Plant-based deodorant and preparation method thereof

Abstract

The invention discloses a plant-based deodorant and a preparation method thereof, and relates to the technical field of high polymer materials. When the plant-based deodorant is prepared, beta-cyclodextrin reacts with paratoluensulfonyl chloride and then reacts with ethylenediamine, and amino modified cyclodextrin is prepared; the plant-based extract is subjected to inclusion with amino modified cyclodextrin, and a cyclodextrin inclusion compound is prepared; the preparation method comprises the following steps: reacting hydroxyethyl cellulose with methacrylic anhydride to prepare double-bond modified cellulose; carrying out hydrothermal reaction on titanium sulfate, the carboxylated multi-walled carbon nanotube, ammonium fluoride and cerous nitrate to prepare a co-doped titanium dioxide / carbon nanotube; coating the co-doped titanium dioxide / carbon nano-tubes with oleic acid to prepare modified nano-particles; and reacting the double-bond modified cellulose with the cyclodextrin inclusion compound, and then copolymerizing with the modified nanoparticles and the comonomer to obtain the plant-based deodorant. The prepared plant-based deodorant has the advantages of good deodorization effect, slow release and photocatalytic degradation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a plant-based deodorant and a preparation method thereof. BACKGROUND

[0002] In recent years, with the rapid development of the national economy and the continuous improvement of the material living standard, people hope to live in a cleaner and more comfortable environment. In daily life, we often encounter many unpleasant odors, such as sweat odor, body odor, cigarette odor, and cooking fume odor, etc. The main chemical components of common odors are ammonia (urine and sweat, etc.), hydrogen sulfide (rotten eggs, etc.), trimethylamine (rotten fish), and methyl mercaptan (rotten green onions), etc. These odors not only have a bad smell, but also can harm human physiological functions and pose a threat to people's health.

[0003] Deodorant is a general term for a class of substances that can reduce or remove foul odor and turbidity. It is mainly used in animal husbandry, factories, homes, sewage treatment, landfills, and hospitals. At present, traditional deodorization methods such as timely manure cleaning, keeping the livestock house dry, and reasonable ventilation still play an important role in small-scale breeding such as family breeding. However, in the context of large-scale breeding, the use of livestock excrement deodorant highlights the characteristics of being more convenient, fast, and economical. However, traditional deodorants have poor deodorizing effect and poor durability, and the price is relatively high. SUMMARY

[0004] The present application aims to provide a plant-based deodorant and a preparation method thereof to solve the problems in the prior art.

[0005] In order to solve the above technical problems, the present application provides the following technical solutions: A plant-based deodorant is prepared by copolymerizing double-bond modified cellulose, cyclodextrin inclusion compound, modified nanoparticles, and comonomer after reaction of the double-bond modified cellulose and the cyclodextrin inclusion compound; The double-bond modified cellulose is prepared by reacting hydroxyethyl cellulose with methacrylic anhydride; The cyclodextrin inclusion compound is prepared by modifying plant-based extract with amino-modified cyclodextrin; The amino-modified cyclodextrin is prepared by reacting beta-cyclodextrin with p-toluenesulfonyl chloride and then with ethylenediamine; The modified nanoparticles are prepared by coating co-doped titanium dioxide / carbon nanotubes with oleic acid; The co-doped titanium dioxide / carbon nanotubes are prepared by hydrothermal reaction of titanium sulfate, carboxylated multi-walled carbon nanotubes, ammonium fluoride, and cerium nitrate; The comonomer is acrylamide, methyl methacrylate, and N,N'-methylenebisacrylamide.

[0006] As an optimization, the plant-based extracts include peppermint oil, tea extract, camphor seed extract, and perilla extract.

[0007] A method for preparing a plant-based deodorant includes the following preparation steps: (1) By mass, mix 6-7 parts of β-cyclodextrin and 40-50 parts of pure water evenly. Add 2-3 parts of 8.2 mol / L sodium hydroxide solution dropwise over 6-7 minutes. Stir at 200-250 r / min for 25-30 minutes at room temperature. Add 3-3.5 parts of 30 wt% p-toluenesulfonyl chloride acetonitrile solution dropwise over 8-9 minutes. Stir at 200-300 r / min for 2-3 hours at room temperature. Adjust the pH to 6-7 with 1 mol / L hydrochloric acid. Then, stir at 2-4... Refrigerate at ℃ for 10-12 hours, filter, wash with anhydrous ethanol, and vacuum dry at 50-60℃ for 10-12 hours to obtain 6-p-toluenesulfonyl-β-cyclodextrin; mix 5-6 parts of 6-p-toluenesulfonyl-β-cyclodextrin and 27-35 parts of ethylenediamine evenly, stir at 70-75℃ and 200-300 r / min for 4-5 hours, cool naturally to room temperature, precipitate in acetone, filter, wash with acetone, and vacuum dry at 40-50℃ for 24-28 hours to obtain amino-modified cyclodextrin; (2) By mass, 2-3 parts of amino-modified cyclodextrin and 8-12 parts of pure water are mixed evenly, 0.6-0.8 parts of plant-based extract are added at 30-40℃, stirred at 500-600 r / min for 60-70 min at 40-45℃, stirred at 500-600 r / min for 3-4 h at room temperature, refrigerated at 2-4℃ for 10-12 h, filtered, and the filtrate is freeze-dried for 12-14 h to obtain cyclodextrin inclusion complex; (3) Mix 2-3 parts of hydroxyethyl cellulose and 100-120 parts of pure water evenly by mass. In an ice-water bath, add 1.2-1.8 parts of methacrylic anhydride dropwise at 1-1.2 ml / min. Adjust the pH to 8-10 with 10 mol / L sodium hydroxide solution at room temperature. Stir the reaction at 200-300 r / min for 3-4 h. Let it stand for 7-8 h. Dialyze it in pure water for 70-74 h. The molecular weight cutoff is 1000. Change the water every 8 h. Freeze dry for 12-14 h to obtain double bond modified cellulose. (4) Mix 0.3-0.4 parts of carboxylated multi-walled carbon nanotubes and 80-100 parts of 0.05 mol / L titanium sulfate solution evenly by mass, sonicate at room temperature for 30-40 min, add 0.18-0.2 parts of ammonium fluoride and 0.04-0.06 parts of cerium nitrate, stir at 300-400 r / min at room temperature for 30-40 min, transfer to polytetrafluoroethylene reactor, react at 180-200℃ for 10-12 h, cool naturally to room temperature, filter, wash with pure water until neutral, and vacuum dry at 60-70℃ for 10-12 h to obtain co-doped titanium dioxide / carbon nanotubes; (5) Mix 3-4 parts of oleic acid and 40-50 parts of acetone evenly by mass, add 1-1.2 parts of co-doped titanium dioxide / carbon nanotubes, stir at 300-400 r / min for 20-30 min, reflux at 50-55℃ and 300-400 r / min for 2-3 h, filter, and vacuum dry the filter residue at 50-60℃ for 10-12 h to obtain modified nanoparticles; (6) Dissolve 3-4 parts of double bond modified cellulose in 150-200 parts of pure water by mass, add 1-2 parts of cyclodextrin inclusion complex, stir at 300-400 r / min for 2-3 h at 40-50 °C, concentrate under reduced pressure to 20% of the original volume, add 8-9 parts of acrylamide, 2-2.5 parts of methyl methacrylate, 1-2 parts of N,N′-methylenebisacrylamide, and 2-3 parts of modified nanoparticles under nitrogen atmosphere and protected from light, stir at 300-400 r / min for 15-20 min at room temperature, add 0.2-0.3 parts of azobisisobutyronitrile, stir at 300-400 r / min for 2-3 h at 60-70 °C, cool to room temperature, filter, wash with anhydrous ethanol, and dry the solid under vacuum at 60-70 °C for 20-24 h to obtain a plant-based deodorant.

