CN114150392A - Preparation method of plant source long-acting mosquito-repelling composite functional filament - Google Patents
Preparation method of plant source long-acting mosquito-repelling composite functional filament Download PDFInfo
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- CN114150392A CN114150392A CN202111430070.7A CN202111430070A CN114150392A CN 114150392 A CN114150392 A CN 114150392A CN 202111430070 A CN202111430070 A CN 202111430070A CN 114150392 A CN114150392 A CN 114150392A
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- porous aerogel
- repellent
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- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 229920002678 cellulose Polymers 0.000 claims abstract description 129
- 239000001913 cellulose Substances 0.000 claims abstract description 129
- 239000004964 aerogel Substances 0.000 claims abstract description 113
- 239000000077 insect repellent Substances 0.000 claims abstract description 88
- 230000004048 modification Effects 0.000 claims abstract description 14
- 238000012986 modification Methods 0.000 claims abstract description 14
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 12
- 241000196324 Embryophyta Species 0.000 claims description 105
- 238000003756 stirring Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000284 extract Substances 0.000 claims description 28
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 210000002700 urine Anatomy 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 20
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 20
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 20
- 229960002218 sodium chlorite Drugs 0.000 claims description 20
- 235000005881 Calendula officinalis Nutrition 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 229940105040 geranium extract Drugs 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- 244000165852 Eucalyptus citriodora Species 0.000 claims description 12
- 235000004722 Eucalyptus citriodora Nutrition 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 10
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 10
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 10
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 229920000742 Cotton Polymers 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000021523 carboxylation Effects 0.000 claims description 7
- 238000006473 carboxylation reaction Methods 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002699 waste material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 4
- 240000000785 Tagetes erecta Species 0.000 claims 2
- 230000003213 activating effect Effects 0.000 claims 1
- 241000255925 Diptera Species 0.000 abstract description 42
- 239000004744 fabric Substances 0.000 abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052681 coesite Inorganic materials 0.000 abstract description 14
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 14
- 239000000377 silicon dioxide Substances 0.000 abstract description 14
- 229910052682 stishovite Inorganic materials 0.000 abstract description 14
- 229910052905 tridymite Inorganic materials 0.000 abstract description 14
- 241000282414 Homo sapiens Species 0.000 abstract description 9
- 239000000341 volatile oil Substances 0.000 abstract description 9
- 238000002791 soaking Methods 0.000 abstract description 8
- 206010020751 Hypersensitivity Diseases 0.000 abstract description 3
- 208000026935 allergic disease Diseases 0.000 abstract description 3
- 230000007815 allergy Effects 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 230000001846 repelling effect Effects 0.000 description 30
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 24
- 239000004594 Masterbatch (MB) Substances 0.000 description 23
- 241000736851 Tagetes Species 0.000 description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 239000004202 carbamide Substances 0.000 description 12
- 230000005496 eutectics Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- 238000000605 extraction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- 235000005979 Citrus limon Nutrition 0.000 description 10
- 244000131522 Citrus pyriformis Species 0.000 description 10
- 230000009471 action Effects 0.000 description 9
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 8
- 235000019743 Choline chloride Nutrition 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 description 8
- 239000006087 Silane Coupling Agent Substances 0.000 description 8
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 description 8
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 8
- 229960003178 choline chloride Drugs 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000287 crude extract Substances 0.000 description 8
- 229940007062 eucalyptus extract Drugs 0.000 description 8
- 238000002074 melt spinning Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 235000006408 oxalic acid Nutrition 0.000 description 8
- 229920000570 polyether Polymers 0.000 description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 description 8
- 238000001338 self-assembly Methods 0.000 description 8
- 229920002545 silicone oil Polymers 0.000 description 8
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 8
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000000419 plant extract Substances 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000000194 supercritical-fluid extraction Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 208000032544 Cicatrix Diseases 0.000 description 1
- 208000001490 Dengue Diseases 0.000 description 1
- 206010012310 Dengue fever Diseases 0.000 description 1
- 241000219927 Eucalyptus Species 0.000 description 1
- 241000208152 Geranium Species 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000002032 cellular defenses Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 208000025729 dengue disease Diseases 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 206010014599 encephalitis Diseases 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 201000004792 malaria Diseases 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 230000037387 scars Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides a preparation method of a plant-derived long-acting mosquito-repelling composite functional filament, which comprises the steps of preparation of a plant-derived mosquito-repelling component, preparation and modification of cellulose nano porous aerogel, preparation of plant-derived mosquito-repelling functional master batches and spinning. Mixing SiO2The embedding cellulose nanometer porous aerogel, the porous structure of cellulose nanometer porous aerogel obtains supporting, is difficult for collapsing, can soak again in plant source mosquito repellent component solution and recycle after washing many times, realizes long-term mosquito repellent, compares environmental protection more with traditional mosquito repellent mode. After the plant source long-acting mosquito-repellent composite functional filament is woven into fabric, the fabric can be washed for more than 50 times, the continuous cyclic use can be realized by soaking and re-adsorbing mosquito-repellent essential oil, the odor emitted by the fabric can purify air and drive mosquitoes, and the mosquitoes can be effectively preventedThe human body is bitten by mosquitoes and does not have any discomfort phenomena such as allergy and the like.
Description
Technical Field
The invention relates to the field of functional textiles, in particular to a preparation method of a plant source long-acting mosquito-repellent composite functional filament.
Background
Mosquitoes not only suck blood but also transmit many diseases, such as: malaria, encephalitis B, dengue fever and the like, which threatens the health of human beings, especially people who work outdoors, such as frontier fighters, firemen, farmers and the like, are infected by mosquitoes and suffer from insanity when working outdoors. The traditional mosquito repelling method is short in action time, limited in use scene and high in cost, such as mosquito repelling water, electric mosquito swatters, mosquito repellent incense and the like, the traditional mosquito repelling products can be used only once and cannot be recycled, and the traditional mosquito repelling products are made of chemical medicines, so that certain influence can be caused on human health while repelling mosquitoes, and especially children with poor resistance can be achieved.
