CN117802801A - Preparation method and application of oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric - Google Patents
Preparation method and application of oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric Download PDFInfo
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Abstract
The invention discloses a preparation method and application of an oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric, wherein the oxidized chitosan amino-terminated hyperbranched compound is dissolved in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid at low temperature, and then the oxidized chitosan amino-terminated hyperbranched compound and the cellulose fabric are catalyzed by sodium hypophosphite to undergo esterification and hemiacetal reaction, so that the fabric is prepared. The method is simple and easy to implement, the reaction rate is high, the reagent dosage is small, the method is environment-friendly, the grafting rate of the oxidized chitosan amino-terminated hyperbranched compound on the surface of the prepared modified cellulose fabric is high, the water-resistance is strong, the antibacterial effect is high and durable, the oxidized chitosan amino-terminated hyperbranched compound is high in water solubility, a large number of amino groups and imino groups in the molecule are easy to protonate in aqueous solution and have positive charges, acidic dyes can be actively combined, inorganic salts and accelerating agents are not used, the dye-uptake and the color fastness are high, and the application potential in the field of ecological dyeing is huge.
Description
Technical Field
The invention belongs to the technical field of functional modification and environmental protection dyeing of textiles, and particularly relates to a preparation method and application of an oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric.
Background
Cellulose fiber is an important textile raw material, has rich sources, is renewable, is biodegradable and has excellent biocompatibility, and cellulose fabrics are soft and comfortable, moisture-absorbing and breathable, smooth and cool, and do not generate static electricity, and are popular with people. However, the cellulose fabric has the defects of easy shrinkage, easy deformation, difficult treatment, easy bacteria breeding and the like; meanwhile, the traditional dyeing of the cellulose fabric needs to use a large amount of inorganic salt, alkali and an accelerating agent in dye liquor to improve the dye uptake and color fastness of the dye, the dyeing process time is long, the dyeing bath temperature is high, the energy and water resource consumption is large, and especially the discharge of printing and dyeing wastewater containing high salt content and auxiliary agents causes serious environmental pollution, and even causes salinization of soil and damage to animal and plant ecosystems. Therefore, chemical grafting, copolymerization or modification is carried out on the cellulose fabric, the dye affinity of the surface of the cellulose fabric is improved, and the development of an environment-friendly ecological salt-free dyeing technology for the cellulose fabric has become a difficult problem which needs to be solved urgently.
In order to enhance the affinity of cellulose fabrics to dyes, amine or quaternary ammonium salt auxiliary agents containing different reactive groups are mainly adopted to carry out surface cationization grafting on the cellulose fabrics at present, but the cationic auxiliary agents have the problems of easy decomposition under heating, low dye adsorption rate, long treatment period, weak dyeing fastness and the like, and are difficult to meet the requirements of salt-free environment-friendly dyeing of the cellulose fabrics [ K.Srikit, zhang Zitao, li Xinmao ] cotton is dyed by cationization reactive dyes [ foreign textile technology, 2001,195:34-38]. In recent years, binary mixtures of acrylic acid, acrylamide, vinyl monomers and the like are grafted and copolymerized into a cellulose macromolecular chain, so that the performances of moisture absorption, mechanical strength, thermal stability, dyeing and the like of a cellulose material are greatly improved, and copolymers of the acrylic acid and the like are crosslinked on the surface of a cellulose fabric in a network structure, so that the clothing performances of the fabric such as hand feeling, ventilation and the like are seriously affected, and the application is limited [ Teli M D, sheikh J.Graft copolymerization ofacrylamide onto bamboo rayon and dyeing with acid dyne.Iranian Polymer Journal,2012,21:43-49; singhaA S, rana R K.functional ofcellulosic fibers by graft copolymerization ofacrylonitrile and ethyl acrylate from their binary Polymers,2012,87 (1): 500-511].
