A progressive reaction type natural long-acting deodorant hydrogel and its preparation method and application

Abstract

The present invention belongs to the field of preparation of air purification materials, and discloses a progressive reaction type natural long-acting deodorant hydrogel, its preparation method and application, which include the following components: chondroitin sulfate 2-10%, chitosan quaternary ammonium salt 2-8%, agar 0.05-0.5%, naringin modifier 1-10%, naringin essential oil 0.1-0.5%, surfactant 0.1-5%, deionized water. The present invention uses naringin as a raw material and is formulated with neohesperidin to obtain a naringin modifier, which contains alcohol hydroxyl groups and phenolic hydroxyl groups that can react with aldehydes, etc. The pH-sensitive hydrogel is used as a carrier to load amphoteric deodorant active substances. The alkaline and acidic groups respectively capture odor components through coordination, chelation, neutralization and other effects with acidic and alkaline substances. The hydrogel participating in the reaction disintegrates to form a solution and sinks to the lower part of the hydrogel, and the unreacted hydrogel is exposed to continue to adsorb and capture odor substances, achieving the purpose of long-acting deodorization.

Description

Technical Field

[0001] The present invention relates to the field of preparation of air purification materials, and particularly to a progressive reaction type natural long-acting deodorant hydrogel, a preparation method thereof, and an application thereof. Background Art

[0002] With the gradual acceleration of the urbanization process, people's living standards have been increasing day by day, and consumers' awareness of environmental health has also become stronger. However, the odors and peculiar smells generated in household environments such as kitchens, bathrooms, clothes, and pets have seriously affected the quality of people's daily lives. In addition, the malodors generated and released in public environments such as landfills, vegetable markets, farms, and carriages will seriously damage people's living environments.

[0003] Currently, air pollution problems encountered in people's daily lives are mainly solved by deodorants. Although traditional spray deodorants have the characteristics of a wide range of action and a fast action speed, in the fast-paced life, the generation of odor substances in household and public environments is constantly ongoing. However, spray deodorants belong to instant reaction type deodorants, which require manual passive deodorization of odor places and cannot truly achieve long-term purification of the air. Moreover, when spray deodorants are used, they need to be sprayed and attached to the surface of the deodorization object, leaving water stains, which will cause inconvenience to people's daily lives more or less. Thus, traditional spray deodorants have certain limitations in deodorization scenarios in the market.

[0004] In recent years, Chinese Patent 201810643094.2 has disclosed a solid gel for removing formaldehyde and peculiar smells in rooms and cars. This patent uses components such as gel powder, essential oil, deodorant, parachlorometaxylenol, etc. to remove peculiar smells. Although the raw materials and manufacturing process are simple, the extraction of one of its main raw materials, essential oil, takes a long time and has a high cost, and its action object is relatively limited, mainly used for removing formaldehyde in rooms and cars, and the effect of removing other peculiar smells is not ideal and it is difficult to meet the deodorization requirements of various daily life scenarios. Chinese Patent 202010705445.5 has disclosed a biological deodorant using microbial metabolism. This patent uses components such as cryoactive bacteria and activated carbon to remove peculiar smells. Its characteristic is that it has a multi-layer slow-release structure and can more quickly, durably, efficiently, conveniently, and environmentally friendly achieve the removal of odors. However, its production process is relatively complex, time-consuming, costly, and there are certain safety hazards. In addition, the waste treatment after using its product will bring inconvenience to consumers and it is difficult to meet long-term requirements.

[0005] Therefore, there is a huge market demand for a biological deodorant hydrogel that can react with odor substances in a long-term and progressive manner, has a low cost, and has multiple functions. Summary of the Invention

[0006] Aiming at the disadvantages and deficiencies of the existing technology, the primary object of the present invention is to provide a progressive reaction type long-acting deodorant hydrogel.

[0007] Another object of the present invention is to provide a preparation method of the above-mentioned progressive reaction type long-acting deodorant hydrogel.

[0008] Another object of the present invention is to provide the application of the above-mentioned progressive reaction type long-acting deodorant hydrogel.