Plants are an important component of the ecosystem and occupy an important place in human productive life. The diversity of the plants endows different functions, for example, the leaves of the eucalyptus citriodora have strong lemon flavor, can be used for refining spices to manufacture perfumed soap, and because the lemon flavor is very strong, mosquitoes, flies and the like are dare away from each other, and the eucalyptus citriodora has the effects of repelling mosquitoes and insects; the geranium essential oil has the natural characteristics of relieving pain, resisting bacteria, extending into scars, enhancing the cellular defense function, deodorizing, stopping bleeding and tonifying body, is suitable for all skins, has the effects of deep purification and convergence, and can balance the oil secretion of the skin; marigold essential oil is an excellent natural insect repellent. Therefore, the method for preparing the functional filament with the long-acting mosquito repelling function by extracting the functional components from the plants and compounding the functional components with the polymer is a green and sustainable method, and has wide application prospect and commercial value.
In the prior art, most of the mosquito repellent fabrics are prepared based on the post-finishing of mosquito repellent essential oil, for example, patent CN201210348712.3 discloses a mosquito repellent summer quilt and a production method thereof. When the sheet is produced, the essential oil of the vanilla and the essential oil of the eucalyptus are added into the core layer by adopting a composite spinning method and a printing finishing process, so that the lasting mosquito repelling effect of the essential oil is ensured. Patent CN201510284983.0 proposes an antibacterial mosquito-repellent fabric with good effect and a preparation method thereof, yarns are respectively immersed in antibacterial mosquito-repellent finishing liquid, and the antibacterial mosquito-repellent finishing yarns are used as warp yarns and weft yarns to weave the antibacterial mosquito-repellent fabric. The existing functional filament realizes a certain antibacterial mosquito-repellent effect, but the problems of general durability, poor water washing resistance and the like of the mosquito-repellent filament are not fundamentally solved, and the phenomenon that a user is easy to generate allergy is caused by the fact that the mosquito-repellent component is coated on the surface of the filament to be contacted with the skin.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a plant source long-acting mosquito-repellent composite functional filament, which realizes the following purposes:
1. the plant source long-acting mosquito-repelling composite functional filament is prepared, the mosquito-repelling effect is good in durability, and the mosquito-repelling effect is basically unchanged after multiple times of washing;
2. the phenomenon that a user is easy to be allergic after the mosquito repellent component is directly coated on the filament is solved;
3. the plant extract is used as a mosquito repellent component, and is non-toxic and harmless to human bodies;
4. the problems of poor stability of the porous structure of the cellulose nano porous aerogel, easy collapse of pores after washing and kneading, poor adsorbability and the like are solved;
5. after the plant source long-acting mosquito-repellent composite functional filament is woven into a fabric, the fabric can be washed for more than 50 times, the continuous cyclic use can be realized by soaking and adsorbing mosquito-repellent essential oil, and the odor emitted by the fabric can purify air and drive mosquitoes, so that the human body can be effectively prevented from being bitten by the mosquitoes.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a plant-derived long-acting mosquito-repelling composite functional filament, which comprises the steps of preparation of a plant-derived mosquito-repelling component, preparation and modification of cellulose nano porous aerogel, preparation of plant-derived mosquito-repelling functional master batches and spinning.
Preparation of plant-derived mosquito-repellent component
The botanical mosquito-repellent component comprises a eucalyptus citriodora extract, a geranium extract and a marigold extract, and the proportion of the eucalyptus citriodora extract, the geranium extract and the marigold extract is 3-5:1-2: 1.
The preparation of the botanical mosquito repellent component comprises ultrasonic stripping and supercritical carbon dioxide extraction.
S1 ultrasonic peeling
Drying flowers or leaves of plants, pulverizing to 80-100 mesh with a pulverizer to obtain powder, dissolving in eutectic solvent to obtain mixed solution, ultrasonic stripping, and concentrating to obtain crude extract.
Preferably, the eutectic solvent comprises choline chloride and oxalic acid, and the mass ratio of the choline chloride to the oxalic acid is 1: 2-3.
Preferably, the specific gravity of the low eutectic solvent in the mixed solution is 90-98 wt%.
Preferably, the frequency of the ultrasonic stripping is 30-50KHz, the power is 100-200W, and the time is 20-30 min.
S2, supercritical carbon dioxide extraction
Filling the crude extract in layers, performing supercritical carbon dioxide extraction at supercritical extraction pressure of 25-30Mpa, extraction temperature of 38-44 deg.C, carbon dioxide flow of 20-24kg/h, and extraction time of 1.5-2h, circulating the extracted supercritical fluid into a separator through an expansion valve, separating in the separator by isothermal pressure reduction separation method at separation temperature of 42-54 deg.C and separation pressure of 7-8Mpa, and recycling the decompressed carbon dioxide to obtain plant extract.
Further, according to the steps of S1 and S2, a lemon eucalyptus extract, a geranium extract and a marigold extract are respectively prepared, and then the plant source mosquito repelling component is prepared according to the proportion of the lemon eucalyptus extract, the geranium extract and the marigold extract being 3-5:1-2: 1.
Preparation of cellulose nano-porous aerogel
Adding cotton short fibers into an alkaline urine solution, stirring for 30-60 min, then stripping and dissolving at a low temperature of-15 to-12 ℃ to prepare a cellulose solution, then obtaining cellulose gel through self-assembly of the cellulose solution, and obtaining the cellulose nano porous aerogel with high porosity through low-temperature freeze drying.
Preferably, the mass ratio of the cotton short fibers to the alkaline urine solution is 1-3: 45-50; the alkaline urine solution contains sodium hydroxide, urea and distilled water, and the ratio of the sodium hydroxide to the urea to the distilled water in the alkaline urine solution is respectively 10-13%, 7-9% and 78-83%.
The hydrogen bond of the cellulose is destroyed by the direct action of the compound formed by the sodium hydroxide and the urea molecules and the cellulose, the urea-NaOH-cellulose inclusion compound is formed by the self-assembly of the solvent micromolecules and the cellulose macromolecules under the low-temperature induction action, and the dissolution of the cellulose is promoted by the alkaline urine solution.
Preferably, the low-temperature freeze drying temperature is-45 to-40 ℃, and the drying time is 36 to 48 hours.
