CN107724074A - 一种水溶性壳聚糖纤维的制备方法 - Google Patents
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- 239000000835 fiber Substances 0.000 title claims abstract description 33
- 229920001661 Chitosan Polymers 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims description 11
- 229920002101 Chitin Polymers 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 230000001476 alcoholic effect Effects 0.000 claims abstract 2
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 239000001632 sodium acetate Substances 0.000 claims 1
- 235000017281 sodium acetate Nutrition 0.000 claims 1
- OVYTZAASVAZITK-UHFFFAOYSA-M sodium;ethanol;hydroxide Chemical compound [OH-].[Na+].CCO OVYTZAASVAZITK-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002537 cosmetic Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003115 biocidal effect Effects 0.000 abstract description 2
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- 239000004744 fabric Substances 0.000 abstract 2
- 239000000376 reactant Substances 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000006473 carboxylation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012620 biological material Substances 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
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- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/73—Polysaccharides
- A61K8/736—Chitin; Chitosan; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/28—Polysaccharides or their derivatives
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0023—Polysaccharides
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
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- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
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Abstract
本发明涉及一种以不溶于水的壳聚糖纤维为原料，采用氯乙酸钠为反应剂制备水溶性壳聚糖纤维的生产工艺新方法，其特征在于：采用氯乙酸钠为反应试剂，反应体系为一定浓度的碱醇溶液。所制备的壳聚糖纤维能够在pH为6.0‑8.0的范围内溶解，并保证干断裂强度≥1.15cN/dtex，取代度为＞70％，纯度≥80％。达到此项技术要求的壳聚糖纤维能够保持高抑菌性、柔软性、透气性及吸湿性，可用于织物及无纺布产品的制造，广泛用于医用敷料及化妆品原料技术领域。
Description
技术领域
本发明属于医用敷料及化妆品原料技术领域，公开了一种水溶性壳聚糖纤维的制备方法。
背景技术：
壳聚糖是一种具有优良的生物相容性、抗菌能力，止血能力和可生物降解的天然高分子材料，具有良好的成纤性。壳聚糖纤维即是以壳聚糖为主要原料，在适当的溶剂中将其溶解，配制成一定浓度的胶体纺丝原液，再经喷丝、凝固成形、拉伸等工艺，制备成具有一定机械强度的高分子功能性材料。
但由于壳聚糖只溶于酸性溶液而不溶于水的特性，目前壳聚糖纤维大部分用于织物及无纺布的产品的制造，限制了其在可溶性医用卫生材料及化妆品等领域的应用。由于纯壳聚糖纤维的高抑菌性、柔软性、透气性及吸湿性非常好，因此如何制备低成本、高性能的水溶性壳聚糖纤维成为医药及化妆品领域技术人员亟待解决的难题。
本发明将壳聚糖纤维进行接枝反应，羧化处理后可保持纤维的形态，并且能够在较广泛的pH范围内溶解，具有优良的吸湿保湿性、生物相容性、广谱抗菌性及生物可降解性等特殊功能，在医药、化妆品和生物保健品等领域有广泛的应用前景，具有巨大的经济效益和社会效益。
发明内容
本发明的目的在于：
针对市场需求及现有技术存在的缺陷，本发明所要解决的技术问题是，提供一种成本低廉、操作简便，节能降耗，应用广泛，具有纤维形态的水溶性壳聚糖纤维，本发明所采取的技术方案是：一种水溶性壳聚糖纤维的制备方法，包括以下制备步骤：
