Multifunctional jasmine, camellia and chamomile fiber and preparation method thereof

Abstract

The invention belongs to the technical field of multifunctional fibers, and particularly relates to a preparation method of multifunctional jasmine, camellia and chamomile fibers, and the preparation method comprises the steps of preparation of beta-cyclodextrin microspheres, modification of carboxyl, adsorption, preparation of bis-aminated polyethylene glycol polycaprolactone and spinning. The prepared multifunctional jasmine, camellia and chamomile fiber has an excellent antibacterial effect and a natural antibacterial effect, the bacteriostasis rate to staphylococcus aureus is 98.5-99.2%, the bacteriostasis rate to candida albicans is 98.2-99%, the bacteriostasis rate to escherichia coli is 97.5-98.7% after the multifunctional jasmine, camellia and chamomile fiber is washed with water for 50 times, and the antibacterial standard of textiles is met; the antibacterial durability is good, and the average antibacterial loss rate after 50 times of washing is lower than 2%; the antioxidant and anti-mite effects are good, and the free radical scavenging rate is more than 96%; and the mite repelling rate is greater than 70%.

Description

Technical Field

[0001] The invention belongs to the technical field of multifunctional fibers, and in particular relates to a preparation method of multifunctional jasmine, camellia and chamomile fibers. Background Art

[0002] As people's living standards gradually improve, they have put forward more demands on textiles. Fibers with antibacterial, anti-ultraviolet, and antioxidant functions are more popular in the market. Most of the active ingredients in plant extracts have antibacterial, antioxidant, and antiviral effects. At the same time, they are natural and environmentally friendly, with no side effects on the environment and human body. Compared with chemical functional additives, they better meet the green concept of contemporary society.

[0003] Jasmine contains abundant bioactive ingredients such as jasmonic acid, jasmone, jasmone, camellia contains various triterpenes, flavonoids, polysaccharides, and chamomile contains apigenin, flavonoids, saponins, and other ingredients. Therefore, adding jasmine, camellia, chamomile, and other ingredients to the fiber can give the fiber natural antibacterial and antioxidant effects. In the prior art, there is a post-finishing method to add plant extracts to the fiber, but after multiple washings, the functional effect of the fiber is greatly reduced.

[0004] When adding plant active ingredients such as jasmine, camellia, and chamomile to spinning solution or molten polymer during fiber preparation, the plant active ingredients have poor acid and alkali resistance and high temperature resistance, and are easily inactivated during the spinning process, resulting in loss of active ingredients and increasing costs. In addition, the compatibility and stability of plant active ingredients in fibers are poor, and the functional durability is insufficient, which can easily affect the mechanical properties of the fiber itself. Summary of the invention

[0005] In order to solve the problems existing in the prior art, the present invention provides a method for preparing multifunctional jasmine, camellia and chamomile fibers, thereby achieving the invention purpose of improving the compatibility and stability of plant active ingredients in the fibers, while avoiding the influence of the addition of plant active ingredients on the mechanical properties of the fibers.

[0006] In order to solve the above technical problems, the present invention adopts the following technical solutions: One of the purposes of the present invention is to provide a method for preparing multifunctional jasmine, camellia and chamomile fibers, the preparation method comprising the following steps: S1. Preparation of β-cyclodextrin microspheres Add β-cyclodextrin to a 30-40°C NaOH solution and stir until dissolved, then add epichlorohydrin while stirring at a rate of 300-500 r / min, and react for 1-2 hours to obtain an aqueous phase; add the oil phase to the aqueous phase, stir at high speed for 5-15 minutes, then heat to 60-75°C and stir at low speed to react for 5-6 hours, after the reaction is completed, let stand to separate the layers to remove the oil layer, centrifuge, and then wash with dilute hydrochloric acid solution, anhydrous ethanol, and deionized water for 2-3 times, then wash with acetone for 2-3 times, and dry at 60-80°C for 24 hours to obtain β-cyclodextrin microspheres.

[0007] Preferably, the mass fraction of the NaOH solution is 20-40%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:4-6.

[0008] Preferably, the molar ratio of epichlorohydrin to β-cyclodextrin is 12 to 15:1.

[0009] Preferably, the volume ratio of the water phase to the oil phase is 1:2-4.

[0010] Preferably, in the oil phase, the emulsifier accounts for 2-3%, and the rest is liquid paraffin.

[0011] Furthermore, the emulsifier is one or more of Span 80 or Toast 20.

[0012] Preferably, the high-speed stirring rate is 1200-1400 r / min, and the low-speed stirring rate is 600-800 r / min.

[0013] S2. Modification of carboxyl groups Add β-cyclodextrin microspheres into DMF, then slowly add succinic anhydride, heat to 70-80°C for reaction for 8-12h, modify the surface of β-cyclodextrin microspheres with carboxyl groups, centrifuge after the reaction, wash the product with acetone and deionized water for 2-3 times, dry at 60-80°C for 24h to obtain carboxylated β-cyclodextrin microspheres with an average particle size of 5-8μm.

[0014] Preferably, the amount of succinic anhydride added is 30-50% of the mass of the β-cyclodextrin microspheres.

[0015] S3, adsorption Add carboxylated β-cyclodextrin microspheres into deionized water to prepare a saturated solution, then add the plant extract, stir at 40-50°C for 6-8h, load the plant extract into the carboxylated β-cyclodextrin microspheres, cool to room temperature, place at 0-5°C for 24h, filter, wash with deionized water and ether in turn, and dry at 40-60°C for 24h to obtain the plant functional agent.