The natural dyeing auxiliary Chitosan is increasingly paid attention to in the textile ecological dyeing and finishing field, chitosan (Chitosan) is obtained by deacetylation of chitin, has a chemical name of (1-4) -2-acetamido-B-D glucose, is rich in content, is easy to obtain in raw materials, is safe and nontoxic, has good biocompatibility, antibacterial property, biodegradability and the like, and has been widely applied to the aspects of medicine, biotechnology, chemical industry, environmental protection, textile dyeing and finishing and the like. However, a large amount of hydrogen bonds exist in chitosan molecules, so that the chitosan has poor swelling resistance and solubility, and the application range of the chitosan is greatly limited. In recent years, scholars at home and abroad carry out chemical modification such as alkylation, acylation, carboxylation, quaternization and the like on chitosan to improve the water solubility and chemical reactivity of chitosan. The trimethoxy benzoyl chitosan modified cotton fabric disclosed in the patent CN106521950A realizes the chemical grafting of chitosan and cotton fabric by taking organic polycarboxylic acid and amino silicone oil emulsion as cross-linking agents, improves the shrink-proof, crease-resistant and dyeing performances of cotton fabric, but the finishing liquid has various components and large reagent dosage, and needs complex finishing procedures such as padding, pre-baking, high-temperature baking and the like, and has longer treatment flow, high process equipment requirements and difficult practical application.
Therefore, the technology of exploring the chitosan grafted cellulose fabric without the cross-linking agent is a hot research direction of textile function finishing in recent years, and if the water solubility and the reactivity of the chitosan can be improved through modifying the chitosan, the chemical cross-linking with the cellulose fabric can be realized, the binding fastness of the surface of the modified cellulose fabric to dye can be enhanced, the environment-friendly dyeing can be realized, and the method has important significance for the green sustainable development of the printing and dyeing industry.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method and application of an oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric, wherein the modified cellulose fabric is obtained by dissolving an oxidized chitosan amino-terminated hyperbranched compound in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid at low temperature, and then carrying out esterification and hemiacetal reaction on the oxidized chitosan amino-terminated hyperbranched compound and the cellulose fabric through sodium hypophosphite catalysis. The grafted modified cellulose fabric has the advantages of affinity to human body, lasting antibacterial effect, strong dye binding force, no salt ecological dyeing and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric comprises the steps of dissolving the oxidized chitosan amino-terminated hyperbranched compound in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid, and then carrying out esterification and hemi-acetal reaction on the oxidized chitosan amino-terminated hyperbranched compound and the cellulose fabric through sodium hypophosphite catalysis to obtain the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric.
The method specifically comprises the following steps:
(1) Stirring and dissolving the oxidized chitosan amino-terminated hyperbranched compound in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid at 20-35 ℃ to prepare an oxidized chitosan amino-terminated hyperbranched compound ionic liquid solution with the mass concentration of 0.5-2.5%, heating to 50-60 ℃, adding sodium hypophosphite as a catalyst for dissolution, and enabling the mass concentration of the catalyst in the ionic liquid solution to be 0.8-3%;
(2) Introducing nitrogen into the ionic liquid solution, adding cellulose fabric according to a bath ratio of 1g to 50-80 mL, and stirring for reaction under the microwave radiation condition; and after the reaction is finished, taking out the cellulose fabric, drying for 15-20 min at 45-60 ℃, immediately baking for 3-5 min at 100-120 ℃ under vacuum regulation, drying at 60-80 ℃ in a steaming machine, washing for multiple times with hot water, soaking in an ethanol water solution with the volume concentration of 50-80% for 8-10 h, taking out, dehydrating, and airing to obtain the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric.
The structural formula of the oxidized chitosan amino-terminated hyperbranched compound in the step (1) is as follows:
the viscosity average molecular weight of the oxidized chitosan amino-terminated hyperbranched compound is 18.5-34.6 ten thousand, the grafting rate of the C2 amino-terminated hyperbranched compound is 50.42-67.95%, the content of C6 aldehyde group is 23.73-40.19%, the deacetylation degree is more than or equal to 80.6%, and the solubility in water is more than or equal to 13.81g/100mL.
In the step (2), the mass ratio of the oxidized chitosan amino-terminated hyperbranched compound to the cellulose fabric is 0.1-0.5:1.
In the step (2), the flow rate of the introduced nitrogen is 40-60 mL/min.
In the step (2), the microwave radiation power is 240-520W, and the microwave radiation temperature is 60-80 ℃.
In the step (2), the steam pressure of the steaming machine is-0.032-0.15 MPa.
The cellulose fabric is a woven fabric, knitted fabric or non-woven fabric of natural cellulose or regenerated cellulose subjected to desizing and scouring.
An application of oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric in acid dye salt-free ecological dyeing.