[0009] The object of the present invention is achieved by the following technical solutions:

[0010] A progressive reaction type long-acting deodorant hydrogel, comprising raw material components in the following mass percentages:

[0011] Chondroitin sulfate: 2% - 10%

[0012] Quaternary ammonium salt of chitosan: 2% - 8%

[0013] Agar: 0.05% - 0.5%

[0014] Naringin modified product: 1% - 10%

[0015] Naringin essential oil: 0.1 - 0.5%

[0016] Surfactant: 0.1% - 5%

[0017] Deionized water: the balance

[0018] The sum of the above raw material components is 100%.

[0019] Preferably, the hydrogel comprises raw material components in the following mass percentages:

[0020] Chondroitin sulfate: 4% - 5.5%

[0021] Quaternary ammonium salt of chitosan: 3.5% - 4.5%

[0022] Agar: 0.05% - 0.1%

[0023] Naringin modified product: 5% - 8%

[0024] Naringin essential oil: 0.1 - 0.2%

[0025] Surfactant: 1% - 3%

[0026] Deionized water: the balance

[0027] The sum of the above raw material components is 100%.

[0028] Preferably, the naringin modifier is prepared by the following method: Mix the naringin active ingredient with neohesperidin and water, heat under reflux in an oil bath, and freeze-dry after cooling to room temperature to obtain the naringin modifier;

[0029] The mass ratio of the naringin active ingredient, neohesperidin and water is 1-3:2-5:3-6.

[0030] Preferably, the mass ratio of the naringin active ingredient, neohesperidin and water is 1:2:3;

[0031] The oil bath heating and refluxing is carried out at 70-90 °C for 1-3 h.

[0032] Preferably, the naringin active ingredient is prepared by the following method:

[0033] Cut the pomelo peel, separate the oil cortex and the albedo layer, crush the albedo layer and add 22-25 times the mass of water, soak and extract at a constant temperature of 100-120 °C for 1-2 hours, filter the extract, and rotate and evaporate and concentrate the obtained filtrate by 2.5-4.5 mass times and then seal it, let it stand and freeze at -4 °C for 21-25 h, and take the lower layer after separating into two layers as the naringin active ingredient.

[0034] Preferably, the pomelo essential oil is prepared by physically cold pressing the oil cortex, and the specific steps are as follows:

[0035] (1) Cut the pomelo peel, separate the oil cortex and the albedo layer, cut the oil cortex into blocks of 3×3 cm - 5×5 cm, crush them into blocks of 1×1 cm by a wall breaker, pour water to rinse the essential oil in the wall breaker to obtain water containing pomelo essential oil, and set aside;

[0036] (2) Load the 1×1 cm oil skin blocks into a juicer, press to extract the essential oil, mix 8-10 times the water of the oil skin residue with the water containing pomelo essential oil in step (1), place the oil skin residue on a 40-mesh sieve, and rinse it 4-6 times;

[0037] (3) Mix the essential oil obtained by pressing with the essential oil aqueous solution obtained by rinsing the oil skin residue in step (2), separate the oil and water, let the separated essential oil stand at 3-5 °C for 4-6 hours, separate the oil and water again, and subject the separated essential oil to vacuum filtration to obtain the finished essential oil.

[0038] A method for preparing the above progressive reaction type long-acting deodorant hydrogel, which is characterized by comprising the following steps:

[0039] Prepare chondroitin sulfate hydrogel, naringin-modified agar hydrogel, and naringin-modified agar-chitosan composite hydrogel in sequence. Under stirring conditions, add chondroitin sulfate hydrogel to the naringin-modified agar-chitosan composite hydrogel, and let it stand in a constant temperature water bath at 35-40 °C to obtain a progressive reaction type long-acting deodorant hydrogel.

[0040] Preferably, the specific steps for preparing the above-mentioned progressive reaction type long-acting deodorant hydrogel are as follows:

[0041] (1) Preparation of chondroitin sulfate hydrogel:

[0042] Add a surfactant to 3-5 times the mass of deionized water and stir for 2-5 minutes to obtain a surfactant solution;

[0043] Add chondroitin sulfate to 3-6 times the mass of deionized water and stir for 5-10 minutes to obtain a chondroitin sulfate solution;

[0044] Under stirring conditions, slowly add the surfactant solution to the chondroitin sulfate solution, stir for 3-5 minutes, seal and let it stand and form to obtain chondroitin sulfate hydrogel;