[0008] As an optimization, the cyclodextrin inclusion complex in step (3) is made by adding different plant-based extracts, namely peppermint oil cyclodextrin inclusion complex, tea extract cyclodextrin inclusion complex, camphor seed extract cyclodextrin inclusion complex, and perilla extract cyclodextrin inclusion complex.

[0009] As an optimization, the cyclodextrin inclusion complex simultaneously includes peppermint oil cyclodextrin inclusion complex, tea extract cyclodextrin inclusion complex, camphor seed extract cyclodextrin inclusion complex, and perilla extract cyclodextrin inclusion complex, and the mass ratio of peppermint oil cyclodextrin inclusion complex, tea extract cyclodextrin inclusion complex, camphor seed extract cyclodextrin inclusion complex, and perilla extract cyclodextrin inclusion complex is 1:(0.1~0.3):(0.4~0.8):(0.2~0.3).

[0010] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing the plant-based deodorant, this invention first reacts β-cyclodextrin with p-toluenesulfonyl chloride and then with ethylenediamine to obtain amino-modified cyclodextrin; then, plant-based extracts are encapsulated with amino-modified cyclodextrin to obtain cyclodextrin inclusion complexes; hydroxyethyl cellulose is reacted with methacrylic anhydride to obtain double-bond modified cellulose; co-doped titanium dioxide / carbon nanotubes are prepared by hydrothermal reaction of titanium sulfate, carboxylated multi-walled carbon nanotubes, ammonium fluoride, and cerium nitrate; the co-doped titanium dioxide / carbon nanotubes are coated with oleic acid to obtain modified nanoparticles; and finally, the double-bond modified cellulose and cyclodextrin inclusion complex are reacted and then copolymerized with the modified nanoparticles and comonomers to obtain the plant-based deodorant.

[0011] First, β-cyclodextrin was reacted with p-toluenesulfonyl chloride and then with ethylenediamine to prepare amino-modified cyclodextrin. Amino modification of β-cyclodextrin primarily improves its water solubility, thus expanding its application range. Additionally, a reactive amino group is introduced onto the β-cyclodextrin, which can participate in subsequent Michael addition reactions, thereby immobilizing it within the chain segment. Plant-based extracts were then encapsulated with amino-modified cyclodextrin to prepare cyclodextrin inclusion complexes. Peppermint oil, tea extract, camphor seed extract, and perilla extract all possess good aroma and deodorizing abilities; however, these plant extracts have high volatility, making long-term use impossible and requiring frequent application, leading to increased labor costs. Therefore, β-cyclodextrin... The inclusion space in dextrin adsorbs and encapsulates volatile plant-based extracts to obtain cyclodextrin inclusion complexes. After inclusion treatment, these volatile plant-based extracts possess a primary immobilization and sustained-release effect, extending their shelf life. Double-bond reactive groups are introduced into hydroxyethyl cellulose using the esterification ability of methacrylic anhydride, resulting in double-bond modified cellulose. Cellulose, as a plant-based raw material, has excellent biodegradability. Modifying it and adding it to deodorants can effectively improve biodegradability and reduce white pollution. Simultaneously, the introduced double bonds allow cellulose to serve as a backbone, participating in polymer chain polymerization through free radical copolymerization and also immobilizing amino-containing cyclodextrin inclusion complexes within the chain segments through Michael addition reactions.