The beneficial effects of the invention are as follows:
1. according to the invention, sodium hypophosphite is adopted to catalyze and oxidize C2 citric acid in the molecule of the amino hyperbranched compound at the chitosan end to form acid anhydride, then esterification crosslinking reaction is carried out on the acid anhydride and hydroxyl groups of cellulose fabrics, and multi-site grafting is carried out on the surface of the cellulose fabrics through the reaction of forming hemiacetal by oxidizing C6 aldehyde groups in the molecule of the amino hyperbranched compound at the chitosan end and the hydroxyl groups of cellulose, so that the prepared modified cellulose fabrics have the advantages of high grafting rate, strong reactivity, lasting antibacterial property, human body affinity and the like.
2. The invention uses 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid as a green solvent for oxidizing chitosan amino-terminated hyperbranched compounds and a grafting reaction medium of cellulose fabrics, and the ionic liquid has the advantages of stable physicochemical property, no toxicity, no pollution, no evaporation pressure, no volatilization, environmental protection, recycling and the like. The ionic liquid 2-methyl-1- (propyl-3-sulfonic) pyridine acetate can directly dissolve the oxidized chitosan amino-terminated hyperbranched compound at normal temperature, so that the molecular chain of the oxidized chitosan amino-terminated hyperbranched compound cannot be degraded and destroyed, and meanwhile, water generated by esterification and crosslinking of the oxidized chitosan amino-terminated hyperbranched compound and the cellulose fabric can be absorbed by the ionic liquid, so that the forward direction of esterification reaction is effectively promoted, and the grafting rate of the fabric is obviously improved.
3. According to the invention, cellulose fabric is immersed in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid solution of the chitosan amine-terminated hyperbranched compound for reaction under the microwave irradiation condition, and the microwave irradiation heating speed is high, the reaction time is short, the uniformity is good, the chitosan amine-terminated hyperbranched compound is fully contacted with the active site of the fabric, the catalytic grafting rate of sodium hypophosphite is obviously accelerated, the aggregation of the chitosan amine-terminated hyperbranched compound on the surface of the fabric caused by long-time treatment is effectively avoided, and the defects of long reaction period, low grafting reaction rate and uneven distribution of reaction products on the surface of the fabric in the traditional water bath heating reaction process are overcome. Meanwhile, the microwave irradiation reaction condition is mild, the process is simple, the production cost is low, the efficiency is high, and the chemical cross-linking agent is not used in the whole process, so that the adverse effects on the excellent characteristics of the cellulose fabric and the human health caused by the coating of the chemical cross-linking agent are avoided.
4. The invention utilizes the steaming machine to treat the cellulose fabric grafted by the amino hyperbranched compound of the oxidized chitosan, the steaming treatment has the advantages of high heating rate, high efficiency, low energy consumption and uniform heating, hot steam can directly permeate into the fabric, the temperature difference between the inside and the outside of the fabric is small, the temperature is easy to control, the migration phenomenon of the amino hyperbranched compound molecules of the oxidized chitosan due to the water evaporation process can be effectively reduced, the amino hyperbranched compound of the oxidized chitosan grafted on the surface of the fabric is uniformly combined, and the fabric has comfortable hand feeling.
5. According to the invention, the chitosan amine-terminated hyperbranched compound is subjected to esterification crosslinking and hemiacetal grafting by sodium hypophosphite catalysis, so that the chitosan amine-terminated hyperbranched compound is grafted on the surface of a cellulose fabric at multiple sites, and the oxidized chitosan amine-terminated hyperbranched compound combined on the surface of the fabric has a large number of amino groups, imino groups and other cationic groups, has strong adsorptivity and affinity to anionic acid dyes, does not use inorganic salts and accelerating agents, is environment-friendly, has good ecological dyeing property, high dyeing strength and color fastness, and is easy to popularize and apply.
Drawings
FIG. 1 is a diagram of the reaction mechanism of the invention for preparing oxidized chitosan amino-terminated hyperbranched compound multi-site grafted cellulose fabric.
FIG. 2 is a scanning electron microscope image of oxidized chitosan amine-terminated hyperbranched compound grafted cellulose fabric according to test item 1 of the present invention.
