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CN1940153A - Chitose graft alginate fibre, its production and use - Google Patents

Chitose graft alginate fibre, its production and use Download PDF

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CN1940153A
CN1940153A CN 200610069064 CN200610069064A CN1940153A CN 1940153 A CN1940153 A CN 1940153A CN 200610069064 CN200610069064 CN 200610069064 CN 200610069064 A CN200610069064 A CN 200610069064A CN 1940153 A CN1940153 A CN 1940153A
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chitosan
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sodium alginate
fiber
mass percentage
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朱平
郭肖青
隋淑英
王炳
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Qingdao University
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Abstract

本发明公开了一种壳聚糖接枝海藻纤维及其制备方法与用途,其中该方法是将适量壳聚糖溶解于质量百分比为1%~2%的冰醋酸溶液中得到质量百分比为2%~6%的壳聚糖溶液;再配制质量百分比2%~5%的氯化钙溶液;然后将上述两种溶液按壳聚糖溶液在混合溶液中所占的质量百分比为25%~75%的比例充分混合,作为凝固浴,使质量百分比为3%~5%的海藻酸钠溶液再此凝固浴中成纤,经拉伸、干燥得壳聚糖接枝海藻纤维,纤维拉伸率为10%~30%。这种纤维由于表面包覆一定的壳聚糖,因而具有良好的吸湿性和抗菌性,且无毒、无害、安全性高及生物可降解性,在医药、环保等领域均有良好的应用前景,尤其适合于制造纱布作伤口敷料用。

Figure 200610069064

The invention discloses a chitosan grafted seaweed fiber and its preparation method and application, wherein the method is to dissolve an appropriate amount of chitosan in a glacial acetic acid solution with a mass percentage of 1% to 2% to obtain a mass percentage of 2% ~6% chitosan solution; then prepare 2%~5% calcium chloride solution by mass percentage; The proportion of the mixture is fully mixed, as a coagulation bath, the sodium alginate solution with a mass percentage of 3% to 5% is then formed into fibers in the coagulation bath, and the chitosan-grafted seaweed fiber is obtained after stretching and drying. The fiber stretching rate is 10% to 30%. Because the surface of this fiber is coated with a certain amount of chitosan, it has good hygroscopicity and antibacterial properties, and is non-toxic, harmless, high in safety and biodegradable, and has good applications in the fields of medicine and environmental protection. Prospect, especially suitable for making gauze for wound dressing.

Figure 200610069064

Description

壳聚糖接枝海藻纤维及其制备方法与用途Chitosan grafted seaweed fiber and its preparation method and application

技术领域technical field

本发明涉及一种可用于制作无纺布和纺织品的壳聚糖接枝海藻纤维,及其制备方法与用途。The invention relates to a chitosan grafted seaweed fiber which can be used for making non-woven fabrics and textiles, and a preparation method and application thereof.

背景技术Background technique

海藻酸钠是从褐藻类的海带或马尾藻中提取的一种多糖碳水化合物,它是由β-D-甘露糖醛酸和α-L-古罗糖醛酸组成的多糖。以含Ca2+的溶液为凝固浴,海藻酸钠可以通过湿法纺丝法制成纤维。纤维制成敷料与伤口接触时,纤维中的Ca2+可以与人体伤口分泌物中的Na+进行离子交换在伤口处形成湿态凝胶。但该凝胶如不及时清除能吸附大量的细菌,导致伤口被感染,在一定程度上也限制了海藻纤维的广泛应用。壳聚糖广泛存在于虾、蟹、蛹及昆虫等动物外壳以及菌类、藻类植物的细胞壁中,是甲壳素最基本、最重要的衍生物,它与生物组织具有良好的亲和性,能被人体内组织液降解而吸收,且具有生物可降解性、抗菌、防腐、止血和促进伤口愈合等优良性能。Sodium alginate is a polysaccharide carbohydrate extracted from brown algae kelp or sargassum, which is a polysaccharide composed of β-D-mannuronic acid and α-L-guluronic acid. Using a solution containing Ca 2+ as a coagulation bath, sodium alginate can be made into fibers by wet spinning. When the dressing made of fiber is in contact with the wound, the Ca 2+ in the fiber can conduct ion exchange with Na + in the wound secretion of the human body to form a wet gel at the wound. However, if the gel is not removed in time, it can absorb a large number of bacteria, leading to wound infection, which also limits the wide application of seaweed fiber to a certain extent. Chitosan widely exists in animal shells such as shrimps, crabs, pupae, and insects, as well as in the cell walls of fungi and algae. It is the most basic and important derivative of chitin. It has good affinity with biological tissues and can It is degraded and absorbed by the tissue fluid in the human body, and has excellent properties such as biodegradability, antibacterial, antiseptic, hemostasis and promotion of wound healing.

