CN110158199B - Preparation method of biomass fiber capable of shielding ultraviolet rays - Google Patents

Preparation method of biomass fiber capable of shielding ultraviolet rays Download PDF

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CN110158199B
CN110158199B CN201910574494.7A CN201910574494A CN110158199B CN 110158199 B CN110158199 B CN 110158199B CN 201910574494 A CN201910574494 A CN 201910574494A CN 110158199 B CN110158199 B CN 110158199B
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agar
solution
biomass fiber
ultraviolet rays
shielding
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CN110158199A (en
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卢麒麟
冉琳琳
陈勤
陈世超
周荣
杨繁
李永贵
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Minjiang University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0036Galactans; Derivatives thereof
    • C08B37/0039Agar; Agarose, i.e. D-galactose, 3,6-anhydro-D-galactose, methylated, sulfated, e.g. from the red algae Gelidium and Gracilaria; Agaropectin; Derivatives thereof, e.g. Sepharose, i.e. crosslinked agarose
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Textile Engineering (AREA)
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  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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Abstract

The invention discloses a preparation method of biomass fiber for shielding ultraviolet rays, which utilizes hydroxyl in an agar structure to react with citric acid and ethylenediamine, introduces a thiazolopyridine carboxylic acid structure with an ultraviolet ray absorption effect on agar, utilizes tannin as a cross-linking agent to improve the mechanical property of the agar, and ensures that the biomass fiber has good air permeability, skin friendliness, comfort and biodegradability of the biomass fiber, also has excellent mechanical property of chemical fiber, and simultaneously has good ultraviolet ray shielding capability. The method has the advantages of simple process, easy operation, rich raw material sources, low cost, no toxicity and high safety, and the prepared biomass fiber has good ultraviolet shielding performance, good stability, high mechanical strength, air permeability, skin friendliness and biodegradability.