Detailed Description
The invention is further described with reference to the drawings and detailed description which follow:
the preparation method of the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric comprises the following steps:
(1) Stirring and dissolving the oxidized chitosan amino-terminated hyperbranched compound in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid at 20-35 ℃ to prepare an oxidized chitosan amino-terminated hyperbranched compound ionic liquid solution with the mass concentration of 0.5-2.5%, heating to 50-60 ℃, adding sodium hypophosphite as a catalyst for dissolving, and enabling the mass concentration of the catalyst in the ionic liquid solution to be 0.8-3%. Wherein the viscosity average molecular weight of the oxidized chitosan amino-terminated hyperbranched compound is 18.5-34.6 ten thousand, the grafting rate of the C2 amino-terminated hyperbranched compound is 50.42-67.95%, the content of C6 aldehyde group is 23.73-40.19%, the deacetylation degree is more than or equal to 80.6%, and the solubility in water is more than or equal to 13.81g/100mL.
(2) Introducing nitrogen into the ionic liquid solution for 10-20 min (the flow is 40-60 mL/min), and adding cellulose fabric (the cellulose fabric is a woven fabric, knitted fabric or non-woven fabric of natural cellulose or regenerated cellulose subjected to desizing and scouring) according to a bath ratio of 1 g:50-80 mL, so that the mass ratio of the oxidized chitosan amino-terminated hyperbranched compound to the cellulose fabric is 0.1-0.5:1; stirring and reacting under the microwave radiation condition (the microwave radiation power is 240-520W, and the microwave radiation temperature is 60-80 ℃); and after the reaction is finished, taking out the cellulose fabric, drying for 15-20 min at 45-60 ℃, immediately baking for 3-5 min at 100-120 ℃ under vacuum regulation, drying at 60-80 ℃ in a steaming machine (steam pressure is-0.032-0.15 MPa), washing for multiple times with hot water, soaking in an ethanol aqueous solution with the volume concentration of 50-80% for 8-10 h, taking out, dehydrating, and airing to obtain the chitosan-oxide end amino hyperbranched compound grafted cellulose fabric.
The oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric prepared by the method can be applied to salt-free ecological dyeing of acid dyes without using inorganic salts and accelerating agents.
Specific examples are as follows:
example 1
(1) The oxidized chitosan amine-terminated hyperbranched compound with the viscosity average molecular weight of 19.6 ten thousand, the grafting rate of the amino-terminated hyperbranched compound at the C2 position of 52.13 percent, the aldehyde group content at the C6 position of 28.06 percent and the deacetylation degree of 90.3 percent, and the solubility of the oxidized chitosan amine-terminated hyperbranched compound in water of 15.25g/100mL are stirred and dissolved in 2-methyl-1- (propyl-3-sulfonic group) pyridine acetate ionic liquid at 25 ℃ to prepare an oxidized chitosan amine-terminated hyperbranched compound ionic liquid solution with the mass concentration of 0.8 percent, and then the solution is heated to 50 ℃ and then added with a catalyst sodium hypophosphite for dissolution, wherein the mass concentration of the sodium hypophosphite in the ionic liquid is 1 percent.
(2) Introducing nitrogen (the flow rate of the nitrogen is 45 mL/min) into the ionic liquid solution for protection for 12min, adding cotton fabric according to the bath ratio of 1g to 50mL, enabling the mass ratio of the oxidized chitosan amino-terminated hyperbranched compound to the cotton fabric to be 0.2:1, and stirring and reacting for 1h under the condition of microwave radiation (the microwave radiation power is 260W and the microwave radiation temperature is 60 ℃). And after the reaction is finished, taking out the cotton fabric, drying for 16min in a vacuum oven at 50 ℃, immediately baking for 4min in the vacuum oven at 100 ℃, drying for 2h at 65 ℃ in a steaming machine (the steam pressure of the steaming machine is 0.12 MPa), washing for 3 times with hot water, soaking in an ethanol water solution with the volume concentration of 50% for 8h, taking out, dehydrating, and airing to obtain the oxidized chitosan amino hyperbranched compound grafted modified cotton fabric sample.
Through tests, the grafting rate of the oxidized chitosan amino-terminated hyperbranched compound grafted modified cotton fabric obtained in the embodiment is 3.17%, and the breaking strength of the modified cotton fabric is 392N; after 50 times of water washing, the antibacterial rate to staphylococcus aureus is 93.19 percent, and the antibacterial rate to escherichia coli is 91.07 percent; after the modified cotton fabric is subjected to salt-free dyeing by the acid lake blue A dye, the dyeing intensity K/S value is 5.305.