[0016] Preferably, the plant extract is a mixture of jasmine essential oil, camellia essential oil and chamomile essential oil.

[0017] Preferably, the mass ratio of the plant extract to the carboxylated β-cyclodextrin microspheres is 2-3:7-12.

[0018] S4. Preparation of bis-aminated polyethylene glycol polycaprolactone Add NH2-PEG-PCL-OH to deionized water, then add aminosilane coupling agent and stir to react for 1 to 2 hours, modify the terminal hydroxyl group of NH2-PEG-PCL-OH with amino group to obtain diamino polyethylene glycol polycaprolactone; add plant functional agent to the system and stir for 10 to 20 minutes, then add 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, adjust the pH to 4 to 5, react for 3 to 4 hours, filter after the reaction, and wash with deionized water to obtain the modified plant functional agent.

[0019] Preferably, the molecular weight of the NH2-PEG-PCL-OH is 2000-5000.

[0020] Preferably, the aminosilane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and the added amount is 12 to 18% of the mass of NH2-PEG-PCL-OH.

[0021] Preferably, the mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 10-12:4-6.

[0022] Preferably, the amount of 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride added is 3.5 to 5.5% of the mass of the plant functional agent, and the amount of N-hydroxysuccinimide added is 1 to 1.6% of the mass of the plant functional agent.

[0023] The terminal hydroxyl group of NH2-PEG-PCL-OH is modified with an amino group to obtain bis-amino polyethylene glycol polycaprolactone. Under the action of 1-3 (dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide, the amino group of the bis-amino polyethylene glycol polycaprolactone reacts with the carboxyl group on the carboxylated β-cyclodextrin microspheres in the plant functional agent to form an amide bond. The bis-amino polyethylene glycol polycaprolactone is coated on the surface of the plant functional agent to improve the acid and alkali resistance and thermal stability of the plant functional agent.

[0024] S5. Spinning The modified plant functional agent is added into the fiber spinning solution or the polymer slice and mixed, and then the mixed fibers are formed by wet spinning or melt spinning to obtain the multifunctional jasmine, camellia and chamomile fibers.

[0025] Preferably, the fiber spinning solution is one of viscose spinning solution, acrylic spinning solution and the like.

[0026] Preferably, the polymer slice is one of PET slice, PA6 slice, PP slice and the like.

[0027] Preferably, the added amount of the modified plant functional agent is 3-6% of the effective ingredient in the fiber spinning solution (referring to the content of methyl cellulose or polyacrylonitrile in the spinning solution) or the mass of the polymer chips.

[0028] Due to the adoption of the above technical solution, the technical effects achieved by the present invention are: 1. The multifunctional jasmine, camellia and chamomile fibers prepared by the present invention have excellent antibacterial effects and natural antibacterial effects. After washing 50 times, the antibacterial rates of Staphylococcus aureus, Candida albicans and Escherichia coli are 98.5-99.2%, 98.2-99% and 97.5-98.7% respectively (determined in accordance with GB / T 20944.3-2008), meeting the antibacterial standards for textiles. The antibacterial durability is good, and the antibacterial loss rate after washing 50 times is less than 2% on average.

[0029] 2. The multifunctional jasmine, camellia and chamomile fibers prepared by the present invention have good antioxidant and anti-mite effects, with a free radical scavenging rate of more than 96% (determined according to the ABTS method of T / CCTA 20102-2023); and a mite repellent rate of more than 70% (determined according to the repellent method of GB / T 24253-2009 / 9.1).

[0030] 3. Jasmine essential oil, camellia essential oil, and chamomile essential oil not only have poor dispersibility in spinning solution and polymer slices, but also have unstable properties. The use of β-cyclodextrin microspheres can play a certain protective role on plant extracts, but the β-cyclodextrin microspheres have poor acid and alkali resistance, especially in an acidic environment, and the fiber coagulation bath is acidic, and the high temperature resistance is relatively poor. In addition, the outer edge of β-cyclodextrin is hydrophilic, and its compatibility with synthetic fibers is even worse. Therefore, the present invention utilizes the amino group of bis-aminated polyethylene glycol polycaprolactone and the carboxyl group on the carboxylated β-cyclodextrin microspheres in the plant functional agent to react to form an amide bond, and the bis-aminated polyethylene glycol polycaprolactone is coated on the surface of the plant functional agent to improve the acid and alkali resistance and thermal stability of the plant functional agent and its compatibility in synthetic fibers; it has been tested that during the fiber preparation process, the loss rate of plant active ingredients is less than 3%.

[0031] 4. The modified plant functional agent prepared by the present invention has good biocompatibility, interface compatibility and dispersibility, avoiding the decrease in fiber strength caused by poor dispersion of plant extracts directly added to fibers, and is suitable for a variety of fibers. DETAILED DESCRIPTION

[0032] The present invention is further described below in conjunction with specific embodiments.