[0045] (2) Preparation of naringin-modified agar hydrogel:

[0046] Based on the mass of the naringin-modified product, add 3-4 times the mass of deionized water and stir for 3-5 minutes to obtain a naringin-modified product solution;

[0047] Based on the mass of agar, first heat 30-40 times the mass of deionized water of agar to boiling, then immediately add agar while boiling, stir for 3-5 minutes, add the naringin-modified product solution, stir evenly, and place it in a constant temperature water bath at 60 °C to let it swell fully to obtain naringin-modified agar hydrogel;

[0048] (3) Preparation of naringin-modified agar-chitosan composite hydrogel:

[0049] Based on the mass of agar, weigh 45-90 times the mass of chitosan quaternary ammonium salt of it, add chitosan quaternary ammonium salt to 2-5 times the mass of deionized water of chitosan quaternary ammonium salt, add and stir while adding, stir for 3-5 minutes to obtain a chitosan quaternary ammonium salt solution;

[0050] Add the chitosan quaternary ammonium salt solution to the naringin-modified agar hydrogel in step (2), and stir and react for 4-5 minutes under the condition of a constant temperature water bath at 60-70 °C, and let it stand for the sol system to crosslink to form naringin-modified agar-chitosan hydrogel;

[0051] (4) Preparation of amphoteric pH-sensitive agar-based chitosan-chondroitin sulfate composite hydrogel:

[0052] Add the chondroitin sulfate hydrocolloid in step (1) to deionized water, conduct the first stirring, add it to the naringin-modified agar-chitosan composite hydrocolloid in step (3), conduct the second stirring, stop the constant temperature water bath at 60-70 °C, and place the entire hydrocolloid system in a constant temperature water bath at 35-40 °C and let it stand for 3-5 h to obtain a progressive reaction type long-acting deodorant hydrogel.

[0053] Preferably, the stirring speed in steps (1), (2), and (3) is 300-400 rpm, the stirring speed in step (4) is 100-200 rpm, and the stirring time for each time is 20-30 minutes.

[0054] Preferably, the surfactant is an amino acid type anionic surfactant.

[0055] Preferably, the amino acid type anionic surfactant is N-acylglutamic acid or N-acylsarcosine.

[0056] Application of the above-mentioned progressive reaction type long-acting deodorant hydrogel in air purification.

[0057] Preferably, the above-mentioned progressive reaction type long-acting deodorant hydrogel is used in the removal of nicotine, formaldehyde, ammonia, hydrogen sulfide, and isovaleric acid.

[0058] In the present invention, first, using naringin as the main raw material, after being modified by being combined with neohesperidin, a naringin-neohesperidin co-cluster with better water solubility than single-component naringin is obtained, and it is prepared into a naringin-modified product. The naringin-modified product contains more alcoholic hydroxyl groups and phenolic hydroxyl groups, which can react with irritating odors such as aldehydes. At the same time, in the present invention, a pH-sensitive hydrogel is used as a carrier, and a broad-spectrum long-acting deodorant hydrogel is prepared by loading an amphoteric deodorant active substance. The basic groups and acidic groups in the amphoteric pH-sensitive hydrogel respectively react with irritating acidic gases such as sulfur dioxide and hydrogen sulfide and basic odor substances such as ammonia and nicotine through coordination, chelation, neutralization, etc., to directionally capture odor components and efficiently convert them into harmless and odorless substances, thereby achieving the effect of quickly expelling odors. Through the reaction of odor substances such as nicotine, ammonia, hydrogen sulfide, sulfur dioxide, and isovaleric acid with amphoteric active substances such as chondroitin sulfate and chitosan quaternary ammonium salt, the hydrogel participating in the reaction disintegrates to form a solution and sinks to the lower part of the hydrogel, while the unreacted active substances remain in the hydrogel to actively and continuously adsorb and capture odor substances, realizing the purpose of long-acting progressive reaction deodorization of the pH-sensitive deodorant hydrogel.