[0012] Secondly, co-doped titanium dioxide / carbon nanotubes were prepared by hydrothermal reaction of titanium sulfate, carboxylated multi-walled carbon nanotubes, ammonium fluoride, and cerium nitrate. Adding raw materials containing fluorine and cerium during the preparation of nano-titanium dioxide allows these elements to be incorporated into the nano-titanium dioxide lattice during the crystal formation process. The co-doping of fluorine and cerium promotes lattice transformation in nano-titanium dioxide, introducing a portion of the rutile crystal form into the intact anatase crystal form. The synergy of these two different crystal structures effectively improves the photocatalytic performance of nano-titanium dioxide. Simultaneously, carboxylated multi-walled carbon nanotubes were added during the synthesis process. The carbon nanotubes, rich in carboxyl groups on their surface, effectively promote the crystallization of nano-titanium dioxide, reducing reaction time. Furthermore, the addition of carbon nanotubes can also serve as electron conduction channels in nano-titanium dioxide. The combination of these two elements further enhances the photocatalytic performance of nano-titanium dioxide, resulting in a strong photocatalytic effect. Catalytic titanium dioxide can effectively catalyze the decomposition of organic odors in the environment, thereby improving deodorization efficiency. Furthermore, the hollow structure of carbon nanotubes provides numerous adsorption sites, effectively adsorbing odor molecules and supplying them to the nano-titanium dioxide for catalytic decomposition. The synergistic effect of both effectively enhances deodorization efficiency. To improve the dispersibility and compatibility of co-doped titanium dioxide / carbon nanotubes, modified nanoparticles are prepared by coating them with oleic acid. Oleic acid adsorbs and fixes itself onto the surface of the co-doped titanium dioxide / carbon nanotubes through esterification reactions with the hydroxyl groups on the carboxyl groups or by forming hydrogen bonds with the carboxyl and hydroxyl groups. Besides improving the dispersibility and compatibility of the modified nanoparticles through the presence of long carbon chains, oleic acid also introduces reactive double bonds on the surface of the modified nanoparticles, allowing them to be fixed within the polymer chain segments through free radical reactions.

[0013] Finally, after reacting the double-bond modified cellulose and cyclodextrin inclusion complex, the plant-based deodorant was copolymerized with modified nanoparticles and comonomers. The double bonds on the double-bond modified cellulose and the amino groups on the cyclodextrin inclusion complex first undergo a Michael addition reaction, thereby fixing the cyclodextrin inclusion complex onto the cellulose chain. Subsequently, the remaining double bonds on the double-bond modified cellulose undergo a free radical copolymerization reaction with the double bonds on the modified nanoparticles, acrylamide, methyl methacrylate, and N,N′-methylenebisacrylamide, thus obtaining the plant-based deodorant. N,N′-methylenebisacrylamide acts as a crosslinking agent, causing the polymer segments synthesized after copolymerization to form a complex crosslinked network structure. This crosslinked network structure further hinders the volatilization of the plant-based extract and improves the sustained-release effect. At the same time, the vacancies in β-cyclodextrin can also act as adsorption sites to adsorb odor molecules after the release of the plant-based extract, thereby maintaining the long-lasting performance of the deodorant. Detailed Implementation

[0014] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0015] The following information is provided for all raw materials used in all examples and comparative examples: Hydroxyethyl cellulose: purchased from Hebei Chaoyan New Material Technology Co., Ltd.; Carboxylated multi-walled carbon nanotubes: Model XFM33, purchased from Jiangsu Xianfeng Nanomaterials Technology Co., Ltd. Peppermint essential oil: L-menthol, purchased from Wuhan Lvjing Fenghua Biotechnology Co., Ltd.; Tea extract: Green tea extract, product number QHSWCDF-339, purchased from Shaanxi Qianhui Biotechnology Co., Ltd.; Camphor seed extract: 100 mesh fineness, purchased from Lanzhou Waterles Biotechnology Co., Ltd. Perilla extract: Product number SHSW-0328-008, purchased from Shanxi Shuohang Biotechnology Co., Ltd.; Cyclodextrin inclusion complexes: These include cyclodextrin inclusion complexes of peppermint essential oil, tea extract, camphor seed extract, and perilla extract, with a mass ratio of 1:0.2:0.6:0.25.

[0016] Example 1: A method for preparing a plant-based deodorant, the method comprising the following steps: (1) By mass fraction, 6 parts of β-cyclodextrin and 40 parts of pure water were mixed evenly, and 2 parts of 8.2 mol / L sodium hydroxide solution were added dropwise over 6 min. The mixture was stirred at 200 r / min for 30 min at room temperature. Then, 3 parts of 30 wt% p-toluenesulfonyl chloride acetonitrile solution were added dropwise over 8 min. The mixture was stirred at 200 r / min for 3 h at room temperature. The pH was adjusted to 6 with 1 mol / L hydrochloric acid. The mixture was refrigerated at 2℃ for 10 h, filtered, washed with anhydrous ethanol, and vacuum dried at 50℃ for 12 h to obtain 6-p-toluenesulfonyl-β-cyclodextrin. 5 parts of 6-p-toluenesulfonyl-β-cyclodextrin and 27 parts of ethylenediamine were mixed evenly, stirred at 70℃ for 5 h at 200 r / min, cooled naturally to room temperature, precipitated in acetone, filtered, washed with acetone, and vacuum dried at 40℃ for 28 h to obtain amino-modified cyclodextrin. (2) By mass, 2 parts of amino-modified cyclodextrin and 8 parts of pure water were mixed evenly, 0.6 parts of plant-based extract were added at 30°C, and stirred at 500 r / min for 70 min at 40°C. Then, stirred at 500 r / min for 4 h at room temperature, and refrigerated at 2°C for 10 h. The mixture was filtered and the filtrate was freeze-dried for 12 h to obtain the cyclodextrin inclusion complex. (3) By mass, 2 parts of hydroxyethyl cellulose and 100 parts of pure water are mixed evenly. In an ice-water bath, 1.2 parts of methacrylic anhydride are added dropwise at 1 ml / min. The pH is adjusted to 8 with 10 mol / L sodium hydroxide solution at room temperature. The mixture is stirred at 200 r / min for 4 h, allowed to stand for 7 h, dialyzed in pure water for 70 h, and the molecular weight cutoff is 1000. The water is changed every 8 h. The mixture is freeze-dried for 12 h to obtain double bond modified cellulose. (4) By mass fraction, 0.3 parts of carboxylated multi-walled carbon nanotubes and 80 parts of 0.05 mol / L titanium sulfate solution were mixed evenly, sonicated at room temperature for 30 min, 0.18 parts of ammonium fluoride and 0.04 parts of cerium nitrate were added, stirred at room temperature at 300 r / min for 40 min, transferred to a polytetrafluoroethylene reactor, reacted at 180℃ for 10 h, cooled naturally to room temperature, filtered, washed with pure water until neutral, and vacuum dried at 60℃ for 12 h to obtain co-doped titanium dioxide / carbon nanotubes; (5) By mass, 3 parts of oleic acid and 40 parts of acetone are mixed evenly, 1 part of co-doped titanium dioxide / carbon nanotubes is added, and the mixture is stirred at 300 r / min for 30 min. The mixture is then stirred and refluxed at 50°C at 300 r / min for 3 h. The mixture is then filtered, and the filter residue is dried under vacuum at 50°C for 12 h to obtain modified nanoparticles. (6) Dissolve 3 parts of double bond modified cellulose in 150 parts of pure water by mass, add 1 part of cyclodextrin inclusion complex, stir at 300 r / min for 3 h at 40 °C, concentrate under reduced pressure to 20% of the original volume, add 8 parts of acrylamide, 2 parts of methyl methacrylate, 1 part of N,N′-methylenebisacrylamide, and 2 parts of modified nanoparticles under nitrogen atmosphere and protected from light, stir at 300 r / min for 20 min at room temperature, add 0.2 parts of azobisisobutyronitrile, stir at 300 r / min for 3 h at 60 °C, cool to room temperature, filter, wash with anhydrous ethanol, and dry the solid under vacuum at 60 °C for 24 h to obtain plant-based deodorant.

