Eicaridin-grafted alginic acid derivative, composite material of alginic acid derivative and polypropylene non-woven fabric as well as preparation method and application of composite material
Through the esterification reaction of sodium alginate and ecaridin and cross-linking of polypropylene non-woven fabrics, an alginate derivative/polypropylene composite material is formed, and the mosquito-resistant textiles in the prior art are solved. The problems of poor mosquito repellency and complex production process have achieved efficient, environmentally friendly and long-lasting mosquito repellency.
Patent Information
- Application Number
- CN202411336788.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-25
- Publication Date
- 2024-12-24
AI Technical Summary
The prior art is difficult to achieve efficient, environmentally friendly and long-lasting mosquito repellent effects in mosquito-resistant textiles, and the production process is complex, so alginic acid is required to be isolated and purified.
By esterification reaction with ecaridin under acidic conditions, an alginate grafted alginic acid derivative was obtained and cross-linked with polypropylene non-woven fabric to form a composite material to achieve mosquito repelling effect .
It achieves efficient and long-lasting mosquito repelling effects, simplifies the production process, improves the reaction efficiency, and maintains good mosquito repellency performance after 50 washes.
Smart Images
Figure CN119176888A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of alginic acid modification and effective mosquito repellent, and particularly relates to a preparation method of an icaridin-grafted alginic acid derivative and an alginic acid derivative / polypropylene non-woven fabric composite. Background Art
[0002] Mosquitoes can carry pathogenic microorganisms such as bacteria, viruses and fungi, and are the medium for the spread of many diseases, including malaria, dengue fever, yellow fever, chikungunya and other serious diseases. After mosquitoes bite sick animals or humans, they will transmit pathogens to healthy people, posing a serious threat to human health. According to statistics from the World Health Organization (WHO), more than 700,000 people die from mosquito bites each year. Mosquitoes are the animals that kill the most humans and are recognized as the top ten deadliest animals on earth. Therefore, effective mosquito repellent is urgent.
[0003] In recent years, mosquito-proof textiles have become one of the key areas of functional textile research. Mosquito-proof textiles can block the moisture sensing holes of mosquitoes or cause nervous system disorders by affecting their sense of smell and touch to prevent mosquitoes from approaching the surface of mosquito-proof textiles. Sodium alginate, as a natural biomass polymer, is a natural polymer material derived from brown algae and seaweed. It has the advantages of being non-toxic, harmless, biodegradable, and biocompatible. It also has good thickening, film-forming and stability properties and is widely used in chemistry, medicine, biology, industrial manufacturing, food, medicine and health, textile manufacturing and other fields. Alginate has many free hydroxyl (-OH) and carboxyl (-COOH) groups distributed along the skeleton. Functional alginate derivatives can be obtained by functionalizing the hydroxyl and carboxyl groups, including alginate derivatives with mosquito repellent function and easy film formation.
[0004] Commonly used mosquito repellents include icaridin, DEET, immonin (repellent) and pyrethroids. Among them, icaridin, also known as Picaridin, is a broad-spectrum repellent with the advantages of good mosquito repellent effect, long protection time, almost colorless and odorless, safe and low toxicity, and no skin irritation. The mosquito repellent principle of icaridin is to reduce the volatility of odor substances mixed with it, and play a role in reducing volatile odor substances to interfere with mosquitoes' recognition of human skin odor. Icaridin is rated by the Centers for Disease Control and Prevention (CDC) of the United States as another most effective mosquito repellent besides DEET. Icaridin has no obvious toxicity when ingested by the digestive tract, inhaled by the respiratory tract, and used on the skin. It is non-irritating to the skin and eyes and does not cause skin allergies and other problems. Because icaridin contains a hydroxyl group (-OH), it can undergo further derivatization reactions. Icaridin can be grafted onto alginate through the esterification reaction of the carboxyl group of alginate to obtain an alginate derivative with mosquito repellent effect, and then a textile with mosquito repellent effect can be obtained through cross-linking with textiles. Summary of the invention
[0005] The purpose of the present invention is to overcome the shortcomings of the prior art and provide an icaridin-grafted alginate derivative and a preparation method thereof, which is obtained by esterifying alginate generated in situ by sodium alginate under acidic conditions with icaridin. The reaction does not require separation and purification of the produced alginate, and an alginate derivative that can effectively repel mosquitoes is obtained by a one-pot method.