Description

Preparation method of biomass fiber capable of shielding ultraviolet rays
Technical Field
The invention belongs to the technical field of natural polymers and textiles, and particularly relates to a preparation method of biomass fibers for shielding ultraviolet rays.
Background
The incidence of skin diseases increases year by year in recent years, and research results show that ultraviolet rays are the most powerful cause of skin wrinkles, aging, laxity and black spots. Ultraviolet radiation causes the skin to generate a large number of free radicals, which results in a peroxidation of cell membranes, producing more melanin and spreading up the stratum corneum, resulting in black spots. Ultraviolet B (UVB) rays act on the surface layer of the skin, which causes denaturation of nucleic acids or proteins in skin cells, skin aging, and in severe cases, skin cancer. Ultraviolet a (uva) penetration into clothes and skin is deeper than UVB, causing pigmentation of melanin, resulting in skin aging. Therefore, the fabric with the ultraviolet shielding function is developed, and the health of the human body is effectively protected.
At present, there are two main methods for producing fabrics with ultraviolet shielding function at home and abroad: one is that ultraviolet screening agent is added in fiber production to produce ultraviolet resistant fiber, and then the ultraviolet resistant fiber is utilized to produce fabric, which has the function of screening ultraviolet; however, the method has high technical requirements, complex process and high production cost, is only suitable for the production of chemical fibers and is not suitable for natural fibers. Another one isThe method adopts nano TiO2The method is simple and easy to implement, but the nano ultraviolet screening agent is only attached to the surface of the fabric, is poor in washing resistance, is easy to abrade and wash off, loses the functionality of the fabric, and is reduced in comfort and hand feeling of the fabric. In a word, the ultraviolet shielding fabric produced according to the current method has poor ultraviolet shielding effect, poor wearability, poor air permeability, strong chemical fiber feeling and poor wearing comfort. Therefore, how to develop a biomass fiber which has good ultraviolet shielding performance, high mechanical strength, air permeability and skin affinity and is biodegradable is a key problem which needs to be solved urgently and is the development trend of the current functional textile materials.
Disclosure of Invention
The invention aims to provide a preparation method of biomass fiber for shielding ultraviolet rays, aiming at the defects of the performance and the preparation method of the existing ultraviolet-resistant fiber. The invention utilizes the reaction of hydroxyl in an agar structure with citric acid and ethylenediamine, introduces a thiazolopyridine carboxylic acid structure with ultraviolet absorption effect on agar, then utilizes a natural plant extract-tannin with rich sources as a cross-linking agent, improves the mechanical property of the biomass fiber based on the hydrogen bond bonding effect between phenolic hydroxyl in tannin molecules and hydroxyl in the agar, and simultaneously can further improve the ultraviolet absorption capacity of the biomass fiber due to the existence of a benzene ring structure in the tannin molecules. Compared with the existing production technology of the anti-ultraviolet fiber, the method has the advantages of simple process, easy operation, rich resources, low cost, no toxicity and high safety because the tannin and the agar are both derived from natural plants, and the prepared biomass fiber has the advantages of good ultraviolet shielding performance, good stability, high mechanical strength, air permeability, skin friendliness and biodegradability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of biomass fiber for shielding ultraviolet rays comprises the following steps:
(1) adding agar into distilled water, heating to 70 ℃ until the agar is completely dissolved to prepare agar solution with a certain concentration, dissolving citric acid and ethylenediamine into the agar solution according to a certain stoichiometric ratio, placing the agar solution into a round-bottomed flask, carrying out condensation reflux reaction, and introducing a thiazolopyridine carboxylic acid structure into the agar to form modified agar suspension;
(2) carrying out centrifugal washing on the modified agar suspension liquid for multiple times by using distilled water, and adding water to prepare a modified agar solution with a certain concentration; dissolving tannic acid in the modified agar solution, adjusting the pH value to 6.5 by using dilute hydrochloric acid, stirring and reacting for 1-3h at 70 ℃ to form uniform mixed solution, and carrying out solution spinning on the mixed solution to obtain the biomass fiber for shielding ultraviolet rays.
In the step (1), the concentration of the agar solution is 5wt% -20wt%, the molar ratio of the citric acid to the ethylenediamine is 1:0.5-1:2, the condensation reflux reaction temperature is 90-130 ℃, and the time is 6-12 h.
The concentration of the modified agar solution prepared in the step (2) is 3wt% -10wt%, and the mass ratio of the tannic acid to the modified agar solution is 1:30-1: 200.
The invention has the following remarkable advantages:
(1) the method has simple process and easy operation, and the tannin and the agar are both from natural plants, so the method has rich resources, low cost, no toxicity and high safety;
(2) the biomass fiber for shielding ultraviolet rays prepared by the invention has the advantages of good ultraviolet ray shielding performance, good stability, high mechanical strength, air permeability, skin friendliness and biodegradability.
Drawings
FIG. 1 is a diagram of a biomass fiber object for shielding ultraviolet rays according to the present invention.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Adding 5g of agar into 95mL of distilled water, heating at 70 ℃ until the agar is completely dissolved to prepare an agar solution with the concentration of 5wt%, respectively dissolving 10M of citric acid and 5M of ethylenediamine into the agar solution, placing the agar solution into a round-bottom flask, and carrying out condensation reflux reaction at 90 ℃ for 12 hours to form a modified agar suspension;
(2) taking the modified agar suspension, carrying out centrifugal washing for many times by using distilled water, and adding water to prepare a modified agar solution with the concentration of 3 wt%; dissolving 2g of tannic acid in 60g of modified agar solution, adjusting pH to 6.5 with dilute hydrochloric acid, stirring at 70 deg.C for 1h to obtain a uniform mixed solution, and performing solution spinning on the mixed solution to obtain the biomass fiber for shielding ultraviolet rays, as shown in FIG. 1.
Example 2
(1) Adding 8g of agar into 92mL of distilled water, heating at 70 ℃ until the agar is completely dissolved to prepare agar solution with the concentration of 8wt%, respectively dissolving 15M of citric acid and 9M of ethylenediamine into the agar solution, placing the agar solution in a round-bottom flask, and carrying out condensation reflux reaction for 7 hours at 90 ℃ to form modified agar suspension;
(2) carrying out centrifugal washing on the modified agar suspension liquid for multiple times by using distilled water, and adding water to prepare a modified agar solution with the concentration of 4 wt%; dissolving 5g of tannic acid in 160g of modified agar solution, adjusting the pH value to 6.5 by using dilute hydrochloric acid, stirring and reacting for 3 hours at 70 ℃ to form uniform mixed solution, and carrying out solution spinning on the mixed solution to obtain the biomass fiber for shielding ultraviolet rays.
Example 3
(1) Adding 10g of agar into 90mL of distilled water, heating at 70 ℃ until the agar is completely dissolved to prepare agar solution with the concentration of 10wt%, respectively dissolving 10M of citric acid and 10M of ethylenediamine into the agar solution, placing the agar solution into a round-bottom flask, and carrying out condensation reflux reaction for 8 hours at 110 ℃ to form modified agar suspension;
(2) carrying out centrifugal washing on the modified agar suspension liquid for multiple times by using distilled water, and adding water to prepare a modified agar solution with the concentration of 7 wt%; dissolving 2g of tannic acid in 200g of modified agar solution, adjusting the pH value to 6.5 by using dilute hydrochloric acid, stirring and reacting for 2 hours at 70 ℃ to form uniform mixed solution, and carrying out solution spinning on the mixed solution to obtain the biomass fiber for shielding ultraviolet rays.
Example 4
(1) Adding 20g of agar into 80mL of distilled water, heating at 70 ℃ until the agar is completely dissolved to prepare agar solution with the concentration of 20wt%, respectively dissolving 10M citric acid and 20M ethylenediamine into the agar solution, placing the agar solution in a round-bottom flask, and carrying out condensation reflux reaction at 125 ℃ for 11 hours to form modified agar suspension;
(2) taking the modified agar suspension, carrying out centrifugal washing for many times by using distilled water, and adding water to prepare a modified agar solution with the concentration of 9 wt%; dissolving 1g of tannic acid in 200g of modified agar solution, adjusting the pH value to 6.5 by using dilute hydrochloric acid, stirring and reacting for 3 hours at 70 ℃ to form uniform mixed solution, and performing solution spinning on the mixed solution to obtain the ultraviolet shielding biomass fiber.
Comparative example 1
(1) Adding 5g of agar into 95mL of distilled water, heating at 70 ℃ until the agar is completely dissolved to prepare an agar solution with the concentration of 5wt%, respectively dissolving 10M of citric acid and 10M of ethylenediamine into the agar solution, placing the agar solution into a round-bottom flask, and carrying out condensation reflux reaction for 10 hours at 100 ℃ to form a modified agar suspension;
(2) and (3) taking the modified agar suspension, carrying out multiple times of centrifugal washing by using distilled water, adding water to prepare a modified agar solution with the concentration of 5wt%, and then carrying out solution spinning to prepare the ultraviolet shielding biomass fiber.
The performance of the ultraviolet shielding biomass fibers prepared in the examples is tested, and the results are shown in table 1.
Table 1 performance testing of different uv-screening biomass fibers
Figure DEST_PATH_IMAGE002
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (6)