[0033] Embodiment 1: A method for preparing multifunctional jasmine, camellia and chamomile fibers, the preparation method comprising the following steps: S1. Preparation of β-cyclodextrin microspheres Add β-cyclodextrin to a 35°C NaOH solution and stir until dissolved. Then add epichlorohydrin while stirring at a rate of 400 r / min, and react for 1.5 hours to obtain an aqueous phase. Add the oil phase to the aqueous phase, stir at high speed for 10 minutes, then heat to 70°C and stir at low speed to react for 5.5 hours. After the reaction is completed, let stand to separate the layers to remove the oil layer, centrifuge, and then wash with dilute hydrochloric acid solution, anhydrous ethanol, and deionized water for 3 times, then wash with acetone for 3 times, and dry at 70°C for 24 hours to obtain β-cyclodextrin microspheres.

[0034] The mass fraction of the NaOH solution is 35%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:5.

[0035] The molar ratio of epichlorohydrin to β-cyclodextrin is 13:1.

[0036] The volume ratio of the water phase to the oil phase is 1:3.

[0037] In the oil phase, the emulsifier accounts for 2.5%, and the rest is liquid paraffin.

[0038] The emulsifier is Span 80.

[0039] The high-speed stirring rate is 1300 r / min, and the low-speed stirring rate is 700 r / min.

[0040] S2. Modification of carboxyl groups β-cyclodextrin microspheres were added into DMF, and then succinic anhydride was slowly added, and the temperature was raised to 70-80°C for reaction for 10 hours to modify the carboxyl groups on the surface of β-cyclodextrin microspheres. After the reaction, the microspheres were centrifuged and then washed three times with acetone and deionized water in turn. After drying at 70°C for 24 hours, carboxylated β-cyclodextrin microspheres were obtained with an average particle size of 6 μm.

[0041] The added amount of succinic anhydride is 40% of the mass of the β-cyclodextrin microspheres.

[0042] S3, adsorption Carboxylated β-cyclodextrin microspheres were added to deionized water to prepare a saturated solution, and then the plant extract was added and stirred at 45°C for 7 hours. The plant extract was loaded into the carboxylated β-cyclodextrin microspheres, cooled to room temperature, and placed at 2°C for 24 hours. After filtration, it was washed with deionized water and ether in turn, and dried at 50°C for 24 hours to obtain a plant functional agent with an adsorption rate of 89%.

[0043] The plant extracts are jasmine essential oil, camellia essential oil and chamomile essential oil in a mass ratio of 1:1:1.

[0044] The mass ratio of the plant extract to the carboxylated β-cyclodextrin microspheres is 2.5:10.

[0045] S4. Preparation of bis-aminated polyethylene glycol polycaprolactone NH2-PEG-PCL-OH was added to deionized water, and then an aminosilane coupling agent was added and stirred for 1.5 hours to modify the terminal hydroxyl group of NH2-PEG-PCL-OH with an amino group to obtain diamino polyethylene glycol polycaprolactone; a plant functional agent was added to the system and stirred for 15 minutes, and then 1-3 (dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added, the pH was adjusted to 4.5, and the reaction was carried out for 3.5 hours. After the reaction was completed, the modified plant functional agent was filtered and washed with deionized water.

[0046] The molecular weight of the NH2-PEG-PCL-OH is 3000.

[0047] The aminosilane coupling agent is 3-aminopropyltriethoxysilane, and the added amount is 15% of the mass of NH2-PEG-PCL-OH.

[0048] The mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 11:5.

[0049] The added amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 4% of the mass of the plant functional agent, and the added amount of the N-hydroxysuccinimide is 1.4% of the mass of the plant functional agent.

[0050] S5. Spinning The modified plant functional agent is added into the viscose spinning solution and mixed, and then the mixed solution is wet-spun to obtain multifunctional jasmine, camellia and chamomile fibers.

[0051] The viscosity of the viscose spinning solution was controlled at 60 s (falling ball method), the maturity was controlled at 12 mL (10% NH4CL), and the methyl cellulose content was 8 wt%.

[0052] The added amount of the modified plant functional agent is 5% of the methyl cellulose content in the viscose spinning solution.

[0053] Embodiment 2: A method for preparing multifunctional jasmine, camellia and chamomile fibers, the preparation method comprising the following steps: S1. Preparation of β-cyclodextrin microspheres Add β-cyclodextrin to a 30°C NaOH solution and stir until dissolved. Then add epichlorohydrin while stirring at a stirring rate of 300r / min, and react for 1 hour to obtain an aqueous phase. Add the oil phase to the aqueous phase, stir at high speed for 5 minutes, then heat to 60°C and stir at low speed to react for 5 hours. After the reaction is completed, let it stand to separate the layers to remove the oil layer, centrifuge, and then wash with dilute hydrochloric acid solution, anhydrous ethanol, and deionized water twice, then wash with acetone three times, and dry at 60°C for 24 hours to obtain β-cyclodextrin microspheres.

[0054] The mass fraction of the NaOH solution is 20%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:4.

[0055] The molar ratio of epichlorohydrin to β-cyclodextrin is 12:1.

[0056] The volume ratio of the water phase to the oil phase is 1:2.

[0057] In the oil phase, the emulsifier accounts for 2%, and the rest is liquid paraffin.

[0058] The emulsifier is Span 80.

[0059] The high-speed stirring rate is 1200 r / min, and the low-speed stirring rate is 600 r / min.

[0060] S2. Modification of carboxyl groups β-cyclodextrin microspheres were added into DMF, and then succinic anhydride was slowly added. The temperature was raised to 70°C for reaction for 8 hours, and carboxyl groups were modified on the surface of β-cyclodextrin microspheres. After the reaction, the product was centrifuged and washed twice with acetone and deionized water in turn. After drying at 60°C for 24 hours, carboxylated β-cyclodextrin microspheres were obtained with an average particle size of 8 μm.