[0017] Example 2: A method for preparing a plant-based deodorant, the method comprising the following steps: (1) By mass, mix 6.5 parts of β-cyclodextrin and 45 parts of pure water evenly. Add 2.5 parts of 8.2 mol / L sodium hydroxide solution dropwise over 6.5 min, and stir at 225 r / min for 28 min at room temperature. Add 3.25 parts of 30 wt% p-toluenesulfonyl chloride acetonitrile solution dropwise over 8 min, and stir at 250 r / min for 2.5 h at room temperature. Adjust the pH to 6.5 with 1 mol / L hydrochloric acid. The mixture was refrigerated at 3℃ for 11 h, filtered, washed with anhydrous ethanol, and dried under vacuum at 55℃ for 11 h to obtain 6-p-toluenesulfonyl-β-cyclodextrin; 5.5 parts of 6-p-toluenesulfonyl-β-cyclodextrin and 31 parts of ethylenediamine were mixed evenly, stirred at 70℃ and 250 r / min for 4.5 h, naturally cooled to room temperature, precipitated in acetone, filtered, washed with acetone, and dried under vacuum at 45℃ for 26 h to obtain amino-modified cyclodextrin; (2) By mass, 2.5 parts of amino-modified cyclodextrin and 10 parts of pure water were mixed evenly, 0.7 parts of plant-based extract were added at 35°C, and stirred at 42°C and 550 r / min for 65 min. Then, at room temperature, the mixture was stirred at 550 r / min for 3.5 h. The mixture was then refrigerated at 3°C ​​for 11 h, filtered, and the filtrate was freeze-dried for 13 h to obtain the cyclodextrin inclusion complex. (3) By mass, 2.5 parts of hydroxyethyl cellulose and 110 parts of pure water were mixed evenly. In an ice-water bath, 1.5 parts of methacrylic anhydride were added dropwise at 1.1 ml / min. The pH was adjusted to 9 with 10 mol / L sodium hydroxide solution at room temperature. The mixture was stirred at 250 r / min for 3.5 h, allowed to stand for 7.5 h, dialyzed in pure water for 72 h, and the molecular weight cutoff was 1000. The water was changed every 8 h. The mixture was freeze-dried for 13 h to obtain double bond modified cellulose. (4) By mass fraction, 0.35 parts of carboxylated multi-walled carbon nanotubes and 90 parts of 0.05 mol / L titanium sulfate solution were mixed evenly, sonicated at room temperature for 35 min, 0.19 parts of ammonium fluoride and 0.05 parts of cerium nitrate were added, stirred at room temperature for 350 r / min for 35 min, transferred to a polytetrafluoroethylene reactor, reacted at 190℃ for 11 h, cooled naturally to room temperature, filtered, washed with pure water until neutral, and vacuum dried at 65℃ for 11 h to obtain co-doped titanium dioxide / carbon nanotubes; (5) By mass, 3.5 parts of oleic acid and 45 parts of acetone were mixed evenly, and 1.1 parts of co-doped titanium dioxide / carbon nanotubes were added. The mixture was stirred at 350 r / min for 25 min, and then refluxed at 50 °C at 350 r / min for 2.5 h. The mixture was then filtered, and the filter residue was vacuum dried at 55 °C for 11 h to obtain modified nanoparticles. (6) By mass, 3.5 parts of double bond modified cellulose were dissolved in 175 parts of pure water, and 1.5 parts of cyclodextrin inclusion complex were added. The mixture was stirred at 350 r / min for 2.5 h at 45 °C, and concentrated under reduced pressure to 20% of the original volume. Under a nitrogen atmosphere and in the dark, 8.5 parts of acrylamide, 2.25 parts of methyl methacrylate, 1.5 parts of N,N′-methylenebisacrylamide, and 2.5 parts of modified nanoparticles were added. The mixture was stirred at 350 r / min for 18 min at room temperature, and 0.25 parts of azobisisobutyronitrile were added. The mixture was stirred at 350 r / min for 2.5 h at 65 °C, cooled to room temperature, filtered, washed with anhydrous ethanol, and the solid was dried under vacuum at 65 °C for 22 h to obtain a plant-based deodorant.