发明内容Contents of the invention

本发明的任务之一在于提供一种综合性能较为理想的壳聚糖接枝海藻纤维,该纤维具有优异的力学性能和抗菌性能。One of the tasks of the present invention is to provide a chitosan-grafted seaweed fiber with ideal comprehensive properties, which has excellent mechanical properties and antibacterial properties.

本发明的任务之二在于提供一种制备壳聚糖接枝海藻纤维的方法。The second task of the present invention is to provide a method for preparing chitosan-grafted seaweed fiber.

本发明任务之三在于提供壳聚糖接枝海藻纤维的用途。The third task of the present invention is to provide the purposes of chitosan grafted seaweed fiber.

为实现本发明任务一,其技术解决方案是:For realizing task one of the present invention, its technical solution is:

一种壳聚糖接枝海藻纤维,在其纤维分子中,壳聚糖大分子接枝海藻酸钠大分子。The invention relates to chitosan grafted seaweed fiber, in which macromolecules of chitosan are grafted with macromolecules of sodium alginate.

上述壳聚糖接枝海藻纤维,其单纤维表层为壳聚糖包覆层。The chitosan-grafted seaweed fiber has a chitosan coating layer on the surface of the single fiber.

为实现本发明任务二,其技术解决方案是:For realizing task two of the present invention, its technical solution is:

一种壳聚糖接枝海藻纤维的制备方法,采取海藻酸钠水溶液与壳聚糖溶液,二者之间进行离子交联获得壳聚糖接枝海藻酸钠,并用湿法纺丝法制成纤维。A preparation method of chitosan-grafted seaweed fiber, which comprises taking sodium alginate aqueous solution and chitosan solution, performing ion cross-linking between the two to obtain chitosan-grafted sodium alginate, and making fibers by wet spinning .

上述制备方法,其有以下具体步骤:Above-mentioned preparation method, it has the following specific steps:

(1)将适量海藻酸钠溶于水制取质量百分比为3%~5%的海藻酸钠溶液;(1) Dissolving an appropriate amount of sodium alginate in water to prepare a sodium alginate solution with a mass percentage of 3% to 5%;

(2)将适量壳聚糖溶于质量百分比为1%~2%的冰醋酸溶液中,制取质量百分比为2%~6%的壳聚糖溶液;(2) Dissolving an appropriate amount of chitosan in a glacial acetic acid solution with a mass percentage of 1% to 2% to prepare a chitosan solution with a mass percentage of 2% to 6%;

(3)将适量氯化钙溶于水中制取质量百分比为2%~5%的氯化钙溶液;(3) Dissolving an appropriate amount of calcium chloride in water to prepare a calcium chloride solution with a mass percentage of 2% to 5%;

(4)将步骤(2)和步骤(3)制取的两种溶液按壳聚糖溶液在混合溶液中所占的体积百分比为25%~75%的比例充分混合,制取凝固浴;(4) two kinds of solutions prepared by step (2) and step (3) are fully mixed in the ratio of 25% to 75% according to the volume percentage of chitosan solution in the mixed solution to prepare a coagulation bath;

(5)将步骤(1)制取的海藻酸钠溶液经过滤、减压脱泡后,于室温在足量的步骤(4)制取的凝固浴中以湿法纺丝法制取壳聚糖接枝海藻纤维,其纤维拉伸率为10%~30%。(5) After the sodium alginate solution prepared in step (1) is filtered and degassed under reduced pressure, chitosan is prepared by wet spinning in a sufficient amount of coagulation bath prepared in step (4) at room temperature The grafted seaweed fiber has a fiber elongation rate of 10% to 30%.

上述制备海藻酸钠溶液、壳聚糖溶液及氯化钙溶液所用的水优选为蒸馏水。The water used for the above-mentioned preparation of sodium alginate solution, chitosan solution and calcium chloride solution is preferably distilled water.