[0061] The added amount of succinic anhydride is 30% of the mass of the β-cyclodextrin microspheres.

[0062] S3, adsorption Add carboxylated β-cyclodextrin microspheres into deionized water to prepare a saturated solution, then add the plant extract, stir at 40°C for 6 hours, load the plant extract into the carboxylated β-cyclodextrin microspheres, cool to room temperature, place at 0°C for 24 hours, filter, wash with deionized water and ether in turn, and dry at 40°C for 24 hours to obtain the plant functional agent.

[0063] The plant extracts are jasmine essential oil, camellia essential oil and chamomile essential oil in a mass ratio of 1:1:1.

[0064] The mass ratio of the plant extract to the carboxylated beta-cyclodextrin microspheres is 2:7.

[0065] S4. Preparation of bis-aminated polyethylene glycol polycaprolactone NH2-PEG-PCL-OH was added to deionized water, and then an aminosilane coupling agent was added and stirred for 1 hour to modify the terminal hydroxyl group of NH2-PEG-PCL-OH with an amino group to obtain diamino polyethylene glycol polycaprolactone; a plant functional agent was added to the system and stirred for 10 minutes, and then 1-3 (dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added, the pH was adjusted to 4, and the reaction was carried out for 3 hours. After the reaction was completed, the modified plant functional agent was filtered and washed with deionized water.

[0066] The molecular weight of the NH2-PEG-PCL-OH is 2000.

[0067] The aminosilane coupling agent is 3-aminopropyltriethoxysilane, and the added amount is 12% of the mass of NH2-PEG-PCL-OH.

[0068] The mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 10:4.

[0069] The added amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 3% of the mass of the plant functional agent, and the added amount of the N-hydroxysuccinimide is 1% of the mass of the plant functional agent.

[0070] S5. Spinning The modified plant functional agent is added into the viscose spinning solution and mixed, and then the mixed solution is wet-spun to obtain multifunctional jasmine, camellia and chamomile fibers.

[0071] The viscosity of the viscose spinning solution was controlled at 60 s (falling ball method), the maturity was controlled at 12 mL (10% NH4CL), and the methyl cellulose content was 8 wt%.

[0072] The added amount of the modified plant functional agent is 3% of the methyl cellulose content in the viscose spinning solution.

[0073] Embodiment 3: A method for preparing multifunctional jasmine, camellia and chamomile fibers, the preparation method comprising the following steps: S1. Preparation of β-cyclodextrin microspheres Add β-cyclodextrin to a 40°C NaOH solution and stir until dissolved, then add epichlorohydrin while stirring at a stirring rate of 500r / min, and react for 2 hours to obtain an aqueous phase; add the oil phase to the aqueous phase, stir at high speed for 15 minutes, then heat to 75°C and stir at low speed to react for 6 hours. After the reaction is completed, let it stand to separate the layers to remove the oil layer, centrifuge, and then wash with dilute hydrochloric acid solution, anhydrous ethanol, and deionized water twice, then wash with acetone three times, and dry at 80°C for 24 hours to obtain β-cyclodextrin microspheres.

[0074] The mass fraction of the NaOH solution is 40%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:6.

[0075] The molar ratio of epichlorohydrin to β-cyclodextrin is 15:1.

[0076] The volume ratio of the water phase to the oil phase is 1:4.

[0077] In the oil phase, the emulsifier accounts for 3%, and the rest is liquid paraffin.

[0078] The emulsifier is Toast 20.

[0079] The high-speed stirring rate is 1400 r / min, and the low-speed stirring rate is 800 r / min.

[0080] S2. Modification of carboxyl groups β-cyclodextrin microspheres were added into DMF, and then succinic anhydride was slowly added. The temperature was raised to 80°C for reaction for 12 hours, and carboxyl groups were modified on the surface of β-cyclodextrin microspheres. After the reaction, the product was centrifuged and washed three times with acetone and deionized water in turn. After drying at 80°C for 24 hours, carboxylated β-cyclodextrin microspheres were obtained with an average particle size of 5 μm.

[0081] The added amount of succinic anhydride is 50% of the mass of the β-cyclodextrin microspheres.

[0082] S3, adsorption Add carboxylated β-cyclodextrin microspheres into deionized water to prepare a saturated solution, then add the plant extract, stir at 50°C for 8 hours, load the plant extract into the carboxylated β-cyclodextrin microspheres, cool to room temperature, place at 5°C for 24 hours, filter, wash with deionized water and ether in turn, and dry at 60°C for 24 hours to obtain the plant functional agent.

[0083] The plant extracts are jasmine essential oil, camellia essential oil and chamomile essential oil in a mass ratio of 1:1:1.

[0084] The mass ratio of the plant extract to the carboxylated β-cyclodextrin microspheres is 3:12.

[0085] S4. Preparation of bis-aminated polyethylene glycol polycaprolactone NH2-PEG-PCL-OH was added to deionized water, and then an aminosilane coupling agent was added and stirred for 2 hours to modify the terminal hydroxyl group of NH2-PEG-PCL-OH with an amino group to obtain diamino polyethylene glycol polycaprolactone; a plant functional agent was added to the system and stirred for 20 minutes, and then 1-3 (dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added, the pH was adjusted to 5, and the reaction was carried out for 4 hours. After the reaction was completed, the modified plant functional agent was filtered and washed with deionized water.