III, modification
S1 carboxylation
Placing the cellulose nano porous aerogel in distilled water according to the proportion of 1:12-15, stirring for 5-8min, adjusting the pH to 10-10.5, adding TEMPO and NaBr, stirring for 10-15min at 35-40 ℃, adding a sodium chlorite solution with the mass fraction of 7-10% for the first time, continuing stirring for 18-25min, adjusting the pH to 4-5, then adding a sodium chlorite solution with the mass fraction of 7-10% for the second time, heating to 60-65 ℃, stirring for 40-60min, and completely oxidizing primary hydroxyl groups on the molecules of the cellulose nano porous aerogel into carboxyl groups to obtain a carboxylated cellulose nano porous aerogel suspension.
Preferably, the addition amount of TEMPO is 0.6-1% of the cellulose nano-porous aerogel, the addition amount of NaBr is 3-5% of the cellulose nano-porous aerogel, the first addition amount of the sodium chlorite solution is 0.4-0.8% of the cellulose nano-porous aerogel, and the second addition amount of the sodium chlorite solution is 1-1.8% of the cellulose nano-porous aerogel.
S2, grafting SiO2
Adding 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated cellulose nano porous aerogel suspension, adjusting the pH to 4-5.5, reacting for 20-30min at 30-35 ℃ to activate carboxyl on the molecules of the carboxylated cellulose nano porous aerogel, and centrifuging to remove waste liquid to obtain an intermediate product;
adding tetraethoxysilane and 0.6-1mol/L glacial acetic acid solution into a reaction kettle, magnetically stirring for 30-40min at room temperature, adding aminosilane coupling agent, carrying out ultrasonic reaction for 1-1.5h at room temperature, heating to 45-50 ℃, carrying out ultrasonic reaction for 5-6h, adding intermediate product, stirring for 8-15min, adjusting pH to 7-7.5, carrying out ultrasonic reaction for 50-60min at 25-30 ℃, and enabling the ultrasonic frequency to be 80-100KHz to enable SiO to be generated2Grafting reaction with carboxylated cellulose nano-porous aerogel, amination of the obtained product2Combines with carboxyl on the carboxylated cellulose nano-porous aerogel molecule, the amino reacts with the carboxyl to generate amido bond, and successfully prepares SiO2The cellulose nano-porous aerogel is embedded, so that the porous structure of the cellulose nano-porous aerogel is supported more firmly and is not easy to collapse; and after the reaction is finished, filtering, washing the product with absolute ethyl alcohol for 3-5 times, and drying at 70-80 ℃ for 3-4h to obtain the composite nano porous aerogel.
Preferably, the addition amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 5-8g/L, and the addition amount of the N-hydroxysuccinimide is 4-6 g/L.
Preferably, the ratio of the ethyl orthosilicate to the glacial acetic acid solution is 1: 7-8; the amino silane coupling agent is one or more of gamma-aminopropyl triethoxysilane, gamma-aminopropyl trimethoxysilane or N-beta (aminoethyl) -gamma-aminopropyl trimethoxysilane, and the addition amount of the amino silane coupling agent is 10-15% of that of the ethyl orthosilicate; the mass ratio of the ethyl orthosilicate to the cellulose nano porous aerogel is 1: 0.3-0.5.
The composite nano porous aerogel has strong adsorbability and low density, and the density is less than 0.03g/cm3The porosity is up to more than 99 percent, the pore structure is complete, and the specific surface area is 142-2/g。
Preparation of plant-derived master batch with mosquito repelling function
Soaking the composite nano-porous aerogel in the plant source mosquito repellent component solution, controlling the temperature at 20-30 ℃, stirring for 6-12h to enable the plant source mosquito repellent component to be fully adsorbed in the modified cellulose nano-porous aerogel, then drying for 2-3h at 100-120 ℃, and crushing and granulating to obtain the plant source mosquito repellent functional master batch.
Preferably, the content of the plant-derived mosquito repelling component in the plant-derived mosquito repelling component solution is 6-10 wt%.
Preferably, the stirring speed is 40-70 r/min.
Fifth, spinning
The plant-derived mosquito-repellent functional master batches and the polymer raw materials are mixed, melted and spun to prepare the plant-derived long-acting mosquito-repellent composite functional filament.
Preferably, the ratio of the mosquito-repellent functional master batch to the polymer raw material is 3-5: 95-97.
Preferably, the polymer raw material is one or more of PET, PA6 and the like.
Preferably, a compatilizer is added in the melt spinning process, so that the compatibility of the plant-derived mosquito-repellent functional master batch and the polymer raw material is better, the compatilizer comprises polyether modified silicone oil, polyvinyl alcohol and sodium carboxymethyl cellulose, and the proportion of the polyether modified silicone oil, the polyvinyl alcohol and the sodium carboxymethyl cellulose is 3-5:2-4:7-8.
Preferably, the compatibilizer is added in an amount of 0.7 to 1.2 wt% of the polymer raw material.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
1. after the plant source long-acting mosquito-repellent composite functional filament is woven into a fabric, the fabric can be washed for more than 50 times, and can be continuously and circularly used by soaking and adsorbing mosquito-repellent essential oil, the odor emitted by the fabric can purify air and drive mosquitoes, the human body is effectively prevented from being bitten by the mosquitoes, and meanwhile, the human body does not have any uncomfortable phenomena such as allergy and the like.
2. The plant-source mosquito-repellent component is extracted from the plant, the composite nano-porous aerogel is used as a carrier to prepare the mosquito-repellent functional master batch, the prepared mosquito-repellent functional master batch maintains the original functions of the plant and resists high temperature at the same time, the traditional processing method is adapted, and the sustainable development concept of the composite application of the plant and the polymer is greatly met, so that the invention is a breakthrough; meanwhile, the botanical mosquito repellent component is natural and environment-friendly and is harmless to human health.
3. Aerogel-forming cellulose nanoporesAfter glue carboxylation, primary hydroxyl on the cellulose nano porous aerogel molecule is completely oxidized into carboxyl, and then the carboxyl is reacted with SiO2Grafting reaction, aminated SiO2Combines with carboxyl on the carboxylated cellulose nano-porous aerogel molecule, the amino reacts with the carboxyl to generate amido bond, and successfully prepares SiO2The embedding cellulose nanometer porous aerogel, the porous structure of cellulose nanometer porous aerogel obtains supporting, is difficult for collapsing, can soak again in plant source mosquito repellent component solution and recycle after washing many times, realizes long-term mosquito repellent, compares environmental protection more with traditional mosquito repellent mode.