Example 2
(1) The method comprises the steps of stirring and dissolving an oxidized chitosan amine-terminated hyperbranched compound with the viscosity average molecular weight of 26.3 ten thousand, the grafting rate of an amino-terminated hyperbranched compound at the C2 position of 57.22%, the aldehyde group content at the C6 position of 34.51% and the deacetylation degree of 88.7% in water with the solubility of 18.14g/100mL in 2-methyl-1- (propyl-3-sulfonic group) pyridine acetate ionic liquid at 30 ℃ to prepare an oxidized chitosan amine-terminated hyperbranched compound ionic liquid solution with the mass concentration of 1.5%, heating to 60 ℃, adding a catalyst sodium hypophosphite for dissolution, and enabling the mass concentration of sodium hypophosphite in the ionic liquid to be 1.6%.
(2) Introducing nitrogen (the flow rate of the nitrogen is 50 mL/min) into the ionic liquid solution for protection for 15min, adding cotton fabric according to the bath ratio of 1g to 60mL, enabling the mass ratio of the oxidized chitosan amino-terminated hyperbranched compound to the cotton fabric to be 0.3:1, and stirring and reacting for 2h under the condition of microwave radiation (the microwave radiation power is 380W and the microwave radiation temperature is 65 ℃). And after the reaction is finished, taking out the cotton fabric, drying the cotton fabric in a vacuum oven at 55 ℃ for 18min, immediately baking the cotton fabric in the vacuum oven at 110 ℃ for 4min, drying the cotton fabric in a steamer (the steam pressure of the steamer is 0.06 MPa) at 70 ℃ for 2h, washing the cotton fabric for 4 times by hot water, soaking the cotton fabric in an ethanol water solution with the volume concentration of 60% for 8h, taking out the cotton fabric, dehydrating the cotton fabric, and airing the cotton fabric to obtain the oxidized chitosan amino-terminated hyperbranched compound grafted modified cotton fabric sample.
Through tests, the grafting rate of the oxidized chitosan amino-terminated hyperbranched compound grafted modified cotton fabric obtained in the embodiment is 7.24%, and the breaking strength of the modified cotton fabric is 411N; after 50 times of water washing, the antibacterial rate to staphylococcus aureus is 94.05 percent, and the antibacterial rate to escherichia coli is 91.62 percent; after the modified cotton fabric is subjected to salt-free dyeing by the acid lake blue A dye, the dyeing intensity K/S value is 8.169.
Example 3
(1) The method comprises the steps of preparing an oxidized chitosan amine-terminated hyperbranched compound ionic liquid solution with the mass concentration of 2% by stirring and dissolving the oxidized chitosan amine-terminated hyperbranched compound with the viscosity average molecular weight of 31.3 ten thousand, the grafting rate of the amino-terminated hyperbranched compound at the C2 position of 63.25%, the aldehyde group content at the C6 position of 38.40% and the deacetylation degree of 86.7% in water with the solubility of 21.13g/100mL in 2-methyl-1- (propyl-3-sulfonic group) pyridine acetate ionic liquid at 30 ℃, heating to 60 ℃ and then adding sodium hypophosphite as a catalyst for dissolving, so that the mass concentration of sodium hypophosphite in the ionic liquid is 2.5%.
(2) Introducing nitrogen (the flow rate of the nitrogen is 50 mL/min) into the ionic liquid solution for protection for 18min, adding cotton fabric according to the bath ratio of 1g to 60mL, enabling the mass ratio of the oxidized chitosan amino-terminated hyperbranched compound to the cotton fabric to be 0.4:1, and stirring and reacting for 3h under the condition of microwave radiation (the microwave radiation power is 480W and the microwave radiation temperature is 70 ℃). And after the reaction is finished, taking out the cotton fabric, drying the cotton fabric in a vacuum oven at 60 ℃ for 18min, immediately baking the cotton fabric in the vacuum oven at 120 ℃ for 5min, drying the cotton fabric in a steamer (the steam pressure of the steamer is minus 0.018 MPa) at 75 ℃ for 3h, washing the cotton fabric for 5 times by hot water, immersing the cotton fabric in an ethanol water solution with the volume concentration of 70% for 10h, taking out the cotton fabric, dehydrating the cotton fabric, and airing the cotton fabric to obtain the oxidized chitosan amino hyperbranched compound grafted modified cotton fabric sample.