[0086] The molecular weight of the NH2-PEG-PCL-OH is 5000.

[0087] The aminosilane coupling agent is 3-aminopropyltriethoxysilane, and the added amount is 18% of the mass of NH2-PEG-PCL-OH.

[0088] The mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 12:6.

[0089] The added amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 5% of the mass of the plant functional agent, and the added amount of the N-hydroxysuccinimide is 1.6% of the mass of the plant functional agent.

[0090] S5. Spinning The modified plant functional agent is added into the viscose spinning solution and mixed, and then the mixed solution is wet-spun to obtain multifunctional jasmine, camellia and chamomile fibers.

[0091] The viscosity of the viscose spinning solution was controlled at 60 s (falling ball method), the maturity was controlled at 12 mL (10% NH4CL), and the methyl cellulose content was 8 wt%.

[0092] The added amount of the modified plant functional agent is 6% of the methyl cellulose content in the viscose spinning solution.

[0093] Example 4: A method for preparing multifunctional jasmine, camellia and chamomile fibers, the preparation method comprising the following steps: S1. Preparation of β-cyclodextrin microspheres Add β-cyclodextrin to a 35°C NaOH solution and stir until dissolved. Then add epichlorohydrin while stirring at a rate of 400 r / min, and react for 1.5 hours to obtain an aqueous phase. Add the oil phase to the aqueous phase, stir at high speed for 10 minutes, then heat to 70°C and stir at low speed to react for 5.5 hours. After the reaction is completed, let stand to separate the layers to remove the oil layer, centrifuge, and then wash with dilute hydrochloric acid solution, anhydrous ethanol, and deionized water for 3 times, then wash with acetone for 3 times, and dry at 70°C for 24 hours to obtain β-cyclodextrin microspheres.

[0094] The mass fraction of the NaOH solution is 35%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:5.

[0095] The molar ratio of epichlorohydrin to β-cyclodextrin is 13:1.

[0096] The volume ratio of the water phase to the oil phase is 1:3.

[0097] In the oil phase, the emulsifier accounts for 2.5%, and the rest is liquid paraffin.

[0098] The emulsifier is Span 80.

[0099] The high-speed stirring rate is 1300 r / min, and the low-speed stirring rate is 700 r / min.

[0100] S2. Modification of carboxyl groups β-cyclodextrin microspheres were added into DMF, and then succinic anhydride was slowly added, and the temperature was raised to 70-80°C for reaction for 10 hours to modify the carboxyl groups on the surface of β-cyclodextrin microspheres. After the reaction, the microspheres were centrifuged and then washed three times with acetone and deionized water in turn. After drying at 70°C for 24 hours, carboxylated β-cyclodextrin microspheres were obtained with an average particle size of 6 μm.

[0101] The added amount of succinic anhydride is 40% of the mass of the β-cyclodextrin microspheres.

[0102] S3, adsorption Carboxylated β-cyclodextrin microspheres were added to deionized water to prepare a saturated solution, and then the plant extract was added and stirred at 45°C for 7 hours. The plant extract was loaded into the carboxylated β-cyclodextrin microspheres, cooled to room temperature, and placed at 2°C for 24 hours. After filtration, it was washed with deionized water and ether in turn, and dried at 50°C for 24 hours to obtain a plant functional agent with an adsorption rate of 89%.

[0103] The plant extracts are jasmine essential oil, camellia essential oil and chamomile essential oil in a mass ratio of 1:1:1.

[0104] The mass ratio of the plant extract to the carboxylated β-cyclodextrin microspheres is 2.5:10.

[0105] S4. Preparation of bis-aminated polyethylene glycol polycaprolactone NH2-PEG-PCL-OH was added to deionized water, and then an aminosilane coupling agent was added and stirred for 1.5 hours to modify the terminal hydroxyl group of NH2-PEG-PCL-OH with an amino group to obtain diamino polyethylene glycol polycaprolactone; a plant functional agent was added to the system and stirred for 15 minutes, and then 1-3 (dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added, the pH was adjusted to 4.5, and the reaction was carried out for 3.5 hours. After the reaction was completed, the modified plant functional agent was filtered and washed with deionized water.

[0106] The molecular weight of the NH2-PEG-PCL-OH is 3000.

[0107] The aminosilane coupling agent is 3-aminopropyltriethoxysilane, and the added amount is 15% of the mass of NH2-PEG-PCL-OH.

[0108] The mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 11:5.

[0109] The added amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 4% of the mass of the plant functional agent, and the added amount of the N-hydroxysuccinimide is 1.4% of the mass of the plant functional agent.

[0110] S5. Spinning The modified plant functional agent was added to PET chips and blended for 20 minutes before melt spinning to obtain multifunctional jasmine, camellia and chamomile fibers.

[0111] The process parameters of the melt spinning are: the temperature of zone 1 is 305°C, the temperature of zone 2 is 320°C, the temperature of zone 3 is 305°C, and the temperature of zone 4 is 300°C.

[0112] The added amount of the modified plant functional agent is 5% of the mass of the PET slices.