[0018] Example 3: A method for preparing a plant-based deodorant, the method comprising the following steps: (1) By mass fraction, 7 parts of β-cyclodextrin and 50 parts of pure water were mixed evenly, and 3 parts of 8.2 mol / L sodium hydroxide solution were added dropwise over 7 min. The mixture was stirred at 250 r / min for 25 min at room temperature. Then, 3.5 parts of 30 wt% p-toluenesulfonyl chloride acetonitrile solution were added dropwise over 9 min. The mixture was stirred at 300 r / min for 2 h at room temperature. The pH was adjusted to 7 with 1 mol / L hydrochloric acid. The mixture was refrigerated at 4℃ for 12 h, filtered, washed with anhydrous ethanol, and vacuum dried at 60℃ for 10 h to obtain 6-p-toluenesulfonyl-β-cyclodextrin. 6 parts of 6-p-toluenesulfonyl-β-cyclodextrin and 35 parts of ethylenediamine were mixed evenly, stirred at 75℃ for 300 r / min for 4 h, cooled naturally to room temperature, precipitated in acetone, filtered, washed with acetone, and vacuum dried at 50℃ for 24 h to obtain amino-modified cyclodextrin. (2) By mass, 3 parts of amino-modified cyclodextrin and 12 parts of pure water were mixed evenly, 0.8 parts of plant-based extract were added at 40°C, and stirred at 600 r / min for 60 min at 45°C. Then, stirred at 600 r / min for 3 h at room temperature, and refrigerated at 4°C for 12 h. The mixture was filtered and the filtrate was freeze-dried for 14 h to obtain the cyclodextrin inclusion complex. (3) Mix 3 parts of hydroxyethyl cellulose and 120 parts of pure water evenly by mass. Add 1.8 parts of methacrylic anhydride dropwise at 1.2 ml / min in an ice-water bath. Adjust the pH to 10 with 10 mol / L sodium hydroxide solution at room temperature. Stir the reaction at 300 r / min for 3 h. Let it stand for 8 h. Dialyze it in pure water for 74 h. The molecular weight cutoff is 1000. Change the water every 8 h. Freeze dry for 14 h to obtain double bond modified cellulose. (4) Mix 0.4 parts of carboxylated multi-walled carbon nanotubes and 100 parts of 0.05 mol / L titanium sulfate solution evenly, ultrasonic for 40 min at room temperature, add 0.2 parts of ammonium fluoride and 0.06 parts of cerium nitrate, stir at 400 r / min for 40 min at room temperature, transfer to a polytetrafluoroethylene reaction kettle, react at 200 °C for 10 h, cool naturally to room temperature, filter by suction, wash with pure water until neutral, and dry in vacuum at 70 °C for 10 h to obtain co-doped titanium dioxide / carbon nanotubes; (5) Mix 4 parts of oleic acid and 50 parts of acetone evenly, add 1.2 parts of co-doped titanium dioxide / carbon nanotubes, stir at 400 r / min for 20 min, stir and reflux at 55 °C and 400 r / min for 2 h, filter by suction, and dry the filter residue in vacuum at 60 °C for 10 h to obtain modified nanoparticles; (6) Dissolve 4 parts of double-bond modified cellulose in 200 parts of pure water by mass, add 2 parts of cyclodextrin inclusion compound, stir at 50 °C and 400 r / min for 2 h, concentrate under reduced pressure to 20% of the original volume, under nitrogen atmosphere and in the dark, add 9 parts of acrylamide, 2.5 parts of methyl methacrylate, 2 parts of N,N′-methylenebisacrylamide, 3 parts of modified nanoparticles, stir at 400 r / min for 15 min at room temperature, add 0.3 parts of azobisisobutyronitrile, stir and react at 70 °C and 400 r / min for 2 h, cool to room temperature, filter by suction, wash with absolute ethanol, and dry the solid in vacuum at 70 °C for 20 h to obtain a plant-based deodorant.

[0019] Comparative Example 1: The difference between the preparation method of the plant-based deodorant in Comparative Example 1 and that in Example 2 is that step (2) is not carried out, and step (6) is modified as follows: Dissolve 3.5 parts of double-bond modified cellulose in 175 parts of pure water by mass, add 1.5 parts of amino-modified cyclodextrin, stir at 45 °C and 350 r / min for 2.5 h, concentrate under reduced pressure to 20% of the original volume, under nitrogen atmosphere and in the dark, add 8.5 parts of acrylamide, 2.25 parts of methyl methacrylate, 1.5 parts of N,N′-methylenebisacrylamide, 2.5 parts of modified nanoparticles, stir at 350 r / min for 18 min at room temperature, add 0.25 parts of azobisisobutyronitrile, stir and react at 65 °C and 350 r / min for 2.5 h, cool to room temperature, filter by suction, wash with absolute ethanol, and dry the solid in vacuum at 65 °C for 22 h to obtain a plant-based deodorant. The remaining steps are the same as those in Example 2.

[0020] Comparative Example 2: The preparation method of the plant-based deodorant in Comparative Example 2 differs from that in Example 2 in that steps (1) and (2) are omitted, and step (6) is modified as follows: 3.5 parts by mass of double-bond modified cellulose are dissolved in 175 parts of pure water, stirred at 350 r / min for 2.5 h at 45 °C, concentrated under reduced pressure to 20% of the original volume, and under a nitrogen atmosphere and protected from light, 8.5 parts of acrylamide, 2.25 parts of methyl methacrylate, 1.5 parts of N,N′-methylenebisacrylamide, and 2.5 parts of modified nanoparticles are added, stirred at 350 r / min for 18 min at room temperature, and 0.25 parts of azobisisobutyronitrile are added. The mixture is stirred at 350 r / min for 2.5 h at 65 °C, cooled to room temperature, filtered, washed with anhydrous ethanol, and the solid is vacuum dried at 65 °C for 22 h to obtain the plant-based deodorant. The remaining steps are the same as in Example 2.