为实现本发明任务三,其技术解决方案是:For realizing task three of the present invention, its technical solution is:

一种壳聚糖接枝海藻纤维,其用于制备无纺布作为伤口敷料或纺织品。A chitosan-grafted seaweed fiber is used to prepare non-woven fabrics as wound dressings or textiles.

本发明中壳聚糖接枝海藻纤维,不仅具有海藻酸钠和壳聚糖的优点,而且由于两者之间的交联,纤维的力学性能较好,且由于这种纤维表面包覆一定的壳聚糖,因而具有良好的吸湿性和抗菌性,无毒、无害、安全性高及生物可降解性,其原料来源丰富,在医药、环保等领域均有良好的应用前景,尤其适合于制造纱布作伤口敷料用。Chitosan grafted seaweed fiber in the present invention not only has the advantages of sodium alginate and chitosan, but also has better mechanical properties of the fiber due to the crosslinking between the two, and because the surface of the fiber is covered with a certain Chitosan, therefore has good hygroscopicity and antibacterial properties, non-toxic, harmless, high safety and biodegradability, its raw material sources are abundant, and it has good application prospects in the fields of medicine and environmental protection, especially suitable Manufacture of gauze for wound dressings.

附图说明Description of drawings

图1为壳聚糖接枝海藻酸钠交联结构式示意简图。Fig. 1 is a schematic diagram of chitosan grafted sodium alginate cross-linked structure.

图2为壳聚糖接枝海藻酸钠纤维的横截面示意图。Figure 2 is a schematic cross-sectional view of chitosan-grafted sodium alginate fibers.

具体实施方式Detailed ways

本发明中,由于海藻酸钠水溶液与壳聚糖溶液带有相反电性的电荷,利用二者之间的离子交联,可以制备壳聚糖接枝海藻酸钠,即在其纤维分子中,壳聚糖大分子接枝海藻酸钠大分子。在制取的壳聚糖接枝海藻纤维中,优选其单纤维表层为壳聚糖包覆层的纤维成品,参见图1及图2。In the present invention, since the sodium alginate aqueous solution and the chitosan solution have opposite electrical charges, the ionic cross-linking between the two can be used to prepare chitosan-grafted sodium alginate, that is, in its fiber molecules, Chitosan macromolecule grafted sodium alginate macromolecule. Among the prepared chitosan-grafted seaweed fibers, it is preferred that the single fiber surface layer is a finished fiber product with a chitosan coating layer, as shown in Fig. 1 and Fig. 2 .

实施例1:取30g海藻酸钠溶于970mL蒸馏水得到3%(质量百分比)的海藻酸钠溶液;取适量的壳聚糖,溶解到1%(质量百分比)的醋酸溶液中得到2%(质量百分比)的壳聚糖溶液;配制5%的氯化钙溶液。将海藻酸钠溶液经过滤、减压脱泡后,于室温在组成为壳聚糖溶液与氯化钙溶液体积比为3∶1的混合液的凝固浴中通过湿法纺丝法制备壳聚糖接枝海藻纤维,纤维拉伸率可达30%。并可进一步作为纤维原料制造无纺纱布作伤口敷料用。Embodiment 1: get 30g sodium alginate and be dissolved in 970mL distilled water and obtain the sodium alginate solution of 3% (mass percentage); Get an appropriate amount of chitosan, be dissolved in the acetic acid solution of 1% (mass percentage) to obtain 2% (mass percentage) percentage) chitosan solution; prepare 5% calcium chloride solution. After the sodium alginate solution is filtered and defoamed under reduced pressure, chitosan is prepared by wet spinning in a coagulation bath composed of a mixture of chitosan solution and calcium chloride solution with a volume ratio of 3:1 at room temperature. Sugar grafted seaweed fiber, the fiber stretch rate can reach 30%. And it can be further used as fiber raw material to make non-woven gauze for wound dressing.