[0113] Example 5: A method for preparing multifunctional jasmine, camellia and chamomile fibers, the preparation method comprising the following steps: S1. Preparation of β-cyclodextrin microspheres Add β-cyclodextrin to a 30°C NaOH solution and stir until dissolved. Then add epichlorohydrin while stirring at a stirring rate of 300r / min, and react for 1 hour to obtain an aqueous phase. Add the oil phase to the aqueous phase, stir at high speed for 5 minutes, then heat to 60°C and stir at low speed to react for 5 hours. After the reaction is completed, let it stand to separate the layers to remove the oil layer, centrifuge, and then wash with dilute hydrochloric acid solution, anhydrous ethanol, and deionized water twice, then wash with acetone three times, and dry at 60°C for 24 hours to obtain β-cyclodextrin microspheres.

[0114] The mass fraction of the NaOH solution is 20%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:4.

[0115] The molar ratio of epichlorohydrin to β-cyclodextrin is 12:1.

[0116] The volume ratio of the water phase to the oil phase is 1:2.

[0117] In the oil phase, the emulsifier accounts for 2%, and the rest is liquid paraffin.

[0118] The emulsifier is Span 80.

[0119] The high-speed stirring rate is 1200 r / min, and the low-speed stirring rate is 600 r / min.

[0120] S2. Modification of carboxyl groups β-cyclodextrin microspheres were added into DMF, and then succinic anhydride was slowly added. The temperature was raised to 70°C for reaction for 8 hours, and carboxyl groups were modified on the surface of β-cyclodextrin microspheres. After the reaction, the product was centrifuged and washed twice with acetone and deionized water in turn. After drying at 60°C for 24 hours, carboxylated β-cyclodextrin microspheres were obtained with an average particle size of 8 μm.

[0121] The added amount of succinic anhydride is 30% of the mass of the β-cyclodextrin microspheres.

[0122] S3, adsorption Add carboxylated β-cyclodextrin microspheres into deionized water to prepare a saturated solution, then add the plant extract, stir at 40°C for 6 hours, load the plant extract into the carboxylated β-cyclodextrin microspheres, cool to room temperature, place at 0°C for 24 hours, filter, wash with deionized water and ether in turn, and dry at 40°C for 24 hours to obtain the plant functional agent.

[0123] The plant extracts are jasmine essential oil, camellia essential oil and chamomile essential oil in a mass ratio of 1:1:1.

[0124] The mass ratio of the plant extract to the carboxylated beta-cyclodextrin microspheres is 2:7.

[0125] S4. Preparation of bis-aminated polyethylene glycol polycaprolactone NH2-PEG-PCL-OH was added to deionized water, and then an aminosilane coupling agent was added and stirred for 1 hour to modify the terminal hydroxyl group of NH2-PEG-PCL-OH with an amino group to obtain diamino polyethylene glycol polycaprolactone; a plant functional agent was added to the system and stirred for 10 minutes, and then 1-3 (dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added, the pH was adjusted to 4, and the reaction was carried out for 3 hours. After the reaction was completed, the modified plant functional agent was filtered and washed with deionized water.

[0126] The molecular weight of the NH2-PEG-PCL-OH is 2000.

[0127] The aminosilane coupling agent is 3-aminopropyltriethoxysilane, and the added amount is 12% of the mass of NH2-PEG-PCL-OH.

[0128] The mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 10:4.

[0129] The added amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 3% of the mass of the plant functional agent, and the added amount of the N-hydroxysuccinimide is 1% of the mass of the plant functional agent.

[0130] S5. Spinning The modified plant functional agent was added to PET chips and blended for 20 minutes before melt spinning to obtain multifunctional jasmine, camellia and chamomile fibers.

[0131] The process parameters of the melt spinning are: the temperature of zone 1 is 305°C, the temperature of zone 2 is 320°C, the temperature of zone 3 is 305°C, and the temperature of zone 4 is 300°C.

[0132] The added amount of the modified plant functional agent is 3% of the mass of the PET slices.

[0133] Example 6: A method for preparing multifunctional jasmine, camellia and chamomile fibers, the preparation method comprising the following steps: S1. Preparation of β-cyclodextrin microspheres Add β-cyclodextrin to a 40°C NaOH solution and stir until dissolved, then add epichlorohydrin while stirring at a stirring rate of 500r / min, and react for 2 hours to obtain an aqueous phase; add the oil phase to the aqueous phase, stir at high speed for 15 minutes, then heat to 75°C and stir at low speed to react for 6 hours. After the reaction is completed, let it stand to separate the layers to remove the oil layer, centrifuge, and then wash with dilute hydrochloric acid solution, anhydrous ethanol, and deionized water twice, then wash with acetone three times, and dry at 80°C for 24 hours to obtain β-cyclodextrin microspheres.

[0134] The mass fraction of the NaOH solution is 40%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:6.

[0135] The molar ratio of epichlorohydrin to β-cyclodextrin is 15:1.

[0136] The volume ratio of the water phase to the oil phase is 1:4.

[0137] In the oil phase, the emulsifier accounts for 3%, and the rest is liquid paraffin.

[0138] The emulsifier is Toast 20.

[0139] The high-speed stirring rate is 1400 r / min, and the low-speed stirring rate is 800 r / min.

[0140] S2. Modification of carboxyl groups β-cyclodextrin microspheres were added into DMF, and then succinic anhydride was slowly added. The temperature was raised to 80°C for reaction for 12 hours, and carboxyl groups were modified on the surface of β-cyclodextrin microspheres. After the reaction, the product was centrifuged and washed three times with acetone and deionized water in turn. After drying at 80°C for 24 hours, carboxylated β-cyclodextrin microspheres were obtained with an average particle size of 5 μm.

