportion of aqueous gelatin solution and sodium alginate soln (volume ratio) is chosen as 10: 100,20: 100,30: 100 or 50: 100, the blend solution brute force is stirred to homogeneous system, vacuum deaerator in the time of 33 ℃; Under 33 ± 1 ℃, at first in bathing, adopt metal freezing wet spinning process to form primary filament, and metal freezing is bathed the CaCl that can be 2%, 4%, 5% or 6% (mass percent)
2, Al
2(SO
4)
3Or ZnCl
2The aqueous solution and the mixed liquor that forms of absolute ethyl alcohol, absolute ethyl alcohol and metal salt solution volume ratio are 30,40,50 or 90: 100, the primary filament extensibility can be 10%, 15% or 20%, then primary filament is further become silk in sour coagulating bath, form high-strength alginic acid/gelatin cross-blend fiber, the total extensibility of fiber can be 10%, 25% or 30%, naturally dry, above-mentioned sour coagulating bath can be hydrochloric acid, phosphoric acid, acetate or DL-aqueous solution of malic acid, and the pH value of sour coagulating bath is 3.2,3.5 or 4.2.
Embodiment 2: get the 60g sodium alginate powder under the normal temperature and be dissolved in 940g distilled water, stirring and dissolving gets sodium alginate soln; Under 70 ℃ the 60g gelatin is dissolved in 440g distilled water, stirring and dissolving gets aqueous gelatin solution; Select NaOH, triethanolamine or Na for use
2HPO
4In any pH value adjusting alkaline agent that waits the aqueous solution as aqueous gelatin solution, the pH value of regulating aqueous gelatin solution is 8.0,8.2,8.25,8.3,8.5 or 9.0, with above-mentioned two kinds of solution blendings, the mixed proportion of aqueous gelatin solution and sodium alginate soln (volume ratio) is chosen as 10: 100,20: 100,30: 100 or 50: 100, the blend solution brute force is stirred to into homogeneous system, vacuum deaerator in the time of 33 ℃; Under 33 ± 1 ℃, at first in bathing, adopt metal freezing wet spinning process to form primary filament, and metal freezing is bathed the CaCl that can be 2%, 4%, 5% or 6% (mass percent)
2, Al
2(SO
4)
3Or ZnCl
2The aqueous solution and the mixed liquor that forms of absolute ethyl alcohol, absolute ethyl alcohol and metal salt solution volume ratio are 30,40,50 or 90: 100, the primary filament extensibility can be 10%, 15% or 20%, secondly primary filament is further become silk in sour coagulating bath, form high-strength alginic acid/gelatin cross-blend fiber, the total extensibility of fiber can be 10%, 25% or 30%, dries naturally, above-mentioned sour coagulating bath can be hydrochloric acid, phosphoric acid, acetate or DL-malic acid, and the pH value of sour coagulating bath is 3.2,3.5 or 4.2.
The alginic acid/gelatin cross-blend fiber of example 1,2 gained is carried out mechanical property and water absorption rate test, and test result sees the following form.
By data among the figure as can be known, alginic acid/gelatin cross-blend fiber has excellent mechanical property and water absorbing properties.
Claims (9)
1, a kind of preparation method of high-strength alginic acid/gelatin cross-blend fiber comprises the steps:
1. produce mass percent and be 3%～6% sodium alginate soln;
2. produce mass percent and be 6%～12%, the pH value is 8.0～9.0 aqueous gelatin solution;
3. with above-mentioned sodium alginate soln and aqueous gelatin solution by volume 10～50: 100 mix, the mixed solution brute force is stirred to into homogeneous system, vacuum deaerator, under 33 ± 1 ℃, adopt wet spinning process to make fibre forming through metal freezing bath and sour coagulating bath successively, the total extensibility of fiber is 10%～30%.
2, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 1, it is characterized in that: described step 3. in, mixed solution at first forms primary filament in metal freezing is bathed, the primary filament extensibility is 10%～20%, then primary filament is further become silk in sour coagulating bath.
3, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 1 is characterized in that: described to produce the sodium alginate that sodium alginate soln selects for use be the food-grade sodium alginate; Describedly produce gelatin that aqueous gelatin solution selects for use for analyzing pure level gelatin, gelatin is dissolved in distilled water, the temperature of distilled water is 30 ℃～70 ℃, and stirring and dissolving obtains aqueous gelatin solution.
4, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 1 is characterized in that: described step 2. in, select NaOH, triethanolamine or Na for use
2HPO
4The aqueous solution is regulated alkaline agent as the pH value of aqueous gelatin solution; The pH value of regulating aqueous gelatin solution is 8.2～8.3.
5, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 4 is characterized in that: selecting mass percent for use is the pH value that 1% the triethanolamine aqueous solution is regulated aqueous gelatin solution.
6, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 1 is characterized in that: it is the CaCl of 2%～6% mass percent that described metal freezing is bathed
2, Al
2(SO
4)
3Or ZnCl
2The aqueous solution and the mixed liquor that forms of absolute ethyl alcohol, absolute ethyl alcohol and metal salt solution volume ratio are 30～100: 100.
7, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 6 is characterized in that: described metal freezing is bathed and is 1: 1 4%CaCl of volume ratio
2Mixed liquor with absolute ethyl alcohol.
8, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 1 is characterized in that: described sour coagulating bath is hydrochloric acid, phosphoric acid, acetate, DL-malic acid or the BTCA aqueous solution, and the pH value of sour coagulating bath is 3.2～4.2.
9, the preparation method of high-strength alginic acid/gelatin cross-blend fiber according to claim 8 is characterized in that: described sour coagulating bath is that the pH value is 4.0 the BTCA aqueous solution.
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| CNB2006100699793A CN100457989C (en) | 2006-11-04 | 2006-11-04 | Method for preparing high-strength alginic acid/gelatin cross-blend fiber and its use |
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| CN100457989C true CN100457989C (en) | 2009-02-04 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007044648B4 (en) * | 2007-09-18 | 2020-11-26 | Carl Freudenberg Kg | Bioresorbable gelatin non-woven fabric |
| CN102321935B (en) * | 2011-07-26 | 2013-04-24 | 武汉理工大学 | Soluble alginate/carboxymethyl carrageenan composite antibacterial fiber and preparation method thereof |
| GB2518199A (en) * | 2013-09-13 | 2015-03-18 | Xiros Ltd | Method of producing a swellable polymer fibre |
| CN104073915A (en) * | 2014-07-01 | 2014-10-01 | 青岛明月生物医用材料有限公司 | Blend fiber material as well as preparation method and use thereof |
| CN104383580A (en) * | 2014-10-30 | 2015-03-04 | 河北考力森生物科技有限公司 | Preparation method of alginate/collagen-containing membrane |
| CN106245153B (en) * | 2016-07-28 | 2019-01-29 | 湖南帝星智能科技有限公司 | Medical fiber mixed by gelatin and bamboo fiber and preparation method thereof |
| CN106435815B (en) * | 2016-09-20 | 2018-07-13 | 大连工业大学 | Chemical crosslinking modified fibroin albumen/alginate composite fiber and preparation method thereof |
| CN106821772B (en) * | 2017-03-06 | 2021-06-25 | 广东石油化工学院 | Preparation method of network interpenetrating surface film base material |
| CN108452366B (en) * | 2018-03-26 | 2021-08-13 | 中国海洋大学 | Cod skin gelatin composite hemostatic dressing and preparation method thereof |
| CN109252245B (en) * | 2018-08-01 | 2020-11-06 | 青岛海赛尔新材料科技有限公司 | Super-absorbent alginate fiber and preparation method thereof |
| CN110067042B (en) * | 2019-04-01 | 2021-12-07 | 东华大学 | Konjac glucomannan-based antibacterial hydrogel fiber and preparation method thereof |
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|---|---|---|---|---|
| GB1515963A (en) * | 1975-07-15 | 1978-06-28 | Massachusetts Inst Technology | Crosslinked collagen-mucopolysaccharide composite materials |
| US4562110A (en) * | 1981-08-18 | 1985-12-31 | Tong David Philip | Process for the production of alginate fibre material and products made therefrom |
| US4614794A (en) * | 1983-10-04 | 1986-09-30 | Johnson & Johnson | Protein/polysaccharide complexes |
| CN1687498A (en) * | 2005-04-27 | 2005-10-26 | 武汉大学 | Blended fiber of sodium alginate/glutin, preparation method and application thereof |
-
2006
- 2006-11-04 CN CNB2006100699793A patent/CN100457989C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1515963A (en) * | 1975-07-15 | 1978-06-28 | Massachusetts Inst Technology | Crosslinked collagen-mucopolysaccharide composite materials |
| US4562110A (en) * | 1981-08-18 | 1985-12-31 | Tong David Philip | Process for the production of alginate fibre material and products made therefrom |
| US4614794A (en) * | 1983-10-04 | 1986-09-30 | Johnson & Johnson | Protein/polysaccharide complexes |
| CN1687498A (en) * | 2005-04-27 | 2005-10-26 | 武汉大学 | Blended fiber of sodium alginate/glutin, preparation method and application thereof |
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Effective date of registration: 20160914 Address after: 266111, Shandong Qingdao hi tech Industrial Development Zone entrepreneurship Service Center SME incubator (Kam Yip Road No. 1), B2-1-A Patentee after: New Qingdao Mstar Technology Ltd Address before: 266071 Ningxia Road, Shandong, China, No. 308, No. Patentee before: Qingdao University |