[0006] The present invention provides a method for preparing an icaridin grafted alginic acid derivative, which adopts a one-pot acidification and esterification reaction and comprises the following main steps:
[0007] (1) mixing sodium alginate and icaridin in a solvent at a molar ratio of 1.5-5:1, adding an acidifying agent, and then adding a coupling agent and a catalyst, and stirring the reaction at a reaction temperature of 0-40° C. for 1-48 hours;
[0008] (2) The solution obtained in step (1) is placed in a refrigerator at -20°C and frozen for 18 hours until it completely becomes solid, and then vacuum dried in a freeze dryer for 36 hours until constant weight is obtained, and then washed with dichloromethane, the volume ratio of the solution obtained in step (1) to dichloromethane is 1:50, filtered with a Buchner funnel, and the washing and filtration are repeated three times, and then washed with anhydrous ethanol, the volume ratio of the solution obtained in step (1) to anhydrous ethanol is 1:50, filtered with a Buchner funnel, and the washing and filtration are repeated three times, and finally dried in a vacuum drying oven at 40°C overnight to obtain an icaridin-grafted alginate derivative.
[0009] In the present invention, the solvent is selected from any one of dichloromethane, chloroform, carbon tetrachloride, trichloroethane benzene, toluene, methanol, ethanol, isopropanol, ethylene glycol, acetone, tetrahydrofuran, n-hexane, cyclohexane, dimethyl sulfoxide, N,N-dimethylformamide or water; the acidifying agent is a hydrochloric acid solution, and the mass fraction of the hydrochloric acid solution is 5-20%; the coupling reagent is at least one of 1,3-dicyclohexylcarbodiimide (DCC), 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDCI), N-cyclohexyl-N′-(2-morpholinoethyl)carbodiimide methyl p-toluenesulfonate (CMC), and N,N′-diisopropylcarbodiimide (DIC); the catalyst is N-hydroxysuccinimide (NHS), N-hydroxysulfosuccinimide sodium salt (Slufo-NHS), 4-dimethylaminopyridine (DMAP) or triethylamine (Et 3 N).
[0010] In the present invention, the molar amount of the coupling reagent is 100-200% of the molar amount of icaridin; the molar amount of the catalyst is 1-20% of the molar amount of icaridin; and the molar amount of the acidifying agent is 300-900% of the molar amount of icaridin.
[0011] The present invention also provides an icaridin-grafted alginic acid derivative prepared by the above method, having a general formula [C 6 H 8 O 6 ] m -[C 18 H 29 NO 8 ] n , as shown in the following structural formula (Ⅰ), m+n is 80-750, and m:n is 1.5-5:1;
[0012]
[0013] The present invention also provides a method for preparing an icaridin-grafted alginic acid derivative / polypropylene non-woven fabric composite material, wherein the icaridin-grafted alginic acid derivative is successfully loaded on a polypropylene non-woven fabric through cross-linking to obtain an icaridin-grafted alginic acid derivative / polypropylene non-woven fabric composite material, comprising the following main steps:
[0014] (i) Icaridin-grafted alginic acid derivatives were synthesized according to the above method;
[0015] (II) Preparation of Alginate Derivative / Polypropylene Nonwoven Fabric Composite Materials
[0016] (1) Prepare 200-400 mL of a mixed solution of water and ethanol, with a volume ratio of water to ethanol of 1:1, cut a number of 4×4 cm polypropylene nonwoven fabrics, place them in the mixed solution and soak for 1 hour until they are completely wet, then take them out;
[0017] (2) At room temperature, add 0.5-1.0 g of the icaridin-grafted alginic acid derivative into a beaker containing 20-40 mL of deionized water, stir and dissolve thoroughly, and after the solution is degassed, apply the solution evenly on the polypropylene non-woven fabric treated in step (1) with a glass rod, with a coating thickness of 3 mm, and then immediately place it evenly in 2-4 L of a cross-linking agent, cross-link it thoroughly for 8 hours, and then take it out;
[0018] (3) The resulting mixture was washed three times with deionized water and then naturally dried at room temperature to obtain an icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material.