实施例2:取40g海藻酸钠溶于960mL蒸馏水得到4%(质量百分比)的海藻酸钠溶液;取适量的壳聚糖,溶解到1.5%(质量百分比)的醋酸溶液中得到4%的壳聚糖溶液;配制4%的氯化钙溶液。将海藻酸钠溶液经过滤、减压脱泡后,于室温在组成为壳聚糖溶液与氯化钙溶液体积比为2∶1的混合液的凝固浴中通过湿法纺丝法制备壳聚糖接枝海藻纤维,纤维拉伸率可达20%。并可进一步作为纤维原料制造无纺纱布作伤口敷料用。Embodiment 2: get 40g sodium alginate and be dissolved in 960mL distilled water and obtain 4% (mass percentage) sodium alginate solution; Take appropriate amount of chitosan, dissolve in the acetic acid solution of 1.5% (mass percentage) to obtain 4% shell Polysaccharide solution; prepare 4% calcium chloride solution. After the sodium alginate solution is filtered and defoamed under reduced pressure, chitosan is prepared by wet spinning in a coagulation bath composed of a mixture of chitosan solution and calcium chloride solution with a volume ratio of 2:1 at room temperature. Sugar grafted seaweed fiber, the fiber stretch rate can reach 20%. And it can be further used as fiber raw material to make non-woven gauze for wound dressing.

实施例3:取50g海藻酸钠溶于950mL蒸馏水得到5%(质量百分比)的海藻酸钠溶液;取适量的壳聚糖,溶解到2%(质量百分比)的醋酸溶液中得到6%(质量百分比)的壳聚糖溶液;配制2%(质量百分比)的氯化钙溶液。将海藻酸钠溶液经过滤、减压脱泡后,于室温在组成为壳聚糖溶液与氯化钙溶液体积比为1∶1的混合液的凝固浴中通过湿法纺丝法制备壳聚糖接枝海藻纤维,纤维拉伸率可达10%。并可进一步作为纤维原料制造无纺纱布作伤口敷料用。Embodiment 3: get 50g sodium alginate and be dissolved in 950mL distilled water and obtain the sodium alginate solution of 5% (mass percentage); Get an appropriate amount of chitosan, be dissolved in the acetic acid solution of 2% (mass percentage) to obtain 6% (mass percentage) percentage) chitosan solution; prepare 2% (mass percentage) calcium chloride solution. After the sodium alginate solution is filtered and defoamed under reduced pressure, chitosan is prepared by wet spinning in a coagulation bath composed of a mixture of chitosan solution and calcium chloride solution with a volume ratio of 1:1 at room temperature. Sugar grafted seaweed fiber, the fiber stretch rate can reach 10%. And it can be further used as fiber raw material to make non-woven gauze for wound dressing.

实施例4:取50g海藻酸钠溶于950mL蒸馏水得到5%(质量百分比)的海藻酸钠溶液;取适量的壳聚糖,溶解到2%(质量百分比)的醋酸溶液中得到6%(质量百分比)的壳聚糖溶液;配制2%(质量百分比)的氯化钙溶液。将海藻酸钠溶液经过滤、减压脱泡后,于室温在组成为壳聚糖溶液与氯化钙溶液体积比为1∶3的混合液的凝固浴中通过湿法纺丝法制备壳聚糖接枝海藻纤维,纤维拉伸率可达10%。并可进一步作为纤维原料制造无纺纱布作伤口敷料用。Embodiment 4: get 50g sodium alginate and be dissolved in 950mL distilled water and obtain the sodium alginate solution of 5% (mass percentage); Get an appropriate amount of chitosan, be dissolved in the acetic acid solution of 2% (mass percentage) to obtain 6% (mass percentage) percentage) chitosan solution; prepare 2% (mass percentage) calcium chloride solution. After the sodium alginate solution is filtered and defoamed under reduced pressure, chitosan is prepared by wet spinning in a coagulation bath composed of a mixture of chitosan solution and calcium chloride solution with a volume ratio of 1:3 at room temperature. Sugar grafted seaweed fiber, the fiber stretch rate can reach 10%. And it can be further used as fiber raw material to make non-woven gauze for wound dressing.

将实施例1、2、3(或4)所得产物进行力学性能和抗菌性能测试,测试结果见下表。The product obtained in Examples 1, 2, 3 (or 4) is tested for mechanical properties and antibacterial properties, and the test results are shown in the table below.