4. The composite nano-porous aerogel prepared by the invention has low density which is less than 0.03g/cm3The porosity is up to more than 99 percent, the pore structure is complete, and the specific surface area is 142-2/g。
5. The compatilizer is added in the melt spinning process, so that the compatibility of the plant-derived mosquito-repellent functional master batch and the polymer raw material is better, and the influence of the addition of the plant-derived mosquito-repellent functional master batch on the performance of the composite functional filament is reduced.
Detailed Description
The invention is further illustrated below with reference to specific examples.
Embodiment 1 preparation method of plant-derived long-acting mosquito-repelling composite functional filament
A preparation method of a plant source long-acting mosquito-repelling composite functional filament comprises the steps of preparation of a plant source mosquito-repelling component, preparation and modification of cellulose nano porous aerogel, preparation of plant source mosquito-repelling functional master batches and spinning.
Preparation of plant-derived mosquito-repellent component
The botanical mosquito-repellent component comprises a eucalyptus citriodora extract, a geranium extract and a marigold extract, and the proportion of the eucalyptus citriodora extract, the geranium extract and the marigold extract is 4:2: 1.
S1 ultrasonic peeling
Drying flowers or leaves of plants, pulverizing to 80 mesh with a pulverizer to obtain powder, dissolving in eutectic solvent to obtain mixed solution, ultrasonic stripping, and concentrating to obtain crude extract.
The eutectic solvent comprises choline chloride and oxalic acid, and the mass ratio of the choline chloride to the oxalic acid is 1: 2; the specific gravity of the low eutectic solvent in the mixed solution is 94 wt%.
The ultrasonic stripping frequency is 40KHz, the power is 150W, and the time is 25 min.
S2, supercritical carbon dioxide extraction
And filling the crude extract layer by layer for supercritical carbon dioxide extraction, wherein the supercritical extraction pressure is 28Mpa, the extraction temperature is 40 ℃, the carbon dioxide flow is 22kg/h, the extraction time is 2h, the supercritical fluid after extraction is circulated into a separator through an expansion valve, the supercritical fluid is separated in the separator through an isothermal pressure reduction separation method, the separation temperature is 48 ℃, the separation pressure is 8Mpa, and the carbon dioxide after pressure reduction is recycled to obtain the plant extract.
Further preparing a lemon eucalyptus extract, a geranium extract and a marigold extract according to the steps of S1 and S2 respectively, and preparing a plant source mosquito repelling component according to the ratio of the lemon eucalyptus extract to the geranium extract to the marigold extract being 4:2: 1.
Preparation of cellulose nano-porous aerogel
Adding cotton short fibers into an alkaline urine solution, stirring for 50min, then stripping and dissolving at a low temperature of-14 ℃ to prepare a cellulose solution, then carrying out self-assembly on the cellulose solution to obtain cellulose gel, and carrying out low-temperature freeze drying to obtain the cellulose nano porous aerogel with high porosity.
The mass ratio of the cotton short fibers to the alkaline urine solution is 2: 47; the alkaline urine solution contains sodium hydroxide, urea and distilled water, wherein the sodium hydroxide, the urea and the distilled water account for 10%, 7% and 83% of the alkaline urine solution respectively; the low-temperature freeze drying temperature is-42 ℃, and the drying time is 42 h.
The hydrogen bond of the cellulose is destroyed by the direct action of the compound formed by the sodium hydroxide and the urea molecules and the cellulose, the urea-NaOH-cellulose inclusion compound is formed by the self-assembly of the solvent micromolecules and the cellulose macromolecules under the low-temperature induction action, and the dissolution of the cellulose is promoted by the alkaline urine solution.
III, modification
S1 carboxylation
Placing the cellulose nano-porous aerogel in distilled water according to the proportion of 1:13, stirring for 8min, adjusting the pH to 10, adding TEMPO and NaBr, stirring for 12min at 38 ℃, adding a sodium chlorite solution with the mass fraction of 8% for the first time, continuously stirring for 22min, adjusting the pH to 4.5, then adding a sodium chlorite solution with the mass fraction of 8% for the second time, heating to 63 ℃, and stirring for 50min to completely oxidize primary hydroxyl groups on the molecules of the cellulose nano-porous aerogel into carboxyl groups, thereby obtaining a carboxylated cellulose nano-porous aerogel suspension.
The addition of TEMPO is 0.8% of the cellulose nano-porous aerogel, the addition of NaBr is 4% of the cellulose nano-porous aerogel, the first addition of a sodium chlorite solution is 0.6% of the cellulose nano-porous aerogel, and the second addition of the sodium chlorite solution is 1.5% of the cellulose nano-porous aerogel.
S2, grafting SiO2
Adding 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated cellulose nano porous aerogel suspension, adjusting the pH to 4.5, reacting for 25min at 33 ℃ to activate carboxyl on the molecules of the carboxylated cellulose nano porous aerogel, and centrifuging to remove waste liquid to obtain an intermediate product;
adding tetraethoxysilane and 0.8mol/L glacial acetic acid solution into a reaction kettle, magnetically stirring for 35min at room temperature, adding aminosilane coupling agent, carrying out ultrasonic reaction for 1.5h at room temperature, heating to 48 ℃, carrying out ultrasonic reaction for 5.5h, adding intermediate product, stirring for 12min, adjusting the pH to 7.2, carrying out ultrasonic reaction for 55min at 28 ℃, and enabling the ultrasonic frequency to be 90KHz to enable SiO to be in contact with the reaction kettle2Grafting reaction with carboxylated cellulose nano-porous aerogel, amination of the obtained product2Combines with carboxyl on the carboxylated cellulose nano-porous aerogel molecule, the amino reacts with the carboxyl to generate amido bond, and successfully prepares SiO2The cellulose nano-porous aerogel is embedded, and the porous structure of the cellulose nano-porous aerogel is supported more firmly and is not easy to collapse(ii) a And after the reaction is finished, filtering, washing the product with absolute ethyl alcohol for 5 times, and drying at 75 ℃ for 3.5 hours to obtain the composite nano porous aerogel.
The addition amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 6g/L, and the addition amount of the N-hydroxysuccinimide is 5 g/L.