[0019] In the present invention, the cross-linking agent is a calcium chloride solution, and the mass fraction of the calcium chloride solution is 1-5%.
[0020] The present invention also provides an icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material prepared by the above method.
[0021] The present invention also provides application of the icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material in mosquito-proof fabrics.
[0022] In the present invention, the in-situ generation of alginic acid by acidifying sodium alginate is achieved, and the sodium alginate is grafted and modified by an esterification reaction involving active carboxyl groups, with the ratio of sodium alginate to icaridin being 1:1. An alginate derivative grafted with icaridin was prepared, and its polypropylene non-woven composite material was prepared. As the proportion of icaridin increased, the repellency rate of the composite material to mosquitoes increased. The esterification reaction can be achieved in the aqueous phase at room temperature under the action of a coupling agent and a catalyst, and has the advantages of mild reaction conditions, high repellency rate and environmental friendliness. At the same time, the coupling agent greatly improves the condensation efficiency in the presence of a catalyst, which is conducive to the reaction. In addition, the reaction does not require separation and purification of the produced alginate, and the icaridin-grafted alginate derivative that can effectively repel mosquitoes is obtained by a one-pot method, which simplifies the experimental steps and improves the reaction yield and efficiency.
[0023] In the present invention, the alginic acid derivative grafted with icaridin is loaded on a polypropylene non-woven fabric by a simple operation to obtain an icaridin-grafted modified alginate derivative / polypropylene non-woven fabric composite material, which is a textile material that effectively repels mosquitoes. The modified alginate derivative grafted with icaridin / polypropylene non-woven fabric in the present invention achieves efficient repelling of mosquitoes under normal temperature conditions. According to the test of the national standard GB / T 30126-2013 and through the domestic and foreign certification of CNAS, the repellency rate of the mosquito-proof fabric produced by the invention reaches Class B and above, and has a good effect of repelling mosquitoes. The alginate derivative grafted with icaridin can be firmly loaded on the polypropylene non-woven fabric, and the mosquito repellency efficiency still shows a good mosquito repellency efficiency of Class B after 50 washings.
[0024] Compared with the prior art, the present invention has the following advantages and progress:
[0025] (1) The present invention modifies sodium alginate with icaridin containing hydroxyl groups through esterification reaction to obtain an icaridin-grafted alginate derivative having mosquito repellent effect. The alginate derivative has the advantages of easy film formation, biodegradability, good biocompatibility, etc.
[0026] (2) The present invention uses an esterification reaction between the hydroxyl group in icaridin and the carboxyl group of the in-situ generated alginic acid to achieve the grafting of icaridin onto alginic acid. The method is simple and easy to operate, the reaction conditions are mild, the raw materials are easily available, and the reaction efficiency and yield are high. There is no need to separate and purify the produced alginic acid, and the alginic acid derivative that can effectively repel mosquitoes can be obtained by a one-pot method, which simplifies the experimental steps and improves the reaction yield and efficiency.
[0027] (3) The icaridin-grafted alginate derivative can be successfully loaded on a polypropylene non-woven fabric through cross-linking to obtain an icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material, which has a good to extremely strong mosquito repellent effect. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] Figure 1 A process for preparing an icaridin-grafted alginic acid derivative;
[0029] Figure 2-4 They are infrared spectra of the icaridin-grafted alginate derivatives (I-1), (I-2) and (I-3) involved in the embodiments of the present invention. DETAILED DESCRIPTION
[0030] The present invention will be further described below by way of embodiments in conjunction with the accompanying drawings.