Through tests, the grafting rate of the oxidized chitosan amino-terminated hyperbranched compound grafted modified cotton fabric obtained in the embodiment is 9.86%, and the breaking strength of the modified cotton fabric is 452N; after 50 times of water washing, the antibacterial rate to staphylococcus aureus is 95.74 percent, and the antibacterial rate to escherichia coli is 92.38 percent; after the modified cotton fabric is subjected to salt-free dyeing by the acid lake blue A dye, the dyeing intensity K/S value is 11.209.
Example 4
(1) The method comprises the steps of preparing an oxidized chitosan amine-terminated hyperbranched compound ionic liquid solution with the mass concentration of 2% by stirring and dissolving the oxidized chitosan amine-terminated hyperbranched compound with the viscosity average molecular weight of 31.3 ten thousand, the grafting rate of the amino-terminated hyperbranched compound at the C2 position of 63.25%, the aldehyde group content at the C6 position of 38.40% and the deacetylation degree of 86.7% in water with the solubility of 21.13g/100mL in 2-methyl-1- (propyl-3-sulfonic group) pyridine acetate ionic liquid at 30 ℃, heating to 60 ℃ and then adding sodium hypophosphite as a catalyst for dissolving, so that the mass concentration of sodium hypophosphite in the ionic liquid is 2.5%.
(2) Introducing nitrogen (the flow rate of the nitrogen is 55 mL/min) into the ionic liquid solution for protection for 20min, adding viscose fabric according to the bath ratio of 1g to 60mL, enabling the mass ratio of the oxidized chitosan amino-terminated hyperbranched compound to the viscose fabric to be 0.4:1, and stirring and reacting for 3h under the condition of microwave radiation (the microwave radiation power is 480W and the microwave radiation temperature is 70 ℃). And after the reaction is finished, taking out the cotton fabric, drying the cotton fabric in a vacuum oven at 60 ℃ for 18min, immediately baking the cotton fabric in the vacuum oven at 120 ℃ for 5min, drying the cotton fabric in a steamer (the steam pressure of the steamer is-0.024 MPa) at 75 ℃ for 3h, washing the cotton fabric for 5 times by hot water, immersing the cotton fabric in an ethanol water solution with the volume concentration of 80% for 10h, taking out the cotton fabric, dehydrating the cotton fabric, and airing the cotton fabric to obtain the chitosan-oxidized amino-terminated hyperbranched compound grafted modified viscose fabric sample.
Through tests, the grafting rate of the oxidized chitosan amino-terminated hyperbranched compound grafted modified viscose fabric obtained in the embodiment is 10.64%, and the breaking strength of the modified viscose fabric is 337N; after 50 times of water washing, the antibacterial rate to staphylococcus aureus is 95.96 percent, and the antibacterial rate to escherichia coli is 92.77 percent; after the modified viscose fabric is subjected to salt-free dyeing by the acid lake blue A dye, the dyeing intensity K/S value is 12.590.
Comparative example
Salt-free dyeing of unmodified cellulose fabrics:
desizing and scouring the cotton fabric to obtain the unmodified cotton fabric. The unmodified cotton fabric obtained in this comparative example was tested to have a breaking strength of 365N. After 50 times of water washing, the antibacterial rate to staphylococcus aureus is 27.25 percent, and the antibacterial rate to escherichia coli is 19.12 percent; after the unmodified cotton fabric is subjected to salt-free dyeing by the acid lake blue A dye, the dyeing intensity K/S value is 1.663.
The sample obtained in the above example was subjected to a detection test
Test item 1: scanning electron microscope analysis of oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric
The microscopic morphology of the cotton fabric surface before and after grafting was observed using a scanning electron microscope (2000×). Taking 3 parts of cotton fabric samples: the 1 st part is a cotton fabric a (blank sample) obtained by desizing and scouring the cotton fabric, the 2 nd part is a modified cotton fabric B having a grafting ratio of 7.24% obtained by grafting the cotton fabric with an oxidized chitosan amino-terminated hyperbranched compound according to the method of example 2, the 3 rd part is a modified cotton fabric C having a grafting ratio of 9.86% obtained by grafting the cotton fabric with an oxidized chitosan amino-terminated hyperbranched compound according to the method of example 3, and the test results are shown in fig. 2 (a) to (C) in order.