The ratio of the ethyl orthosilicate to the glacial acetic acid solution is 1: 8; the amino silane coupling agent is gamma-aminopropyl triethoxysilane, and the addition amount of the amino silane coupling agent is 12 percent of that of the tetraethoxysilane; the mass ratio of the ethyl orthosilicate to the cellulose nano-porous aerogel is 1: 0.4.
The composite nano porous aerogel has stronger adsorbability and low density of 0.026g/cm3The porosity is as high as 99.3%, the pore structure is complete, and the specific surface area is 158m2/g。
Preparation of plant-derived master batch with mosquito repelling function
Soaking the composite nano-porous aerogel in the plant-derived mosquito-repellent component solution, controlling the temperature at 25 ℃, stirring for 9 hours to enable the plant-derived mosquito-repellent component to be fully adsorbed in the modified cellulose nano-porous aerogel, then drying for 2.5 hours at 110 ℃, and crushing and granulating to obtain the plant-derived mosquito-repellent functional master batch.
The content of the plant-derived mosquito repelling component in the plant-derived mosquito repelling component solution is 8 wt%, and the stirring speed is 60 r/min.
Fifth, spinning
The plant source mosquito repelling functional master batches and PET are mixed according to the proportion of 4:96 and are subjected to melt spinning to prepare the plant source long-acting mosquito repelling composite functional filament, wherein the screw temperature is 291 ℃, the spinning box temperature is 295 ℃, the process control air temperature of cross air is 18-20 ℃, the relative humidity is 77-83%, and the air speed of the cross air is 0.4 m/s.
The compatilizer is added in the melt spinning process, so that the compatibility of the plant-source mosquito-repellent functional master batch and the polymer raw material is better, the compatilizer comprises polyether modified silicone oil, polyvinyl alcohol and sodium carboxymethylcellulose, and the ratio of the polyether modified silicone oil to the polyvinyl alcohol to the sodium carboxymethylcellulose is 4:3:8.
The addition amount of the compatibilizer is 1 wt% of PET.
The plant-derived long-acting mosquito-repellent composite functional filament prepared in the embodiment 1 has the fineness of 3.0dtex, the breaking strength of 2.93cN/dtex and good mechanical properties.
The plant source long-acting mosquito-repellent composite functional filament prepared in the example 1 is woven into a fabric, the fabric is cut into the size of 20cm multiplied by 20cm, the fabric is washed by water for 50 times, the plant source mosquito-repellent component solution is adsorbed again, and the fabric is dried and weighed, so that the adsorption rate is measured to be 6.9%.
Embodiment 2 preparation method of plant source long-acting mosquito-repellent composite functional filament
A preparation method of a plant source long-acting mosquito-repelling composite functional filament comprises the steps of preparation of a plant source mosquito-repelling component, preparation and modification of cellulose nano porous aerogel, preparation of plant source mosquito-repelling functional master batches and spinning.
Preparation of plant-derived mosquito-repellent component
The botanical mosquito-repellent component comprises a eucalyptus citriodora extract, a geranium extract and a marigold extract, and the proportion of the eucalyptus citriodora extract, the geranium extract and the marigold extract is 3:1: 1.
S1 ultrasonic peeling
Drying flowers or leaves of plants, pulverizing to 100 mesh with a pulverizer to obtain powder, dissolving in eutectic solvent to obtain mixed solution, ultrasonic stripping, and concentrating to obtain crude extract.
The eutectic solvent comprises choline chloride and oxalic acid, and the mass ratio of the choline chloride to the oxalic acid is 1: 2; the specific gravity of the low eutectic solvent in the mixed solution is 90 wt%.
The frequency of ultrasonic stripping is 30KHz, the power is 100W, and the time is 20 min.
S2, supercritical carbon dioxide extraction
And filling the crude extract layer by layer for supercritical carbon dioxide extraction, wherein the supercritical extraction pressure is 25Mpa, the extraction temperature is 38 ℃, the carbon dioxide flow is 20kg/h, the extraction time is 1.5h, the supercritical fluid after extraction is circulated into a separator through an expansion valve, the supercritical fluid is separated in the separator through an isothermal pressure reduction separation method, the separation temperature is 42 ℃, the separation pressure is 7Mpa, and the carbon dioxide after pressure reduction is recycled to obtain the plant extract.
Further preparing a lemon eucalyptus extract, a geranium extract and a marigold extract according to the steps of S1 and S2 respectively, and preparing a plant source mosquito repelling component according to the ratio of the lemon eucalyptus extract to the geranium extract to the marigold extract being 3:1: 1.
Preparation of cellulose nano-porous aerogel
Adding cotton short fibers into an alkaline urine solution, stirring for 30min, then stripping and dissolving at a low temperature of-15 ℃ to prepare a cellulose solution, then carrying out self-assembly on the cellulose solution to obtain cellulose gel, and carrying out low-temperature freeze drying to obtain the cellulose nano porous aerogel with high porosity.
The mass ratio of the cotton short fibers to the alkaline urine solution is 1: 45; the alkaline urine solution contains sodium hydroxide, urea and distilled water, and the ratio of the sodium hydroxide, the urea and the distilled water in the alkaline urine solution is respectively 13%, 9% and 78%; the low-temperature freeze drying temperature is-45 ℃, and the drying time is 36 h.
The hydrogen bond of the cellulose is destroyed by the direct action of the compound formed by the sodium hydroxide and the urea molecules and the cellulose, the urea-NaOH-cellulose inclusion compound is formed by the self-assembly of the solvent micromolecules and the cellulose macromolecules under the low-temperature induction action, and the dissolution of the cellulose is promoted by the alkaline urine solution.
III, modification
S1 carboxylation
Placing the cellulose nano-porous aerogel in distilled water according to the proportion of 1:12, stirring for 5min, adjusting the pH to 10.5, adding TEMPO and NaBr, stirring for 10min at 35 ℃, adding a sodium chlorite solution with the mass fraction of 7% for the first time, continuously stirring for 18min, adjusting the pH to 5, then adding a sodium chlorite solution with the mass fraction of 10% for the second time, heating to 60 ℃, stirring for 40min, and completely oxidizing primary hydroxyl groups on the molecules of the cellulose nano-porous aerogel into carboxyl groups to obtain a carboxylated cellulose nano-porous aerogel suspension.