[0031] 1. Alginate derivatives grafted with icaridin
[0032] Example 1-1 Preparation of Icaridin-grafted Alginate Derivative (I-1)
[0033] This embodiment provides an icaridin-grafted alginic acid derivative, the structural formula of which is as follows (m:n=5:1):
[0034]
[0035] The above-mentioned icaridin-grafted alginic acid derivative is prepared by a one-pot acidification and esterification reaction, which includes the following main steps:
[0036] (1) At room temperature, prepare 20 mL of 10% hydrochloric acid solution in a beaker, add 0.5 g of sodium alginate, 0.108 g of icaridin, 0.0904 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.0542 g of N-hydroxysuccinimide into the beaker in sequence, and stir to react at room temperature for 48 hours;
[0037] (2) The solution obtained in step (1) was placed in a -20°C refrigerator and frozen for 18 hours until it completely solidified, then vacuum dried in a freeze dryer for 36 hours until constant weight was reached, washed with 25 mL of dichloromethane and filtered, the washing and filtering were repeated three times, then washed with 25 mL of anhydrous ethanol and filtered, the washing and filtering were repeated three times, and finally dried in a vacuum drying oven at 40°C overnight to obtain an icaridin-grafted alginate derivative (I-1).
[0038] The infrared spectrum data of the product (I-1) obtained in this example are as follows Figure 2 Shown: IR(film)ν max 3432,2921,1747,1631,1384,1263,1034cm -1 .
[0039] Example 1-2 Preparation of Icaridin-grafted Alginate Derivative (I-2)
[0040] This embodiment provides an icaridin-grafted alginic acid derivative, the structural formula of which is as follows (m:n=2:1):
[0041]
[0042] The above-mentioned icaridin-grafted alginic acid derivative is prepared by a one-pot acidification and esterification reaction, which includes the following main steps:
[0043] (1) At room temperature, prepare 20 mL of 10% hydrochloric acid solution in a beaker, add 0.5 g of sodium alginate, 0.27 g of icaridin, 0.226 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.1355 g of N-hydroxysuccinimide into the beaker in sequence, and stir to react at room temperature for 48 hours;
[0044] (2) The solution obtained in step (1) was placed in a refrigerator at -20°C and frozen for 18 hours until it completely solidified, then vacuum dried in a freeze dryer for 36 hours until constant weight was reached, washed with 25 mL of dichloromethane and filtered, the washing and filtering were repeated three times, then washed with 25 mL of anhydrous ethanol and filtered, the washing and filtering were repeated three times, and finally dried in a vacuum drying oven at 40°C overnight to obtain an icaridin-grafted alginate derivative (I-2).
[0045] The infrared spectrum data of the product (I-2) obtained in this example are as follows Figure 3 Shown: IR(film)ν max 3444,2918,1725,1631,1409,1380,1097,1033cm -1 .
[0046] Example 1-3 Preparation of Icaridin-grafted Alginate Derivative (I-3)
[0047] This embodiment provides an icaridin-grafted alginic acid derivative, the structural formula of which is as follows (m:n=1.5:1):
[0048]
[0049] The above-mentioned icaridin-grafted alginic acid derivative is prepared by a one-pot acidification and esterification reaction, which includes the following main steps:
[0050] (1) At room temperature, prepare 20 mL of 10% hydrochloric acid solution in a beaker, add 0.5 g of sodium alginate, 0.36 g of icaridin, 0.3 g of 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.18 g of N-hydroxysuccinimide into the beaker in sequence, and stir to react at room temperature for 48 hours;
[0051] (2) The solution obtained in step (1) was placed in a refrigerator at -20°C and frozen for 18 hours until it completely became solid, then vacuum dried in a freeze dryer for 36 hours until constant weight was reached, washed with 25 mL of dichloromethane and filtered, the washing and filtering were repeated three times, then washed with 25 mL of anhydrous ethanol and filtered, the washing and filtering were repeated three times, and finally dried in a vacuum drying oven at 40°C overnight to obtain an icaridin-grafted alginate derivative (I-3).