[0021] Comparative Example 3: The preparation method of the plant-based deodorant in Comparative Example 3 differs from that in Example 2 in that step (3) is omitted, and step (6) is modified as follows: 3.5 parts by mass of hydroxyethyl cellulose are dissolved in 175 parts of pure water, 1.5 parts of cyclodextrin inclusion complex are added, and the mixture is stirred at 350 r / min for 2.5 h at 45 °C. The mixture is then concentrated under reduced pressure to 20% of its original volume. Under a nitrogen atmosphere and in the dark, 8.5 parts of acrylamide, 2.25 parts of methyl methacrylate, 1.5 parts of N,N′-methylenebisacrylamide, and 2.5 parts of modified nanoparticles are added. The mixture is stirred at 350 r / min for 18 min at room temperature, and 0.25 parts of azobisisobutyronitrile are added. The mixture is stirred at 350 r / min for 2.5 h at 65 °C. After cooling to room temperature, the mixture is filtered, washed with anhydrous ethanol, and the solid is vacuum dried at 65 °C for 22 h to obtain the plant-based deodorant. The remaining steps are the same as in Example 2.

[0022] Comparative Example 4: The difference between the preparation method of the plant-based deodorant in Comparative Example 4 and Example 2 lies in step (4). Step (4) is modified as follows: 90 parts by mass of 0.05 mol / L titanium sulfate solution are sonicated at room temperature for 35 min, 0.19 parts of ammonium fluoride and 0.05 parts of cerium nitrate are added, and the mixture is stirred at 350 r / min for 35 min at room temperature. The mixture is then transferred to a polytetrafluoroethylene reactor and reacted at 190℃ for 11 h. After natural cooling to room temperature, the mixture is filtered, washed with pure water until neutral, and vacuum dried at 65℃ for 11 h to obtain co-doped titanium dioxide / carbon nanotubes. The remaining steps are the same as in Example 2.

[0023] Comparative Example 5: The difference between the preparation method of the plant-based deodorant in Comparative Example 5 and Example 2 lies in step (4). Step (4) is modified as follows: 0.35 parts by mass of carboxylated multi-walled carbon nanotubes and 90 parts by mass of 0.05 mol / L titanium sulfate solution are mixed evenly, sonicated at room temperature for 35 min, 0.05 parts of cerium nitrate are added, and the mixture is stirred at 350 r / min for 35 min at room temperature. The mixture is then transferred to a polytetrafluoroethylene reactor and reacted at 190°C for 11 h. After natural cooling to room temperature, the mixture is filtered, washed with pure water until neutral, and vacuum dried at 65°C for 11 h to obtain co-doped titanium dioxide / carbon nanotubes. The remaining steps are the same as in Example 2.

[0024] Comparative Example 6: The difference between the preparation method of the plant-based deodorant in Comparative Example 6 and Example 2 lies in step (4). Step (4) is modified as follows: 0.35 parts by mass of carboxylated multi-walled carbon nanotubes and 90 parts by mass of 0.05 mol / L titanium sulfate solution are mixed evenly, sonicated at room temperature for 35 min, 0.19 parts of ammonium fluoride are added, and the mixture is stirred at 350 r / min at room temperature for 35 min. The mixture is then transferred to a polytetrafluoroethylene reactor and reacted at 190°C for 11 h. After natural cooling to room temperature, the mixture is filtered, washed with pure water until neutral, and vacuum dried at 65°C for 11 h to obtain co-doped titanium dioxide / carbon nanotubes. The remaining steps are the same as in Example 2.

[0025] Comparative Example 7: The difference between the preparation method of the plant-based deodorant in Comparative Example 7 and Example 2 lies in step (4). Step (4) is modified as follows: 0.35 parts by mass of carboxylated multi-walled carbon nanotubes and 90 parts by mass of 0.05 mol / L titanium sulfate solution are mixed evenly, sonicated at room temperature for 35 min, transferred to a polytetrafluoroethylene reactor, reacted at 190°C for 11 h, naturally cooled to room temperature, filtered, washed with pure water until neutral, and vacuum dried at 65°C for 11 h to obtain co-doped titanium dioxide / carbon nanotubes. The remaining steps are the same as in Example 2.

[0026] Comparative Example 8: The preparation method of the plant-based deodorant in Comparative Example 8 differs from that in Example 2 in that step (5) is omitted, and step (6) is modified as follows: 3.5 parts by mass of double-bond modified cellulose are dissolved in 175 parts of pure water, 1.5 parts of cyclodextrin inclusion complex are added, and the mixture is stirred at 350 r / min for 2.5 h at 45 °C. The mixture is then concentrated under reduced pressure to 20% of its original volume. Under a nitrogen atmosphere and in the dark, 8.5 parts of acrylamide, 2.25 parts of methyl methacrylate, 1.5 parts of N,N′-methylenebisacrylamide, and 2.5 parts of co-doped titanium dioxide / carbon nanotubes are added. The mixture is stirred at 350 r / min for 18 min at room temperature, and 0.25 parts of azobisisobutyronitrile are added. The mixture is stirred at 350 r / min for 2.5 h at 65 °C. After cooling to room temperature, the mixture is filtered, washed with anhydrous ethanol, and the solid is vacuum dried at 65 °C for 22 h to obtain the plant-based deodorant. The remaining steps are the same as in Example 2.

[0027] Comparative Example 9: The preparation method of the plant-based deodorant in Comparative Example 9 differs from that in Example 2 in that steps (4) and (5) are omitted, and step (6) is modified as follows: 3.5 parts by mass of double-bond modified cellulose are dissolved in 175 parts of pure water, 1.5 parts of cyclodextrin inclusion complex are added, and the mixture is stirred at 350 r / min for 2.5 h at 45 °C. The mixture is then concentrated under reduced pressure to 20% of its original volume. Under a nitrogen atmosphere and in the dark, 8.5 parts of acrylamide, 2.25 parts of methyl methacrylate, and 1.5 parts of N,N′-methylenebisacrylamide are added. The mixture is stirred at 350 r / min for 18 min at room temperature, and 0.25 parts of azobisisobutyronitrile are added. The mixture is stirred at 350 r / min for 2.5 h at 65 °C. After cooling to room temperature, the mixture is filtered, washed with anhydrous ethanol, and the solid is vacuum dried at 65 °C for 22 h to obtain the plant-based deodorant. The remaining steps are the same as in Example 2.