The addition amount of TEMPO is 0.6% of the cellulose nano-porous aerogel, the addition amount of NaBr is 3% of the cellulose nano-porous aerogel, the first addition amount of a sodium chlorite solution is 0.8% of the cellulose nano-porous aerogel, and the second addition amount of the sodium chlorite solution is 1% of the cellulose nano-porous aerogel.
S2, grafting SiO2
Adding 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated cellulose nano porous aerogel suspension, adjusting the pH to 4, reacting for 20min at 30 ℃ to activate carboxyl on the molecules of the carboxylated cellulose nano porous aerogel, and centrifuging to remove waste liquid to obtain an intermediate product;
adding tetraethoxysilane and 0.6mol/L glacial acetic acid solution into a reaction kettle, magnetically stirring for 30min at room temperature, adding aminosilane coupling agent, carrying out ultrasonic reaction for 1h at room temperature, heating to 45 ℃, carrying out ultrasonic reaction for 5h, adding intermediate product, stirring for 8min, adjusting pH to 7, carrying out ultrasonic reaction for 50min at 25 ℃, wherein the ultrasonic frequency is 80KHz, and enabling SiO to be obtained2Grafting reaction with carboxylated cellulose nano-porous aerogel, amination of the obtained product2Combines with carboxyl on the carboxylated cellulose nano-porous aerogel molecule, the amino reacts with the carboxyl to generate amido bond, and successfully prepares SiO2The cellulose nano-porous aerogel is embedded, so that the porous structure of the cellulose nano-porous aerogel is supported more firmly and is not easy to collapse; and after the reaction is finished, filtering, washing the product with absolute ethyl alcohol for 3 times, and drying at 70 ℃ for 4 hours to obtain the composite nano porous aerogel.
The addition amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 5g/L, and the addition amount of the N-hydroxysuccinimide is 6 g/L.
The ratio of the ethyl orthosilicate to the glacial acetic acid solution is 1: 7; the amino silane coupling agent is gamma-aminopropyl triethoxysilane, and the addition amount of the amino silane coupling agent is 10 percent of that of the tetraethoxysilane; the mass ratio of the ethyl orthosilicate to the cellulose nano-porous aerogel is 1: 0.3.
The composite nano porous aerogel has stronger adsorbability and low density of 0.027g/cm3The porosity is up to 99 percent, the pore structure is complete, and the specific surface area is 142m2/g。
Preparation of plant-derived master batch with mosquito repelling function
Soaking the composite nano-porous aerogel in the plant-derived mosquito-repellent component solution, controlling the temperature at 20 ℃, stirring for 12 hours to enable the plant-derived mosquito-repellent component to be fully adsorbed in the modified cellulose nano-porous aerogel, then drying for 3 hours at 100 ℃, and crushing and granulating to obtain the plant-derived mosquito-repellent functional master batch.
The content of the plant-derived mosquito repelling component in the plant-derived mosquito repelling component solution is 6 wt%, and the stirring speed is 40 r/min.
Fifth, spinning
The plant source mosquito repelling functional master batch and PET are mixed according to the proportion of 3:97, and are subjected to melt spinning to prepare the plant source long-acting mosquito repelling composite functional filament, wherein the screw temperature is 291 ℃, the spinning box temperature is 295 ℃, the process control air temperature of cross air is 18-20 ℃, the relative humidity is 77-83%, and the air speed of the cross air is 0.4 m/s.
The compatilizer is added in the melt spinning process, so that the compatibility of the plant-source mosquito-repellent functional master batch and the polymer raw material is better, the compatilizer comprises polyether modified silicone oil, polyvinyl alcohol and sodium carboxymethylcellulose, and the ratio of the polyether modified silicone oil to the polyvinyl alcohol to the sodium carboxymethylcellulose is 3:2: 7.
The addition amount of the compatibilizer was 0.7 wt% of PET.
The plant-derived long-acting mosquito-repellent composite functional filament prepared in the embodiment 2 has the fineness of 3.4dtex, the breaking strength of 2.79cN/dtex and good mechanical properties.
The plant source long-acting mosquito-repellent composite functional filament prepared in the example 2 is woven into a fabric, the fabric is cut into the size of 20cm multiplied by 20cm, the fabric is washed by water for 50 times, the plant source mosquito-repellent component solution is adsorbed again, and the fabric is dried and weighed, so that the adsorption rate is measured to be 6.1%.
Embodiment 3 preparation method of plant-derived long-acting mosquito-repelling composite functional filament
A preparation method of a plant source long-acting mosquito-repelling composite functional filament comprises the steps of preparation of a plant source mosquito-repelling component, preparation and modification of cellulose nano porous aerogel, preparation of plant source mosquito-repelling functional master batches and spinning.
Preparation of plant-derived mosquito-repellent component
The botanical mosquito-repellent component comprises a eucalyptus citriodora extract, a geranium extract and a marigold extract, and the proportion of the eucalyptus citriodora extract, the geranium extract and the marigold extract is 5:2: 1.
S1 ultrasonic peeling
Drying flowers or leaves of plants, pulverizing to 90 mesh with a pulverizer to obtain powder, dissolving in eutectic solvent to obtain mixed solution, ultrasonic stripping, and concentrating to obtain crude extract.
The eutectic solvent comprises choline chloride and oxalic acid, and the mass ratio of the choline chloride to the oxalic acid is 1: 3; the specific gravity of the low eutectic solvent in the mixed solution is 98 wt%.
The ultrasonic stripping frequency is 50KHz, the power is 200W, and the time is 30 min.
S2, supercritical carbon dioxide extraction
And filling the crude extract layer by layer for supercritical carbon dioxide extraction, wherein the supercritical extraction pressure is 30Mpa, the extraction temperature is 44 ℃, the carbon dioxide flow is 24kg/h, the extraction time is 2h, the supercritical fluid after extraction is circulated into a separator through an expansion valve, the supercritical fluid is separated in the separator through an isothermal pressure reduction separation method, the separation temperature is 54 ℃, the separation pressure is 8Mpa, and the carbon dioxide after pressure reduction is recycled to obtain the plant extract.
Further preparing a lemon eucalyptus extract, a geranium extract and a marigold extract according to the steps of S1 and S2 respectively, and preparing a plant source mosquito repelling component according to the proportion of the lemon eucalyptus extract, the geranium extract and the marigold extract of 5:2: 1.