[0052] The infrared spectrum data of the product (I-3) obtained in this example are as follows Figure 4 Shown: IR(film)ν max 3435,2924,1738,1631,1348,1262,1092,1031cm -1 .
[0053] 2. Icaridin-grafted alginate derivative / polypropylene non-woven fabric composites
[0054] Example 2-1 Preparation of Icaridin-grafted Alginate Derivative / Polypropylene Nonwoven Fabric Composite Material (II)
[0055] This embodiment provides a method for preparing an icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material (II), comprising the following main steps:
[0056] (I) The icaridin-grafted alginic acid derivative (I-1) was synthesized according to the above method;
[0057] (II) Preparation of Icaridin-grafted Alginate Derivative / Polypropylene Nonwoven Fabric Composites
[0058] (1) Prepare 200-400 mL of a mixed solution of water and ethanol in a volume ratio of 1:1, cut a number of 4×4 cm polypropylene non-woven fabrics and soak them in the mixed solution for 1 hour until they are completely wetted and then take them out;
[0059] (2) At room temperature, 0.5-1.0 g of the alginate derivative grafted with icaridin (I) was added to a beaker containing 20-40 mL of deionized water, and the mixture was stirred thoroughly to dissolve. After the solution was degassed, the solution was evenly applied to the polypropylene non-woven fabric treated in step (1) using a glass rod, and the coating thickness was 3 mm. The mixture was then immediately evenly placed in 2-4 L of a 5% calcium chloride crosslinking agent, and the mixture was fully crosslinked for 8 hours before being taken out. (3) The mixture was washed three times with deionized water, and then naturally dried at room temperature to obtain the alginate derivative grafted with icaridin / polypropylene non-woven fabric composite material (II-1).
[0060] Using the same method as above, the alginate derivative grafted with icaridin (Ⅰ-2) is used to obtain the alginate derivative grafted with icaridin / polypropylene composite material (Ⅱ-2); the alginate derivative grafted with icaridin (Ⅰ-3) is used to obtain the alginate derivative grafted with icaridin / polypropylene composite material (Ⅱ-3).
[0061] 3. Test of repellency rate
[0062] Example 3-1 Mosquito repellency test of icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material (II)
[0063] This example tests the mosquito repellency rate of the icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material (II) according to GB / T 30126-2013 "Testing and evaluation of mosquito repellency of textiles":
[0064] The composites of picaridin-grafted alginate derivatives / polypropylene non-woven fabrics (Ⅱ-1, Ⅱ-2, Ⅱ-3) and the picaridin-grafted alginate derivatives / polypropylene composites (Ⅱ-1, Ⅱ-2, Ⅱ-3) after 50 times of washing were respectively cut into two groups of 4×4 cm specimens. In addition, the polypropylene non-woven fabrics were cut into two groups of 4×4 cm specimens without any treatment as the blank control group. According to the detection of the national standard GB / T 30126-2013, the picaridin-grafted alginate derivatives / polypropylene composite (Ⅱ-1) was detected by four groups of personnel. Among them, the repellency rate measured by Subject 1 was 60.00%, the repellency rate measured by Subject 2 was 57.14%, the repellency rate measured by Subject 3 was 58.33%, and the repellency rate measured by Subject 4 was 50.00%. The final average repellency rate was 56.4%. According to the national standard, the repellency rate of this mosquito-proof fabric is 50% < R < 70%, and the detection result is identified as Class B, indicating that the picaridin-grafted alginate derivatives / polypropylene composite (Ⅱ-1) has a good effect on repelling mosquitoes.