                             壳聚糖接枝海藻纤维的力学性能   干态抗张强度cN/dtex   干态断裂伸长率%   湿态抗张强度cN/dtex 湿态断裂伸长率%   实施例1实施例2实施例3   1.932.112.04   22.3420.5821.77   2.562.782.69 56.4462.3660.91 Mechanical Properties of Chitosan Grafted Seaweed Fiber Dry Tensile StrengthcN/dtex Dry elongation at break% Wet tensile strengthcN/dtex Wet elongation at break% Example 1 Example 2 Example 3 1.932.112.04 22.3420.5821.77 2.562.782.69 56.4462.3660.91

              壳聚糖接枝海藻纤维的抗菌性能     金黄色葡萄球菌          大肠杆菌   抑菌性   杀菌性   抑菌性   杀菌性   实施例1实施例2实施例3   2.89333.25273.0139   0.25840.40000.3782   2.65123.00242.9278   0.20140.36910.3235 Antibacterial properties of chitosan-grafted seaweed fiber Staphylococcus aureus Escherichia coli Bacteriostatic Bactericidal Bacteriostatic Bactericidal Example 1 Example 2 Example 3 2.89333.25273.0139 0.25840.40000.3782 2.65123.00242.9278 0.20140.36910.3235

从上述数据可以看出,壳聚糖接枝海藻纤维具有良好的力学性能和抗菌性能。It can be seen from the above data that the chitosan-grafted seaweed fiber has good mechanical properties and antibacterial properties.

制取的壳聚糖接枝海藻酸钠纤维的横截面参见图2,其中1为壳聚糖包覆层,2为海藻酸钠纤维芯。The cross-section of the prepared chitosan-grafted sodium alginate fiber is shown in Fig. 2, wherein 1 is the chitosan coating layer, and 2 is the sodium alginate fiber core.

Claims (6)

1, a kind of chitose graft alginate fibre is characterised in that: in its fiber molecule, and the big molecule of the big molecule grafting of shitosan sodium alginate.
2, chitose graft alginate fibre according to claim 1 is characterized in that: its filament top layer is the shitosan clad.
3, a kind of preparation method of chitose graft alginate fibre is characterized in that: take sodium alginate aqueous solution and chitosan solution, carry out ionomer between the two and obtain the chitosan graft sodium alginate, and make fiber with wet spinning.
4, the preparation method of chitose graft alginate fibre according to claim 3, it has following concrete steps:
(1) be 3%~5% sodium alginate soln with the water-soluble mass percent of producing of an amount of sodium alginate;
(2) an amount of shitosan being dissolved in mass percent is in 1%~2% the glacial acetic acid solution, produces mass percent and be 2%~6% chitosan solution;
(3) be 2%~5% calcium chloride solution with an amount of calcium chloride mass percent of producing soluble in water;
(4) two kinds of solution that step (2) and step (3) are produced are that 25%~75% ratio is fully mixed in chitosan solution shared percent by volume in mixed solution, produce coagulating bath;
(5) sodium alginate soln that step (1) is produced after filtration, behind the vacuum deaerator, in the coagulating bath that the step (4) of capacity is produced, produce chitose graft alginate fibre with wet spinning process in room temperature, its tensile fiber rate is 10%~30%.
5, the preparation method of chitose graft alginate fibre according to claim 4 is characterized in that: described preparation sodium alginate soln, chitosan solution and the used water of calcium chloride solution are preferably distilled water.
6, a kind of chitose graft alginate fibre, it is used to prepare nonwoven fabric as wound dressing.
CN 200610069064 2006-09-21 2006-09-21 Chitose graft alginate fibre, its production and use Pending CN1940153A (en)