1. A preparation method of biomass fiber for shielding ultraviolet rays is characterized by comprising the following steps: the method comprises the following steps:
(1) adding agar into distilled water, heating to 70 ℃ until the agar is completely dissolved to prepare agar solution with a certain concentration, dissolving citric acid and ethylenediamine into the agar solution according to a certain stoichiometric ratio, placing the agar solution into a round-bottomed flask, carrying out condensation reflux reaction, and introducing a thiazole-like ropyridine carboxylic acid structure into the agar to form modified agar suspension;
(2) carrying out centrifugal washing on the modified agar suspension liquid for multiple times by using distilled water, and adding water to prepare a modified agar solution with a certain concentration; dissolving tannic acid in the modified agar solution, adjusting the pH value to 6.5 by using dilute hydrochloric acid, stirring and reacting for 1-3h at 70 ℃ to form uniform mixed solution, and carrying out solution spinning on the mixed solution to obtain the biomass fiber for shielding ultraviolet rays.
2. The method for preparing biomass fiber for shielding ultraviolet rays as set forth in claim 1, wherein: in the step (1), the concentration of the agar solution is 5wt% -20wt%, and the molar ratio of the citric acid to the ethylenediamine is 1:0.5-1: 2.
3. The method for preparing biomass fibers for shielding ultraviolet rays as claimed in claim 1, wherein: in the step (1), the temperature of the condensation reflux reaction is 90-130 ℃, and the time is 6-12 h.
4. The method for preparing biomass fiber for shielding ultraviolet rays as set forth in claim 1, wherein: the concentration of the modified agar solution prepared in the step (2) is 3wt% -10 wt%.
5. The method for preparing biomass fiber for shielding ultraviolet rays as set forth in claim 1, wherein: the mass ratio of the tannic acid to the modified agar solution in the step (2) is 1:30-1: 200.
6. The ultraviolet shielding biomass fiber prepared by the method of any one of claims 1 to 5.
CN201910574494.7A 2019-06-28 2019-06-28 Preparation method of biomass fiber capable of shielding ultraviolet rays Active CN110158199B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101358382A (en) * 2008-08-26 2009-02-04 东华大学 Antibacterial nano fiber material and preparation method thereof
CN102154738A (en) * 2011-05-10 2011-08-17 青岛大学 Method for preparing red algae agar fiber
CN104562438A (en) * 2013-10-17 2015-04-29 中国科学院理化技术研究所 Gelatin-based micro-nano fiber membrane material and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10301440B2 (en) * 2016-02-15 2019-05-28 Modern Meadow, Inc. Biofabricated material containing collagen fibrils

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101358382A (en) * 2008-08-26 2009-02-04 东华大学 Antibacterial nano fiber material and preparation method thereof
CN102154738A (en) * 2011-05-10 2011-08-17 青岛大学 Method for preparing red algae agar fiber
CN104562438A (en) * 2013-10-17 2015-04-29 中国科学院理化技术研究所 Gelatin-based micro-nano fiber membrane material and preparation method and application thereof

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