[0065] The picaridin-grafted alginate derivatives / polypropylene composite (Ⅱ-2) was detected by four groups of personnel. Among them, the repellency rate measured by Subject 1 was 80.00%, the repellency rate measured by Subject 2 was 73.68%, the repellency rate measured by Subject 3 was 66.67%, and the repellency rate measured by Subject 4 was 72.22%. The final average repellency rate was 73.1%. According to the national standard, the repellency rate of this mosquito-proof fabric is R > 70%, and the detection result is identified as Class A, indicating that the picaridin-grafted alginate derivatives / polypropylene composite (Ⅱ-3) has a very strong effect on repelling mosquitoes.
[0066] The picaridin-grafted alginate derivatives / polypropylene composite (Ⅱ-3) was detected by four groups of personnel. Among them, the repellency rate measured by Subject 1 was 84.21%, the repellency rate measured by Subject 2 was 90.00%, the repellency rate measured by Subject 3 was 80.95%, and the repellency rate measured by Subject 4 was 89.47%. The final average repellency rate was 86.2%. According to the national standard, the repellency rate of this mosquito-proof fabric is R > 70%, and the detection result is identified as Class A, indicating that the picaridin-grafted alginate derivatives / polypropylene composite (Ⅱ-3) has a very strong effect on repelling mosquitoes.
[0067] The icaridin-grafted alginate derivative / polypropylene composite material (Ⅱ-1) was subjected to 50 wash resistance tests. The samples were tested by four groups of personnel. The repellency rate measured by Subject 1 was 50.00%, the repellency rate measured by Subject 2 was 45.45%, the repellency rate measured by Subject 3 was 36.36%, and the repellency rate measured by Subject 4 was 50.00%. The final average repellency rate was 45.5%. According to the national standard, for the repellency rate of this mosquito-repellent fabric, 30% < R < 50%, the test result was rated as Class C, indicating that the icaridin-grafted alginate derivative / polypropylene composite material (Ⅱ-1) still had the effect of repelling mosquitoes after 50 washes, but the effect had decreased.
[0068] The icaridin-grafted alginate derivative / polypropylene composite material (Ⅱ-2) was subjected to 50 wash resistance tests. The samples were tested by four groups of personnel. The repellency rate measured by Subject 1 was 60.00%, the repellency rate measured by Subject 2 was 58.82%, the repellency rate measured by Subject 3 was 46.67%, and the repellency rate measured by Subject 4 was 64.71%. The final average repellency rate was 57.6%. According to the national standard, for the repellency rate of this mosquito-repellent fabric, 50% < R < 70%, the test result was rated as Class B, indicating that the icaridin-grafted alginate derivative / polypropylene composite material (Ⅱ-2) still had a good effect of repelling mosquitoes after 50 washes.
[0069] The icaridin-grafted alginate derivative / polypropylene composite material (Ⅱ-3) was subjected to 50 wash resistance tests. The samples were also tested by four groups of personnel. The repellency rate measured by Subject 1 was 60.00%, the repellency rate measured by Subject 2 was 62.50%, the repellency rate measured by Subject 3 was 60.71%, and the repellency rate measured by Subject 4 was 65.22%. The final average repellency rate was 62.1%. According to the national standard, for the repellency rate of this mosquito-repellent fabric, 50%
Claims
1. A method for preparing an icaridin grafted alginic acid derivative, using a one-pot acidification and esterification reaction, characterized in that: The main steps include: (1) mixing sodium alginate and icaridin in a solvent at a molar ratio of 1.5-5:1, adding an acidifying agent, and then adding a coupling agent and a catalyst, and stirring the reaction at a reaction temperature of 0-40° C. for 1-48 hours; (2) placing the solution obtained in step (1) in a refrigerator and freezing it for 18 hours until it completely becomes solid, then vacuum drying it in a freeze dryer for 36 hours until constant weight, then washing it with dichloromethane, filtering it with a Buchner funnel, the volume ratio of the solution obtained in step (1) to dichloromethane being 1:50, and repeating the washing and filtering three times; then washing it with anhydrous ethanol, filtering it with a Buchner funnel, the volume ratio of the solution obtained in step (1) to anhydrous ethanol being 1:50, and repeating the washing and filtering three times; finally drying it in a vacuum drying oven at 40° C. overnight to obtain an icaridin-grafted alginate derivative.