称取一定量的壳聚糖纤维投入到反应器中，加入10～20倍壳聚糖纤维重量的5～15％浓度的Na0H乙醇溶液，乙醇溶液浓度为60％～80％，再将2.0～3.0倍壳聚糖纤维重量的氯乙酸钠加入到体系中，在50～70℃保温条件下反应3.0～6.0h。反应结束后固液分离，用稀酸在乙醇溶液中调物料pH至中性，再用70～80％浓度的乙醇溶液洗涤两次，90～99％浓度乙醇脱水一次，晾干得产物。产物干断裂强度≥1.15cN/dtex，pH 6.0-8.0，取代度＞70％，纯度≥80％。
本发明相比现有壳聚糖羧化反应技术具有制备过程简单、易于控制、成本低等优点，具体如下：
1、此发明采用氯乙酸钠代替常规的氯乙酸进行反应，便于运输、储存，无刺激性及腐蚀性，操作简便，对反应设备材质的要求极低，极大地改善了生产环境。
2、此发明反应时间较短，碱的用量较少，原材料成本较低，工序简单，简化了生产流程配套设备，大幅降低了产品的制造成本。
3、此发明制备的产品水溶性较好，在广泛的pH范围内均能够完全溶解，产物具有纤维柔软形态，干断裂强度≥1.15cN/dtex，pH 6.0-8.0，取代度＞70％，纯度≥80％。
总之，本发明制备的壳聚糖纤维是一种新型水溶性生物材料，其制备过程简单，工作环境无刺激，生产流程较传统工艺简化，生产成本及对设备的要求极低，具有纤维形态的水溶性壳聚糖必将为医用敷料及化妆品行业的发展带来巨大的潜力。
附图说明
附图为水溶性壳聚糖纤维制备过程示意图，详见说明书附图。
具体实施方式
下面通过具体实施例进一步说明对本发明实施方式。
实施例1：
向安装有电动搅拌器的烧杯中加入200ml 65％的乙醇溶液，称量20gNaOH投入烧杯中，开启搅拌使其溶解均匀，加入20g壳聚糖纤维，再称量50g氯乙酸钠加入反应体系中，60℃保温条件下反应4.0h，反应结束后沥干反应液，用稀酸在乙醇溶液中调物料pH至中性，再用75％浓度的乙醇溶液洗涤两次，95％浓度乙醇脱水一次，晾干得产物，检测干断裂强度1.15cN/dtex，pH 7.4，取代度96.9％，纯度87.0％。
实施例2：
向安装有电动搅拌器的烧杯中加入200ml 70％的乙醇溶液，称量25gNaOH投入烧杯中，开启搅拌使其溶解均匀，加入20g壳聚糖纤维，再称量60g氯乙酸钠加入反应体系中，65℃保温条件下反应4.5h，反应结束后沥干反应液，用稀酸在乙醇溶液中调物料pH至中性，再用75％浓度的乙醇溶液洗涤两次，95％浓度乙醇脱水一次，晾干得产物，检测干断裂强度1.18cN/dtex，pH 7.5，取代度85.5％，纯度97.4％。
Claims (3)
1.一种水溶性壳聚糖纤维的制备方法，其特征在于：制备方法
称取一定量的壳聚糖纤维投入到反应器中，加入10～20倍壳聚糖纤维重量的10～20％浓度的NaOH乙醇溶液，乙醇溶液浓度为60％～80％，再将2.0～3.0倍壳聚糖纤维重量的氯乙酸钠加入到体系中，在50～70℃保温条件下反应3.0～6.0h。反应结束后固液分离，用稀酸在乙醇溶液中调物料pH至中性，再用70～80％浓度的乙醇溶液洗涤两次，90～99％浓度乙醇脱水一次，晾干得产物。
2.如权利要求1所述的水溶性壳聚糖纤维的制备方法，其特征在于：采用氯乙酸钠为反应试剂，采用一定浓度的碱醇溶液为反应体系。
3.如权利要求1所述的水溶性壳聚糖纤维的制备方法，其特征在于：所述水溶性羧甲基壳聚糖纤维的干断裂强度≥1.15cN/dtex，pH6.0-8.0，取代度为＞70％，纯度≥80％。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049513A (zh) * | 2007-05-13 | 2007-10-10 | 刘万顺 | 水溶性壳聚糖基纤维止血愈创材料及其制备方法和应用 |
| CN101368328A (zh) * | 2008-08-04 | 2009-02-18 | 东华大学 | 一种羟乙基壳聚糖纤维的制备方法 |
| CN103120802A (zh) * | 2012-07-26 | 2013-05-29 | 佛山市优特医疗科技有限公司 | 可溶性止血纱布及其制备方法 |
| US20140316361A1 (en) * | 2011-01-11 | 2014-10-23 | Medtrade Products Ltd. | Process for the manufacture of a dressing and dressing obtained |
| CN105153325A (zh) * | 2015-09-16 | 2015-12-16 | 中华全国供销合作总社南京野生植物综合利用研究所 | 一种羧甲基壳聚糖生产工艺技术的改进 |
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- 2017-07-31 CN CN201710658163.2A patent/CN107724074A/zh active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049513A (zh) * | 2007-05-13 | 2007-10-10 | 刘万顺 | 水溶性壳聚糖基纤维止血愈创材料及其制备方法和应用 |
| CN101368328A (zh) * | 2008-08-04 | 2009-02-18 | 东华大学 | 一种羟乙基壳聚糖纤维的制备方法 |
| US20140316361A1 (en) * | 2011-01-11 | 2014-10-23 | Medtrade Products Ltd. | Process for the manufacture of a dressing and dressing obtained |
| CN103120802A (zh) * | 2012-07-26 | 2013-05-29 | 佛山市优特医疗科技有限公司 | 可溶性止血纱布及其制备方法 |
| CN105153325A (zh) * | 2015-09-16 | 2015-12-16 | 中华全国供销合作总社南京野生植物综合利用研究所 | 一种羧甲基壳聚糖生产工艺技术的改进 |
Non-Patent Citations (1)
| Title |
|---|
| 于兹东等: "羧甲基壳聚糖的制备研究", 《广西轻工业》 * |
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