[0059] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0060] (1) The product of the present invention belongs to a progressive reaction type solid deodorant, which can deodorize for a long time with good effect. The present invention mainly reacts odor substances such as nicotine, ammonia, hydrogen sulfide, sulfur dioxide, formaldehyde, and isovaleric acid with naringin modified substances rich in alcohol hydroxyl groups and phenolic hydroxyl groups, as well as amphoteric active substances such as chondroitin sulfate and chitosan quaternary ammonium salt, to actively and continuously adsorb and capture odor substances, and remove various irritating gas components. Among them, the removal effects on air pollutants such as nicotine, isovaleric acid, ammonia, and formaldehyde are extremely good, and the removal rates are as high as 99.52%, 98.4%, 93.5%, and 95% respectively.

[0061] (2) The product of the present invention uses plant-based and animal-based raw materials, has good biodegradability, is non-toxic and harmless, is convenient to dispose of after being discarded, and is environmentally friendly.

[0062] (3) The progressive reaction type product of the present invention can remove many types of odors, and has good removal effects on irritating odor and stench components such as formaldehyde, hydrogen sulfide, ammonia, isovaleric acid, nicotine, and tar in the air.

[0063] (4) The deodorant product of the present invention can actively, continuously, and long-term deodorize, effectively solving the disadvantages of traditional liquid deodorants such as passive deodorization, single-effect, limited application objects, and easy pollution of deodorization objects. In addition, its progressive reaction with odor substances makes the product utilization rate high, effectively avoiding the problem of difficult control of the dosage of liquid deodorants and resulting in waste.

[0064] (5) The product of the present invention has multifunctionality and has many functions such as deodorization, formaldehyde removal, and antibacterial. Chitosan quaternary ammonium salt has strong antibacterial properties and belongs to a natural antibacterial agent.

[0065] (6) The present invention has the characteristics of high-value utilization of agricultural waste. The naringin modified substance in the present invention is obtained from pomelo peel, and pomelo peel accounts for 40% - 55% of the mass of the whole pomelo fruit. Pomelo peel waste is easy to pollute the environment.

[0066] (7) The manufacturing process of the present invention is simple, time-consuming, and low-cost.

[0067] (8) The product of the present invention has a wide range of applications and can meet the deodorization needs of various daily life scenarios. The present invention is suitable for removing nicotine and formaldehyde in rooms and cars, removing ammonia in bathrooms, removing hydrogen sulfide in kitchen waste, removing isovaleric acid from the human body, etc. Description of the Drawings

[0068] Figure 1 For comparison of the forming effects of deodorant hydrogels.

[0069] Figure 2 For the determination of the removal effect of deodorant hydrogel on nicotine by SPME-GC-MS method in Example 1.

[0070] Figure 3 It is for the determination of the removal effect of the odor-removing hydrogel on isovaleric acid by the SPME-GC-MS method in Example 2. Specific implementation mode

[0071] The present invention will be further described in detail below in conjunction with specific embodiments, but the implementation mode of the present invention is not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.

[0072] Neohesperidin was purchased from Guangzhou Chemical Reagent Factory.

[0073] The degree of substitution of chitosan is 98%, and the degree of deacetylation is above 95%.

[0074] Removal effect of the odor-removing hydrogel on nicotine in Example 1

[0075] A progressive reaction type long-acting odor-removing hydrogel was prepared according to the following formula:

[0076] Chondroitin sulfate: 5.5%, quaternary ammonium salt of chitosan: 4.5%, agar: 0.1%, naringin modified product: 8%, pomelo essential oil: 0.1%, surfactant: 3%, deionized water: the balance.

[0077] The preparation method of the odor-removing hydrogel with this formula is as follows:

[0078] (1) Preparation of naringin modified product:

[0079] 1) The pomelo peel was cut with a fruit peel cutter to separate the oil cortex and the white vesicle layer.

[0080] 2) After the oil cortex was crushed, essential oil was obtained by physical cold pressing method, bottled and sealed, and then placed in a constant temperature and humidity box and refrigerated at 4°C for later use;

[0081] The specific process of the physical cold pressing method is as follows: First, the oil cortex of the pomelo peel was manually cut into pieces with an area of about 3×3 cm, then put into a wall breaker and further broken with the fruit and vegetable juice function, taken out and broken into pieces with an area of about 1×1 cm, poured 200 ml of water to wash out the essential oil in the wall breaker for later use, then the broken oil skin pieces were loaded into a (screw type) juicer and squeezed to extract the essential oil, the squeezed oil skin residue was taken out, 8 times the mass of water was mixed with the water containing pomelo essential oil reserved, then the oil skin residue was placed on a 40-mesh sieve and washed 4 times with water, and finally the essential oil obtained by pressing was mixed with the essential oil aqueous solution obtained by washing the oil skin residue, and oil-water separation was carried out. The separated essential oil was left standing at 3°C for 4 hours, and oil-water separation was carried out again, and then the separated essential oil was subjected to reduced pressure filtration with filter paper to finally obtain the finished essential oil.