2. The method for preparing an icaridin grafted alginate derivative according to claim 1, characterized in that: The solvent is selected from any one of dichloromethane, chloroform, carbon tetrachloride, trichloroethane benzene, toluene, methanol, ethanol, isopropanol, ethylene glycol, acetone, tetrahydrofuran, n-hexane, cyclohexane, dimethyl sulfoxide, N,N-dimethylformamide or water; the acidifying agent is a hydrochloric acid solution, and the mass fraction of the hydrochloric acid solution is 5-20%; the coupling reagent is at least one of 1,3-dicyclohexylcarbodiimide, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, N-cyclohexyl-N′-(2-morpholinoethyl)carbodiimide methyl p-toluenesulfonate, and N,N′-diisopropylcarbodiimide; and the catalyst is at least one of N-hydroxysuccinimide, N-hydroxysulfosuccinimide sodium salt, 4-dimethylaminopyridine or triethylamine.
3. The method for preparing an icaridin grafted alginate derivative according to claim 1, characterized in that: The molar dosage of the coupling reagent is 100-200% of the molar dosage of icaridin; the molar dosage of the catalyst is 1-20% of the molar dosage of icaridin; and the molar dosage of the acidifying agent is 300-900% of the molar dosage of icaridin.
4. The icaridin-grafted alginic acid derivative prepared by the method according to any one of claims 1 to 3, characterized in that: The icaridin-grafted alginic acid derivative has the general formula [C6H8O6] m -[C 18 H 29 NO8] n , as shown in the following structural formula (Ⅰ), m+n is 80-750, and m:n is 1.5-5:
1.
5. A method for preparing an icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material, characterized in that: The main steps include: (i) Synthesis of an icaridin-grafted alginic acid derivative, prepared according to any one of claims 1 to 3; (II) Preparation of Alginate Derivative / Polypropylene Nonwoven Fabric Composite Materials (1) Prepare 200-400 mL of a mixed solution of water and ethanol, with a volume ratio of water to ethanol of 1:1, cut a number of 4×4 cm polypropylene non-woven fabrics, place them in the mixed solution and soak for 1 hour until they are completely wet, then take them out; (2) At room temperature, add 0.5-1.0 g of the icaridin-grafted alginic acid derivative into a beaker containing 20-40 mL of deionized water, stir and dissolve thoroughly, and after the solution is degassed, apply the solution evenly on the polypropylene non-woven fabric treated in step (1) with a glass rod, with a coating thickness of 3 mm, and then immediately place it evenly in 2-4 L of a cross-linking agent, cross-link it thoroughly for 8 hours, and then take it out; (3) The resulting mixture was washed three times with deionized water and then naturally dried at room temperature to obtain an icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material.
6. The preparation method according to claim 5, characterized in that: The cross-linking agent is a calcium chloride solution, and the mass fraction of the calcium chloride solution is 1-5%.
7. The icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material prepared by the method according to any one of claims 5-6.
8. The composite material according to claim 7, characterized in that The mosquito repellency rate of the mosquito-repellent fabric of the alginate derivative / polypropylene non-woven fabric composite material grafted with icaridin under room temperature conditions reaches Class B or above, and after 50 washes, the mosquito repellency efficiency still shows a good Class B mosquito repellency efficiency.
9. Use of the icaridin-grafted alginate derivative / polypropylene non-woven fabric composite material according to claim 7 or 8 in mosquito-proof fabrics.