Preparation of cellulose nano-porous aerogel
Adding cotton short fibers into an alkaline urine solution, stirring for 60min, then stripping and dissolving at a low temperature of-12 ℃ to prepare a cellulose solution, then carrying out self-assembly on the cellulose solution to obtain cellulose gel, and carrying out low-temperature freeze drying to obtain the cellulose nano porous aerogel with high porosity.
The mass ratio of the cotton short fibers to the alkaline urine solution is 3: 50; the alkaline urine solution contains sodium hydroxide, urea and distilled water, and the ratio of the sodium hydroxide, the urea and the distilled water in the alkaline urine solution is respectively 13%, 7% and 80%; the low-temperature freeze drying temperature is-40 ℃, and the drying time is 48 h.
The hydrogen bond of the cellulose is destroyed by the direct action of the compound formed by the sodium hydroxide and the urea molecules and the cellulose, the urea-NaOH-cellulose inclusion compound is formed by the self-assembly of the solvent micromolecules and the cellulose macromolecules under the low-temperature induction action, and the dissolution of the cellulose is promoted by the alkaline urine solution.
III, modification
S1 carboxylation
Placing the cellulose nano-porous aerogel in distilled water according to the proportion of 1:15, stirring for 8min, adjusting the pH to 10, adding TEMPO and NaBr, stirring for 15min at 40 ℃, adding a sodium chlorite solution with the mass fraction of 10% for the first time, continuously stirring for 25min, adjusting the pH to 4, adding a sodium chlorite solution with the mass fraction of 7% for the second time, heating to 65 ℃, stirring for 60min, and completely oxidizing primary hydroxyl groups on the molecules of the cellulose nano-porous aerogel into carboxyl groups to obtain a carboxylated cellulose nano-porous aerogel suspension.
The adding amount of TEMPO is 1% of that of the cellulose nano-porous aerogel, the adding amount of NaBr is 5% of that of the cellulose nano-porous aerogel, the adding amount of the sodium chlorite solution for the first time is 0.4% of that of the cellulose nano-porous aerogel, and the adding amount of the sodium chlorite solution for the second time is 1.8% of that of the cellulose nano-porous aerogel.
S2, grafting SiO2
Adding 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into the carboxylated cellulose nano porous aerogel suspension, adjusting the pH value to 5.5, reacting at 35 ℃ for 30min to activate carboxyl on the molecules of the carboxylated cellulose nano porous aerogel, and centrifuging to remove waste liquid to obtain an intermediate product;
adding ethyl orthosilicate and 1mol/L glacial acetic acid solution into a reaction kettle, magnetically stirring for 40min at room temperature, adding aminosilane coupling agent, performing ultrasonic reaction for 1.5h at room temperature, and performing ultrasonic reactionHeating to 50 deg.C, ultrasonic reacting for 6h, adding intermediate product, stirring for 15min, adjusting pH to 7.5, ultrasonic reacting at 30 deg.C for 60min with ultrasonic frequency of 100KHz to obtain SiO2Grafting reaction with carboxylated cellulose nano-porous aerogel, amination of the obtained product2Combines with carboxyl on the carboxylated cellulose nano-porous aerogel molecule, the amino reacts with the carboxyl to generate amido bond, and successfully prepares SiO2The cellulose nano-porous aerogel is embedded, so that the porous structure of the cellulose nano-porous aerogel is supported more firmly and is not easy to collapse; and after the reaction is finished, filtering, washing the product with absolute ethyl alcohol for 5 times, and drying at 80 ℃ for 3 hours to obtain the composite nano porous aerogel.
The addition amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 8g/L, and the addition amount of the N-hydroxysuccinimide is 4 g/L.
The ratio of the ethyl orthosilicate to the glacial acetic acid solution is 1: 8; the amino silane coupling agent is gamma-aminopropyl triethoxysilane, and the addition amount of the amino silane coupling agent is 15 percent of that of the tetraethoxysilane; the mass ratio of the ethyl orthosilicate to the cellulose nano-porous aerogel is 1: 0.5.
The composite nano porous aerogel has stronger adsorbability and low density of 0.027g/cm3The porosity is as high as 99.1%, the pore structure is complete, and the specific surface area is 151m2/g。
Preparation of plant-derived master batch with mosquito repelling function
Soaking the composite nano-porous aerogel in the plant-derived mosquito-repellent component solution, controlling the temperature at 30 ℃, stirring for 6 hours to enable the plant-derived mosquito-repellent component to be fully adsorbed in the modified cellulose nano-porous aerogel, then drying for 2 hours at 120 ℃, and crushing and granulating to obtain the plant-derived mosquito-repellent functional master batch.
The content of the plant-derived mosquito repelling component in the plant-derived mosquito repelling component solution is 10 wt%, and the stirring speed is 70 r/min.
Fifth, spinning
The plant source mosquito repelling functional master batch and PET are mixed according to the proportion of 5:95, and are subjected to melt spinning to prepare the plant source long-acting mosquito repelling composite functional filament, wherein the screw temperature is 291 ℃, the spinning box temperature is 295 ℃, the process control air temperature of cross air is 18-20 ℃, the relative humidity is 77-83%, and the air speed of the cross air is 0.4 m/s.
The compatilizer is added in the melt spinning process, so that the compatibility of the plant-source mosquito-repellent functional master batch and the polymer raw material is better, the compatilizer comprises polyether modified silicone oil, polyvinyl alcohol and sodium carboxymethylcellulose, and the ratio of the polyether modified silicone oil to the polyvinyl alcohol to the sodium carboxymethylcellulose is 5:4: 8.
The addition amount of the compatibilizer was 1.2 wt% of PET.
The plant-derived long-acting mosquito-repellent composite functional filament prepared in the embodiment 3 has the fineness of 3.3dtex, the breaking strength of 2.86cN/dtex and good mechanical properties.
The plant source long-acting mosquito-repellent composite functional filament prepared in the example 3 is woven into a fabric, the fabric is cut into the size of 20cm multiplied by 20cm, the fabric is washed by water for 50 times, the plant source mosquito-repellent component solution is adsorbed again, and the fabric is dried and weighed, so that the adsorption rate is measured to be 6.5%.