[0082] 3) After pulverizing the pericarpium citri reticulatae blanco layer, add 22 times its mass of water and soak it at a constant temperature of 100 °C for 1 hour for extraction. Then, filter the extract through gauze, concentrate the filtrate by rotary evaporation 2.5 times its mass, bottle and seal it, and place it in the freezer (-4 °C) of the refrigerator for static freezing for 21 h. After the extract is layered, separate the lower layer to obtain the active ingredient of naringin.

[0083] 4) Based on the mass of the active ingredient of naringin, take 2 times its mass of neohesperidin and 3 times its mass of deionized water. Place the three in a round-bottom flask, heat and reflux in an oil bath at 70 °C for 2 hours until the solution is transparent. Take it out, and after it cools to room temperature, freeze-dry it at -4 °C for 24 h to obtain a naringin-neohesperidin co-cluster with better water solubility than single-component naringin, that is, the modified naringin.

[0084] (2) Chondroitin sulfate hydrogel:

[0085] 1) Add the amino acid-type anionic surfactant to 5 times its mass of deionized water and stir at a speed of 300 revolutions per minute for 2 minutes to make it disperse evenly.

[0086] 2) Add chondroitin sulfate to 6 times its mass of deionized water and stir at a speed of 300 revolutions per minute for 5 minutes to make it dissolve completely.

[0087] 3) At a rotation speed of 300 revolutions per minute, slowly add the amino acid-type anionic surfactant solution in 1) to the chondroitin sulfate solution obtained in 2), stir for 5 minutes, then seal the bottle and let it stand to form a hydrogel for standby.

[0088] (3) Preparation of agar hydrogel loaded with modified naringin:

[0089] Based on the mass of the modified naringin, add 3 times its mass of deionized water and stir at a speed of 300 revolutions per minute for 3 minutes to obtain a modified naringin solution. Taking the mass of agar as a reference, first heat 40 times its mass of deionized water to boiling, then immediately add agar while boiling and stir at a speed of 300 revolutions per minute for 3 minutes. During the process of stirring and dissolving agar, add the modified naringin solution in small amounts and multiple times, and then place the evenly stirred agar hydrogel loaded with modified naringin in a constant temperature water bath and let it stand to fully swell, and keep it in a constant temperature water bath at 60 °C for standby.

[0090] (4) Preparation of agar-chitosan composite hydrogel loaded with modified naringin:

[0091] 1) Based on the mass of agar, weigh 45 times its mass of chitosan quaternary ammonium salt. Add the chitosan quaternary ammonium salt to 5 times its mass of deionized water, stir while adding, and stir at a speed of 300 revolutions per minute for 3 minutes to obtain a chitosan quaternary ammonium salt solution.

[0092] (2) Add the chitosan quaternary ammonium salt solution to the naringin-modified agar sol in (3), and stir and react together at a speed of 300 revolutions per minute under the condition of a constant temperature water bath at 60 °C for 4 minutes, and then let it stand until the sol system crosslinks to form a naringin-modified agar-chitosan hydrogel.

[0093] Basic characteristics of chitosan quaternary ammonium salt: degree of substitution is 98%, and degree of deacetylation is above 95%.

[0094] (5) Preparation of amphoteric pH-sensitive agar-based chitosan-chondroitin sulfate composite hydrogel:

[0095] First, add the chondroitin sulfate hydrogel in (2) to deionized water for the first stirring, and then add it to the naringin-modified agar-chitosan composite hydrogel in (4) for the second stirring. At this time, stop the constant temperature water bath. Both stirrings are carried out at a speed of 100 revolutions per minute for 20 minutes each time to cool down and crosslink and reorganize the sol system. Finally, place the entire sol system in a constant temperature standing water bath at 35 °C. After 24 hours, add naringin essential oil to the formed jelly-like gel to obtain an amphoteric pH-sensitive agar-based chitosan-chondroitin sulfate composite hydrogel, that is, a progressive reaction type long-acting deodorant hydrogel described in the present invention.