As shown in fig. 2, the surface of the raw cotton fiber a of the blank sample is flat, and more longitudinal stripes exist; whereas cotton fibers B and C grafted with oxidized chitosan amine-terminated hyperbranched compounds exhibited unique surface morphology, the modified cotton fibers had significant deposits and small lumps on the surface, many elongated stripes on the surface disappeared, and the oxidized chitosan amine-terminated hyperbranched compounds immobilized on the surface of the modified cotton fibers with a grafting ratio of 9.86% had formed a uniformly crosslinked film (see fig. 2C). Therefore, the oxidized chitosan amino-terminated hyperbranched compound is grafted on the cotton fiber molecular chain, and is coated on the cotton fiber surface to form a film.
In conclusion, sodium hypophosphite is catalyzed to oxidize an amino hyperbranched chitosan compound at the end of chitosan in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid to generate esterification and hemiacetal reaction with cellulose fabric, so that the modified cellulose fabric which is compatible with human body, durable in antibacterial activity, free of salt dyeing, safe and comfortable is obtained. The invention adopts the technology of catalytic grafting modified cellulose fabric, has simple flow, strong affinity to acid dye, high dye-uptake and color fastness, good ecological dyeing performance, no use of inorganic salt and alkali, environmental protection, low cost and easy popularization and application.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (9)
1. A preparation method of an oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric is characterized by comprising the following steps of: dissolving the oxidized chitosan amino-terminated hyperbranched compound in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid, and then catalyzing the oxidized chitosan amino-terminated hyperbranched compound to perform esterification and hemiacetal reaction with the cellulose fabric through sodium hypophosphite to obtain the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric.
2. The preparation method of the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric as claimed in claim 1, which is characterized by comprising the following steps:
(1) Stirring and dissolving the oxidized chitosan amino-terminated hyperbranched compound in 2-methyl-1- (propyl-3-sulfonic) pyridine acetate ionic liquid at 20-35 ℃ to prepare an oxidized chitosan amino-terminated hyperbranched compound ionic liquid solution with the mass concentration of 0.5-2.5%, heating to 50-60 ℃, adding sodium hypophosphite as a catalyst for dissolution, and enabling the mass concentration of the catalyst in the ionic liquid solution to be 0.8-3%;
(2) Introducing nitrogen into the ionic liquid solution, adding cellulose fabric according to a bath ratio of 1g to 50-80 mL, and stirring for reaction under the microwave radiation condition; and after the reaction is finished, taking out the cellulose fabric, drying at 45-60 ℃, immediately baking at 100-120 ℃ under vacuum regulation, drying at 60-80 ℃ in a steaming machine, washing for multiple times with hot water, soaking in an ethanol water solution with the volume concentration of 50-80% for 8-10 hours, taking out, dehydrating, and airing to obtain the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric.
3. The method for preparing the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric according to claim 2, which is characterized in that: the structural formula of the oxidized chitosan amino-terminated hyperbranched compound in the step (1) is as follows:
the viscosity average molecular weight of the oxidized chitosan amino-terminated hyperbranched compound is 18.5-34.6 ten thousand, the grafting rate of the C2 amino-terminated hyperbranched compound is 50.42-67.95%, the content of C6 aldehyde group is 23.73-40.19%, the deacetylation degree is more than or equal to 80.6%, and the solubility in water is more than or equal to 13.81g/100mL.
4. The method for preparing the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric according to claim 2, which is characterized in that: in the step (2), the mass ratio of the oxidized chitosan amino-terminated hyperbranched compound to the cellulose fabric is 0.1-0.5:1.
5. The method for preparing the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric according to claim 2, which is characterized in that: in the step (2), the flow rate of the introduced nitrogen is 40-60 mL/min.
6. The method for preparing the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric according to claim 2, which is characterized in that: in the step (2), the microwave radiation power is 240-520W, and the microwave radiation temperature is 60-80 ℃.
7. The method for preparing the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric according to claim 2, which is characterized in that: in the step (2), the steam pressure of the steaming machine is-0.032-0.15 MPa.
8. The method for preparing the oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric according to claim 2, which is characterized in that: the cellulose fabric is a woven fabric, knitted fabric or non-woven fabric of natural cellulose or regenerated cellulose subjected to desizing and scouring.
9. Use of an oxidized chitosan amino-terminated hyperbranched compound grafted cellulose fabric prepared according to the method of any one of claims 1-8 in salt-free ecological dyeing of acid dyes.
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