Comparative example 1
Selecting representative example 1, removing the modification step, directly soaking the cellulose nano porous aerogel in the plant source mosquito repellent component solution to prepare the plant source mosquito repellent functional master batch, wherein the rest is consistent with example 1, and taking the master batch as comparative example 1. Weaving the plant source long-acting mosquito-repellent composite functional filament prepared in the comparative example 1 into a fabric, cutting the fabric into the size of 20cm multiplied by 20cm, washing the fabric for 50 times, adsorbing the plant source mosquito-repellent component solution again, drying and weighing the fabric, and determining that the adsorption rate is 1.1 percent, which indicates that the unmodified cellulose nano porous aerogel has unstable porous structure, and the adsorption rate is greatly reduced because the cellulose nano porous aerogel collapses pores due to multiple times of washing; to form SiO2The cellulose nano-porous aerogel is embedded, the porous structure of the cellulose nano-porous aerogel is supported and is not easy to collapse, and the cellulose nano-porous aerogel can be soaked in the plant source mosquito-repellent component solution for recycling after being washed for multiple times.
Comparative example 2
Representative example 1 was selected, and the compatibilizer was removed, and the remainder was the same as example 1, and used as comparative example 2. The titer of the plant-derived long-acting mosquito-repellent composite functional filament prepared by the comparative example 2 is 3.8dtex, the breaking strength is 1.7cN/dtex, and the mechanical property is reduced, which shows that the addition of the compatilizer enables the compatibility of the plant-derived mosquito-repellent functional master batch and the polymer raw material to be better, and reduces the influence of the addition of the plant-derived mosquito-repellent functional master batch on the mechanical property of the composite functional filament.
Unless otherwise specified, the proportions are mass proportions, and the percentages are mass percentages; the raw materials are all purchased from the market.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a plant source long-acting mosquito-repelling composite functional filament is characterized by comprising the steps of preparation of a plant source mosquito-repelling component, preparation and modification of cellulose nano porous aerogel, preparation of plant source mosquito-repelling functional master batches and spinning.
2. The preparation method of the plant-derived long-acting mosquito-repelling composite functional filament yarn according to claim 1, wherein the preparation of the plant-derived mosquito-repelling component comprises ultrasonic stripping and supercritical carbon dioxide extraction;
the botanical mosquito-repellent component comprises a eucalyptus citriodora extract, a geranium extract and a marigold extract, and the proportion of the eucalyptus citriodora extract, the geranium extract and the marigold extract is 3-5:1-2: 1.
3. The preparation method of the plant-derived long-acting mosquito-repellent composite functional filament is characterized in that the cellulose nano porous aerogel is prepared by adding cotton short fibers into an alkaline urine solution, stirring for 30-60 min, then stripping and dissolving at a low temperature of-15 to-12 ℃ to prepare a cellulose solution, then self-assembling the cellulose solution to obtain cellulose gel, and performing low-temperature freeze drying to obtain the cellulose nano porous aerogel with high porosity.
4. The preparation method of the plant-derived long-acting mosquito-repellent composite functional filament according to claim 1, wherein the modification comprises carboxylation and SiO grafting2。
5. The preparation method of the plant-derived long-acting mosquito-repellent composite functional filament is characterized in that carboxylation is carried out, cellulose nano porous aerogel is placed in distilled water according to the proportion of 1:12-15, the mixture is stirred for 5-8min, the pH value is adjusted to 10-10.5, TEMPO and NaBr are added, the mixture is stirred for 10-15min at 35-40 ℃, a sodium chlorite solution with the mass fraction of 7-10% is added for the first time, the mixture is continuously stirred for 18-25min, the pH value is adjusted to 4-5, a sodium chlorite solution with the mass fraction of 7-10% is added for the second time, the temperature is raised to 60-65 ℃, and the mixture is stirred for 40-60min, so that a carboxylated cellulose nano porous aerogel suspension is obtained.
6. The preparation method of the plant-derived long-acting mosquito-repelling composite functional filament according to claim 5, wherein the TEMPO is added in an amount of 0.6-1% of the cellulose nano-porous aerogel, the NaBr is added in an amount of 3-5% of the cellulose nano-porous aerogel, the sodium chlorite solution is added in an amount of 0.4-0.8% of the cellulose nano-porous aerogel for the first time, and the sodium chlorite solution is added in an amount of 1-1.8% of the cellulose nano-porous aerogel for the second time.
7. The preparation method of the plant source long-acting mosquito-repellent composite functional filament according to claim 4, wherein the grafted SiO is2Comprises adding 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide into a carboxylated cellulose nano-porous aerogel suspension, adjusting the pH to 4-5.5, reacting at 30-35 ℃ for 20-30min,activating carboxyl on the molecules of the carboxylated cellulose nano porous aerogel, and centrifuging to remove waste liquid to obtain an intermediate product.
8. The preparation method of the plant source long-acting mosquito-repellent composite functional filament according to claim 7, wherein the grafted SiO is2Adding tetraethoxysilane and 0.6-1mol/L glacial acetic acid solution into a reaction kettle, magnetically stirring for 30-40min at room temperature, adding aminosilane coupling agent, carrying out ultrasonic reaction for 1-1.5h at room temperature, heating to 45-50 ℃, carrying out ultrasonic reaction for 5-6h, adding intermediate product, stirring for 8-15min, adjusting pH to 7-7.5, carrying out ultrasonic reaction for 50-60min at 25-30 ℃, wherein the ultrasonic frequency is 80-100KHz, filtering after the reaction is finished, washing the product for 3-5 times by absolute ethyl alcohol, and drying for 3-4h at 70-80 ℃ to obtain the composite nano porous aerogel.
9. The preparation method of the plant-derived long-acting mosquito-repellent composite functional filament according to claim 7, wherein the addition amount of the 1-3 (dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride is 5-8g/L, and the addition amount of the N-hydroxysuccinimide is 4-6 g/L.
10. The preparation method of the plant-derived long-acting mosquito-repellent composite functional filament according to claim 8, wherein the ratio of the ethyl orthosilicate to the glacial acetic acid solution is 1: 7-8; the addition amount of the aminosilane coupling agent is 10-15% of that of the tetraethoxysilane; the mass ratio of the ethyl orthosilicate to the cellulose nano porous aerogel is 1: 0.3-0.5.
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