[0028] Test Example 1: Deodorization performance test: The deodorization performance of the prepared plant-based deodorant was evaluated by testing its deodorization efficiency against hydrogen sulfide, ammonia, methanethiol, and dimethyl sulfide. The test method was carried out in accordance with the test method in 6.21 of standard CJ / T 516-2017. The large bubble absorption tube containing 10ml of deodorant was replaced with a gas absorption tube containing the same volume of the plant-based deodorant prepared in this invention, and transparent tubes were used. Simulated natural light was used for irradiation. The remaining tests were carried out in accordance with the standard. Each group was tested in parallel 5 times, and the average value was recorded.

[0029] The results are shown in Table 1.

[0030] ; A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-9 in Table 1 reveals that the plant-based deodorant prepared in this invention has good deodorization efficiency.

[0031] By comparing the data in the table, the data in Comparative Example 1 shows that the addition of plant-based extracts removes odors by neutralizing them, thus improving deodorization performance.

[0032] By comparing the data in the table, the data in Comparative Example 2 shows that the addition of cyclodextrin inclusion complexes improves the adsorption and decomposition efficiency of odors. Even without plant-based extracts, the adsorption properties of cyclodextrin can still provide adsorption of odors.

[0033] The data comparison in the table shows that the doping of nano-titanium dioxide with fluorine and cerium, as well as the use of composite carboxylated multi-walled carbon nanotubes, effectively improves the photocatalytic performance of titanium dioxide and can effectively decompose organic odors.

[0034] By comparing the data in the table, the data in Comparative Example 8 shows that surface modification and coating of co-doped titanium dioxide / carbon nanotubes with oleic acid improves dispersibility and compatibility, allowing the modified nanoparticles to be effectively dispersed in the matrix and avoiding performance degradation caused by agglomeration.

[0035] By comparing the data in the table, the data in Comparative Example 9 shows that the addition of modified nanoparticles effectively improves the deodorization performance through their photocatalytic properties and the adsorption properties of carbon nanotubes.

[0036] Test Example 2: Slow-release performance test: The prepared plant-based deodorant was placed in an open environment at 20℃, 40%RH and wind speed of 2m / s for 30 days. The deodorization efficiency was tested again according to the test method in Test Example 1, and the performance retention rate was calculated. Each group was tested in parallel 5 times, and the average value was recorded.

[0037] The results are shown in Table 2.

[0038] ; A comparison of the experimental data from Examples 1-3 and Comparative Examples 1-9 in Table 2 reveals that the plant-based deodorant prepared in this invention has good sustained-release properties.

[0039] The data in the table shows that when no plant-based extracts are added, the performance of the deodorant decreases less.

[0040] The data comparison in the table shows that the addition of double-bond modified cellulose provides an increase in the polymer backbone and cross-linking density, effectively improving the sustained-release performance.

[0041] By comparing the data in the table, the data in Comparative Examples 8 and 9 show that the oleic acid coating modification of the modified nanoparticles effectively improves their dispersibility and compatibility. At the same time, the introduction of surface double bonds allows them to act as crosslinking agents, thereby increasing the crosslinking density and improving the sustained-release performance.

[0042] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A plant-based deodorant, characterized in that, The plant-based deodorant is prepared by reacting double-bond modified cellulose and cyclodextrin inclusion complex, and then copolymerizing them with modified nanoparticles and comonomers. The double bond modified cellulose is prepared by reacting hydroxyethyl cellulose with methacrylic anhydride; The cyclodextrin inclusion complex is prepared by incorporating plant-based extracts with amino-modified cyclodextrin. The amino-modified cyclodextrin is prepared by reacting β-cyclodextrin with p-toluenesulfonyl chloride and then with ethylenediamine. The modified nanoparticles are prepared by coating co-doped titanium dioxide / carbon nanotubes with oleic acid. The co-doped titanium dioxide / carbon nanotubes are prepared by hydrothermal reaction of titanium sulfate, carboxylated multi-walled carbon nanotubes, ammonium fluoride, and cerium nitrate. The comonomers are acrylamide, methyl methacrylate, and N,N′-methylenebisacrylamide.

2. The plant-based deodorant according to claim 1, characterized in that, The plant-based extracts include peppermint oil, tea extract, camphor seed extract, and perilla extract.

3. A method for preparing the plant-based deodorant according to claim 1, characterized in that, The preparation steps include the following: (1) Mix β-cyclodextrin and pure water evenly, add sodium hydroxide solution dropwise, stir at room temperature, add acetonitrile solution of p-toluenesulfonyl chloride dropwise, stir at room temperature, adjust pH to 6~7, refrigerate, filter, wash, and dry to obtain 6-p-toluenesulfonyl-β-cyclodextrin; mix 6-p-toluenesulfonyl-β-cyclodextrin and ethylenediamine evenly, stir to react, cool, precipitate, filter, wash, and dry to obtain amino-modified cyclodextrin; (2) Mix amino-modified cyclodextrin and pure water evenly, add plant-based extract, stir, stir at room temperature, refrigerate, filter, and freeze-dry the filtrate to obtain cyclodextrin inclusion complex; (3) Mix hydroxyethyl cellulose and pure water evenly, add methacrylic anhydride dropwise in an ice-water bath, adjust the pH to 8-10 at room temperature, stir the reaction, let stand, dialyze, freeze dry, and obtain double bond modified cellulose. (4) Mix carboxylated multi-walled carbon nanotubes and 0.05 mol / L titanium sulfate solution evenly, sonicate at room temperature, add ammonium fluoride and cerium nitrate, stir at room temperature, transfer to polytetrafluoroethylene reactor, react at 180~200℃, cool, filter, wash, dry, and obtain co-doped titanium dioxide / carbon nanotubes. (5) Mix oleic acid and acetone evenly, add co-doped titanium dioxide / carbon nanotubes, stir, reflux at 50~55℃, filter, dry the filter residue, and obtain modified nanoparticles. (6) Dissolve double bond modified cellulose in pure water, add cyclodextrin inclusion complex, stir, concentrate under reduced pressure, add acrylamide, methyl methacrylate, N,N′-methylenebisacrylamide and modified nanoparticles under nitrogen atmosphere and protected from light, stir at room temperature, add azobisisobutyronitrile, stir to react, cool, filter, wash, dry solid to obtain plant-based deodorant.