[0141] The added amount of succinic anhydride is 50% of the mass of the β-cyclodextrin microspheres.

[0142] S3, adsorption Add carboxylated β-cyclodextrin microspheres into deionized water to prepare a saturated solution, then add the plant extract, stir at 50°C for 8 hours, load the plant extract into the carboxylated β-cyclodextrin microspheres, cool to room temperature, place at 5°C for 24 hours, filter, wash with deionized water and ether in turn, and dry at 60°C for 24 hours to obtain the plant functional agent.

[0143] The plant extracts are jasmine essential oil, camellia essential oil and chamomile essential oil in a mass ratio of 1:1:1.

[0144] The mass ratio of the plant extract to the carboxylated β-cyclodextrin microspheres is 3:12.

[0145] S4. Preparation of bis-aminated polyethylene glycol polycaprolactone NH2-PEG-PCL-OH was added to deionized water, and then an aminosilane coupling agent was added and stirred for 2 hours to modify the terminal hydroxyl group of NH2-PEG-PCL-OH with an amino group to obtain diamino polyethylene glycol polycaprolactone; a plant functional agent was added to the system and stirred for 20 minutes, and then 1-3 (dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added, the pH was adjusted to 5, and the reaction was carried out for 4 hours. After the reaction was completed, the modified plant functional agent was filtered and washed with deionized water.

[0146] The molecular weight of the NH2-PEG-PCL-OH is 5000.

[0147] The aminosilane coupling agent is 3-aminopropyltriethoxysilane, and the added amount is 18% of the mass of NH2-PEG-PCL-OH.

[0148] The mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 12:6.

[0149] The added amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 5% of the mass of the plant functional agent, and the added amount of the N-hydroxysuccinimide is 1.6% of the mass of the plant functional agent.

[0150] S5. Spinning The modified plant functional agent was added to PET chips and blended for 20 minutes before melt spinning to obtain multifunctional jasmine, camellia and chamomile fibers.

[0151] The process parameters of the melt spinning are: the temperature of zone 1 is 305°C, the temperature of zone 2 is 320°C, the temperature of zone 3 is 305°C, and the temperature of zone 4 is 300°C.

[0152] The added amount of the modified plant functional agent is 6% of the mass of the PET slices.

[0153] Comparative Example 1: Representative Example 1 was selected, S4 was removed, and the rest were consistent with Example 1, as Comparative Example 1.

[0154] Comparative Example 2: Representative Example 4 was selected, S4 was removed, and the rest were consistent with Example 1, as Comparative Example 2.

[0155] Comparative Example 3: Select the representative Example 1, remove the aminosilane coupling agent in S4, directly react NH2-PEG-PCL-OH with the plant functional agent, and the rest are consistent with Example 1, as Comparative Example 3.

[0156] Comparative Example 4: Representative Example 4 was selected, the aminosilane coupling agent in S4 was removed, and NH2-PEG-PCL-OH was directly reacted with the plant functional agent. The rest was consistent with Example 1, as Comparative Example 4.

[0157] The properties of the fibers in Examples 1-6 and the comparative example were measured, as shown in Table 1.

[0158] Table 1 Test items (Dry) breaking strength (cN / dtex) Wet breaking strength (cN / dtex) Antibacterial loss rate after 50 washes (%) Loss rate of plant active ingredients (%) Example 1 2.36 1.68 1.06 1.13 Example 2 2.15 1.57 1.64 1.85 Example 3 2.24 1.62 1.33 1.68 Example 4 3.53 / 1.12 2.16 Example 5 3.37 / 1.59 2.77 Example 6 3.45 / 1.3 2.32 Comparative Example 1 2.19 1.53 12.41 7.8 Comparative Example 2 2.9 / 12.83 26.7 Comparative Example 3 2.25 1.6 7.82 5.9 Comparative Example 4 3.47 / 7.65 13.8 As can be seen from Table 1, by removing S4 from Comparative Examples 1 and 2, the mechanical properties are reduced, especially for Comparative Example 2; the antibacterial loss rate and the loss rate of plant active ingredients after 50 washings are also greatly reduced, indicating that the use of β-cyclodextrin microspheres can play a certain protective role on plant extracts. However, the acid and alkali resistance and high temperature resistance of β-cyclodextrin microspheres are also relatively poor, especially high temperature resistance, and the outer edge of β-cyclodextrin is hydrophilic, and its compatibility with synthetic fibers is worse. Therefore, the strength of the fiber in Comparative Example 2 and the loss rate of plant active ingredients have decreased more significantly.

[0159] In Comparative Examples 3 and 4, the aminosilane coupling agent in S4 is removed, and NH2-PEG-PCL-OH is directly reacted with the plant functional agent. There is only one amino group in NH2-PEG-PCL-OH, so the coating effect on the plant functional agent is poor. Although the interfacial compatibility of the plant functional agent can be improved, the acid and alkali resistance, high temperature resistance and water washing durability are not as good as those in the embodiment, but better than Comparative Examples 1 and 2.

[0160] The comparative example shows that the amino group of bis-amino polyethylene glycol polycaprolactone reacts with the carboxyl group on the carboxylated β-cyclodextrin microspheres in the plant functional agent to form an amide bond, and the bis-amino polyethylene glycol polycaprolactone is coated on the surface of the plant functional agent to improve the acid and alkali resistance and thermal stability of the plant functional agent and its compatibility in synthetic fibers.