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CN101665995B (en) * 2008-09-05 2011-09-14 中国科学院大连化学物理研究所 Sodium alga acid/chitosan composite fluid spinning method
CN101736440B (en) * 2010-01-08 2012-04-18 武汉科技学院 Manufacturing method of dyeable alginate fiber
CN103174017A (en) * 2013-04-15 2013-06-26 青岛明月生物医用材料有限公司 Sodium alginate oxide modified chitosan fiber and preparation method and application thereof
CN103243557A (en) * 2013-05-22 2013-08-14 青岛明月生物医用材料有限公司 Oxidized sodium alginate modified textile fiber as well as preparation method and application thereof
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CN106637504A (en) * 2016-10-21 2017-05-10 周荣 Preparation method of sodium alginate fiber for surgical dressing
CN109234849A (en) * 2018-09-05 2019-01-18 重庆爱阳生物科技有限公司 A kind of medical ocean fiber of chitosan oligosaccharide and preparation method thereof
CN109629041A (en) * 2018-11-01 2019-04-16 泰州乐宁智能科技有限公司 A kind of fibrosis production technology of marine algae extract
CN110227175A (en) * 2019-05-13 2019-09-13 浙江惠龙医疗科技股份有限公司 It is a kind of with antibacterial, the medical dressing that can promote wound healing and preparation method thereof
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CN111533825A (en) * 2020-06-17 2020-08-14 昆山京昆油田化学科技有限公司 Glucosamine grafted sodium alginate derivative and preparation method and application thereof
CN113638078A (en) * 2021-07-20 2021-11-12 东华大学 A kind of polyelectrolyte composite hydrogel fiber and preparation method thereof
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CN100457990C (en) * 2007-04-16 2009-02-04 青岛大学 Producing method and use for common and functional calcium alginate fiber
CN101665995B (en) * 2008-09-05 2011-09-14 中国科学院大连化学物理研究所 Sodium alga acid/chitosan composite fluid spinning method
CN101736440B (en) * 2010-01-08 2012-04-18 武汉科技学院 Manufacturing method of dyeable alginate fiber
CN103174017A (en) * 2013-04-15 2013-06-26 青岛明月生物医用材料有限公司 Sodium alginate oxide modified chitosan fiber and preparation method and application thereof
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CN103243557A (en) * 2013-05-22 2013-08-14 青岛明月生物医用材料有限公司 Oxidized sodium alginate modified textile fiber as well as preparation method and application thereof
CN103966693A (en) * 2014-04-23 2014-08-06 安徽依采妮纤维材料科技有限公司 Mould-proof plant fiber fabric and preparation method thereof
CN104674375A (en) * 2015-02-09 2015-06-03 大连工业大学 Preparation method of composite fiber for wig
CN104674375B (en) * 2015-02-09 2016-08-17 大连工业大学 A kind of preparation method of wig composite fibre
CN105239199A (en) * 2015-10-20 2016-01-13 湖州申祥丝织有限责任公司 Novel composite fiber based on sweet sorghum skin fiber and preparation method thereof
CN106637504A (en) * 2016-10-21 2017-05-10 周荣 Preparation method of sodium alginate fiber for surgical dressing
CN109234849B (en) * 2018-09-05 2021-04-09 重庆爱阳生物科技有限公司 Chitosan oligosaccharide medical marine fiber and preparation method thereof
CN109234849A (en) * 2018-09-05 2019-01-18 重庆爱阳生物科技有限公司 A kind of medical ocean fiber of chitosan oligosaccharide and preparation method thereof
CN109629041A (en) * 2018-11-01 2019-04-16 泰州乐宁智能科技有限公司 A kind of fibrosis production technology of marine algae extract
CN110227175A (en) * 2019-05-13 2019-09-13 浙江惠龙医疗科技股份有限公司 It is a kind of with antibacterial, the medical dressing that can promote wound healing and preparation method thereof
CN111118711A (en) * 2019-09-09 2020-05-08 宁波大千纺织品有限公司 Alginate fiber health-care antibacterial fabric and manufacturing method thereof
CN110670220A (en) * 2019-11-06 2020-01-10 宁波大千纺织品有限公司 Anti-radiation knitted fabric and knitting method thereof
CN111466612A (en) * 2020-05-11 2020-07-31 湖北中烟工业有限责任公司 A cellulose-containing cigarette filter adsorption material
CN111534090A (en) * 2020-06-02 2020-08-14 金寨宏伟新材料有限公司 Cavity type nylon heat insulation strip and preparation method thereof
CN111533825A (en) * 2020-06-17 2020-08-14 昆山京昆油田化学科技有限公司 Glucosamine grafted sodium alginate derivative and preparation method and application thereof
CN111533825B (en) * 2020-06-17 2022-03-01 昆山京昆油田化学科技有限公司 Glucosamine grafted sodium alginate derivative and preparation method and application thereof
CN113638078A (en) * 2021-07-20 2021-11-12 东华大学 A kind of polyelectrolyte composite hydrogel fiber and preparation method thereof
CN116411365A (en) * 2021-12-30 2023-07-11 江南大学 A kind of preparation method of chitosan/calcium alginate composite monofilament
CN116411365B (en) * 2021-12-30 2025-03-11 江南大学 Preparation method of chitosan/calcium alginate composite monofilament

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