4. The method for preparing a plant-based deodorant according to claim 3, characterized in that, In step (1), the amino-modified cyclodextrin is prepared by mixing 6-7 parts by weight of β-cyclodextrin and 40-50 parts by weight of pure water. Then, 2-3 parts by weight of 8.2 mol / L sodium hydroxide solution are added dropwise over 6-7 minutes, and the mixture is stirred at room temperature for 25-30 minutes. Next, 3-3.5 parts by weight of 30 wt% p-toluenesulfonyl chloride acetonitrile solution are added dropwise over 8-9 minutes, and the mixture is stirred at room temperature for 2-3 hours. The pH is then adjusted to 1 mol / L hydrochloric acid. 6-7. Refrigerate at 2-4℃ for 10-12 hours, filter, wash, and vacuum dry at 50-60℃ for 10-12 hours to obtain 6-p-toluenesulfonyl-β-cyclodextrin; mix 5-6 parts of 6-p-toluenesulfonyl-β-cyclodextrin and 27-35 parts of ethylenediamine evenly, stir and react at 70-75℃ for 4-5 hours, cool naturally to room temperature, precipitate in acetone, filter, wash, and vacuum dry at 40-50℃ for 24-28 hours to obtain the final product.

5. The method for preparing a plant-based deodorant according to claim 3, characterized in that, The cyclodextrin inclusion complex in step (2) is prepared by mixing 2-3 parts of amino-modified cyclodextrin and 8-12 parts of pure water by mass, adding 0.6-0.8 parts of plant-based extract at 30-40℃, stirring at 40-45℃ for 60-70 min, stirring at room temperature for 3-4 h, refrigerating at 2-4℃ for 10-12 h, filtering, and freeze-drying the filtrate for 12-14 h.

6. The method for preparing a plant-based deodorant according to claim 5, characterized in that, The cyclodextrin inclusion complexes are prepared by adding different plant-based extracts, namely peppermint oil cyclodextrin inclusion complexes, tea extract cyclodextrin inclusion complexes, camphor seed extract cyclodextrin inclusion complexes, and perilla extract cyclodextrin inclusion complexes. Each cyclodextrin inclusion complex includes peppermint oil cyclodextrin inclusion complexes, tea extract cyclodextrin inclusion complexes, camphor seed extract cyclodextrin inclusion complexes, and perilla extract cyclodextrin inclusion complexes, and the mass ratio of peppermint oil cyclodextrin inclusion complexes, tea extract cyclodextrin inclusion complexes, camphor seed extract cyclodextrin inclusion complexes, and perilla extract cyclodextrin inclusion complexes is 1:(0.1~0.3):(0.4~0.8):(0.2~0.3).

7. The method for preparing a plant-based deodorant according to claim 3, characterized in that, The double bond modified cellulose described in step (3) is prepared by mixing 2-3 parts of hydroxyethyl cellulose and 100-120 parts of pure water by mass, adding 1.2-1.8 parts of methacrylic anhydride dropwise at 1-1.2 ml / min in an ice-water bath, adjusting the pH to 8-10 with 10 mol / L sodium hydroxide solution at room temperature, stirring for 3-4 hours, letting stand for 7-8 hours, dialyzing in pure water for 70-74 hours, retaining a molecular weight cutoff of 1000, changing the water every 8 hours, and freeze-drying for 12-14 hours.

8. The method for preparing a plant-based deodorant according to claim 3, characterized in that, The co-doped titanium dioxide / carbon nanotubes in step (4) are prepared by mixing 0.3-0.4 parts by mass of carboxylated multi-walled carbon nanotubes and 80-100 parts by mass of 0.05 mol / L titanium sulfate solution, sonicating at room temperature for 30-40 min, adding 0.18-0.2 parts by mass of ammonium fluoride and 0.04-0.06 parts by mass of cerium nitrate, stirring at room temperature for 30-40 min, transferring to a polytetrafluoroethylene reactor, reacting at 180-200℃ for 10-12 h, naturally cooling to room temperature, filtering, washing with pure water until neutral, and vacuum drying at 60-70℃ for 10-12 h.

9. The method for preparing a plant-based deodorant according to claim 3, characterized in that, The modified nanoparticles in step (5) are prepared by mixing 3-4 parts of oleic acid and 40-50 parts of acetone by mass, adding 1-1.2 parts of co-doped titanium dioxide / carbon nanotubes, stirring for 20-30 minutes, stirring and refluxing at 50-55°C for 2-3 hours, filtering, and vacuum drying the filter residue at 50-60°C for 10-12 hours.

10. The method for preparing a plant-based deodorant according to claim 3, characterized in that, The plant-based deodorant described in step (6) is prepared by dissolving 3-4 parts of double-bond modified cellulose in 150-200 parts of pure water, adding 1-2 parts of cyclodextrin inclusion complex, stirring at 40-50℃ for 2-3 hours, concentrating under reduced pressure to 20% of the original volume, adding 8-9 parts of acrylamide, 2-2.5 parts of methyl methacrylate, 1-2 parts of N,N′-methylenebisacrylamide, and 2-3 parts of modified nanoparticles under a nitrogen atmosphere and protected from light, stirring at room temperature for 15-20 minutes, adding 0.2-0.3 parts of azobisisobutyronitrile, stirring and reacting at 60-70℃ for 2-3 hours, cooling to room temperature, filtering, washing, and drying the solid under vacuum at 60-70℃ for 20-24 hours.