[0161] In addition, the multifunctional jasmine, camellia and chamomile fibers prepared by Examples 1-6 have excellent antibacterial effects and natural antibacterial effects. After washing 50 times, the antibacterial rates of Staphylococcus aureus, Candida albicans and Escherichia coli are 98.5-99.2%, 98.2-99% and 97.5-98.7% respectively (determined in accordance with GB / T 20944.3-2008), meeting the antibacterial standards for textiles. The fibers have good antioxidant and anti-mite effects, with a free radical scavenging rate of more than 96% (determined in accordance with T / CCTA 20102-2023 ABTS method); and a mite repellent rate of more than 70% (determined in accordance with GB / T 24253-2009 / 9.1 repellency method).

[0162] Unless otherwise specified, the ratios and percentages described in the present invention are all weight ratios and weight percentages; and the raw materials are all commercially available.

[0163] Finally, it should be noted that the above is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention is described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing multifunctional jasmine, camellia and chamomile fibers, characterized in that: The preparation method comprises the preparation of beta-cyclodextrin microspheres, modification of carboxyl groups, adsorption, preparation of diaminated polyethylene glycol polycaprolactone and spinning.

2. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 1, characterized in that: The preparation of the β-cyclodextrin microspheres comprises the following steps: adding β-cyclodextrin to a 30-40° C. NaOH solution and stirring until dissolved; then adding epichlorohydrin while stirring at a stirring rate of 300-500 r / min; and reacting for 1-2 hours to obtain an aqueous phase; adding an oil phase to the aqueous phase, stirring at a high speed for 5-15 minutes, heating to 60-75° C. and stirring at a low speed for 5-6 hours; after the reaction is completed, standing to separate the layers to remove the oil layer, centrifuging, and then washing with a dilute hydrochloric acid solution, anhydrous ethanol, and deionized water for 2-3 times in sequence, and then washing with acetone for 2-3 times, and drying at 60-80° C. for 24 hours to obtain the β-cyclodextrin microspheres.

3. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 2, characterized in that: The mass fraction of the NaOH solution is 20-40%; the mass ratio of the β-cyclodextrin to the NaOH solution is 1:4-6; The molar ratio of epichlorohydrin to β-cyclodextrin is 12 to 15:1; The volume ratio of the water phase to the oil phase is 1:2-4; In the oil phase, the emulsifier accounts for 2-3%, and the rest is liquid paraffin; The high-speed stirring rate is 1200-1400 r / min, and the low-speed stirring rate is 600-800 r / min.

4. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 1, characterized in that: The modification of the carboxyl group is as follows: adding β-cyclodextrin microspheres to DMF, then slowly adding succinic anhydride, heating to 70-80° C. for reaction for 8-12 hours, centrifuging after the reaction, washing the product with acetone and deionized water for 2-3 times, and drying at 60-80° C. for 24 hours to obtain carboxylated β-cyclodextrin microspheres; The added amount of succinic anhydride is 30-50% of the mass of the β-cyclodextrin microspheres.

5. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 1, characterized in that: The adsorption is as follows: carboxylated β-cyclodextrin microspheres are added to deionized water to prepare a saturated solution, then the plant extract is added, stirred at 40-50° C. for 6-8 hours, cooled to room temperature, placed at 0-5° C. for 24 hours, filtered, washed with deionized water and ether in turn, and dried at 40-60° C. for 24 hours to obtain the plant functional agent.

6. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 5, characterized in that: The plant extract is a mixture of jasmine essential oil, camellia essential oil and chamomile essential oil; The mass ratio of the plant extract to the carboxylated beta-cyclodextrin microspheres is 2-3:7-12.

7. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 1, characterized in that: The preparation of the bis-amino polyethylene glycol polycaprolactone is as follows: NH2-PEG-PCL-OH is added to deionized water, and then an aminosilane coupling agent is added and stirred for reaction for 1 to 2 hours to obtain the bis-amino polyethylene glycol polycaprolactone; a plant functional agent is added to the system and stirred for 10 to 20 minutes, and then 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide are added, the pH is adjusted to 4 to 5, and the reaction is carried out for 3 to 4 hours. After the reaction is completed, the modified plant functional agent is filtered and washed with deionized water to obtain the modified plant functional agent.

8. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 7, characterized in that: The aminosilane coupling agent is one or more of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and the added amount is 12-18% of the mass of NH2-PEG-PCL-OH; The mass ratio of the added amount of the plant functional agent to NH2-PEG-PCL-OH is 10-12:4-6; The amount of 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride added is 3.5 to 5.5% of the mass of the plant functional agent, and the amount of N-hydroxysuccinimide added is 1 to 1.6% of the mass of the plant functional agent.

9. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 1, characterized in that: The spinning comprises adding the modified plant functional agent to the fiber spinning solution or polymer slices, blending the mixture, and then wet spinning or melt spinning to obtain multifunctional jasmine, camellia, or chamomile fibers; The fiber spinning solution is one of a viscose spinning solution, an acrylic spinning solution, etc.; The polymer slice is one of PET slice, PA6 slice, PP slice and the like.

10. The method for preparing multifunctional jasmine, camellia and chamomile fiber according to claim 9, characterized in that: The added amount of the modified plant functional agent is 3-6% of the effective component in the fiber spinning solution (referring to the content of methyl cellulose or polyacrylonitrile in the spinning solution) or the mass of the polymer slice.