[0096] Nicotine removal effect test:

[0097] (1) Test equipment: Agilent gas chromatography-mass spectrometry GC-MS chromatograph, solid-phase microextraction equipment.

[0098] (2) Test method: Take 0.07 g of 1% concentration nicotine (using ethanol as a solvent) in 2 headspace transparent glass bottles, one of which is blank, and add 0.1 g of deodorant hydrogel to the other. After reacting for 24 hours, extract nicotine by the solid-phase microextraction method. The test conditions are a water bath at 45 °C for 2 hours, and then inject into the GC-MS chromatograph. The GC-MS program is: the initial temperature is 50 °C, hold for 2 minutes, the temperature rising gradient is 10 °C / minute, rise to 280 °C, and hold for 5 minutes. Take the peak area as an index to measure the nicotine removal rate, and the test results are shown in Table 1.

[0099] Table 1 Removal effect of deodorant hydrogel on nicotine determined by SPME-GC-MS method

[0100] Blank value After treatment Removal rate Nicotine (peak area) 866302055 4165498 99.52％

[0101] Deodorant hydrogel removal effect of isovaleric acid in Example 2

[0102] Prepare a progressive reaction type long-acting deodorant hydrogel according to the following formula:

[0103] Chondroitin sulfate: 5%, quaternary ammonium salt of chitosan: 4%, agar: 0.08%, naringin modified product: 7%, naringin essential oil: 0.1%, surfactant: 2%, deionized water: the balance.

[0104] The preparation method of this formula deodorant hydrogel is as follows:

[0105] (1) Preparation of naringin modified product:

[0106] The preparation method is the same as that in Example 1.

[0107] (2) Preparation of chondroitin sulfate hydrocolloid:

[0108] 1) Add the amino acid type anionic surfactant to 5 times the mass of deionized water, stir at a speed of 300 revolutions per minute for 2 minutes to make it disperse evenly.

[0109] 2) Add chondroitin sulfate to 5 times the mass of deionized water, stir at a speed of 300 revolutions per minute for 5 minutes to make it fully dissolve.

[0110] 3) At a rotation speed of 300 revolutions per minute, slowly add the amino acid type anionic surfactant solution in 1) to the chondroitin sulfate solution obtained in 2), stir for 5 minutes, then seal and bottle it and let it stand to form a sol for standby.

[0111] (3) Preparation of agar sol loaded with naringin modified product:

[0112] The preparation method is the same as that in Example 1.

[0113] (4) Preparation of agar-chitosan composite hydrocolloid loaded with naringin modified product:

[0114] 1) Based on the mass of agar, weigh 50 times the mass of its quaternary ammonium salt of chitosan, add the quaternary ammonium salt of chitosan to 4 times the mass of deionized water, add while stirring, and stir at a speed of 300 revolutions per minute for 3 minutes to obtain a quaternary ammonium salt of chitosan solution.

[0115] 2) Add the quaternary ammonium salt of chitosan solution to the agar sol loaded with naringin modified product in (3), and stir and react at a speed of 300 revolutions per minute under the condition of a constant temperature water bath at 60 °C for 4 minutes, then let it stand until the sol system crosslinks to form an agar-chitosan hydrocolloid loaded with naringin modified product.

[0116] Basic characteristics of quaternary ammonium salt of chitosan: degree of substitution is 98%, degree of deacetylation is above 95%.

[0117] (5) Preparation of amphoteric pH-sensitive agar-based chitosan-chondroitin sulfate composite hydrogel:

[0118] The operation steps are the same as those in Example 1.

[0119] Test for the effect of removing isovaleric acid:

[0120] (1) Test equipment: Agilent gas chromatography-mass spectrometry (GC-MS) chromatograph, solid-phase microextraction equipment.

[0121] (2) Test method: Take 0.04 g of 1% concentration isovaleric acid (using water as the solvent) in 2 headspace transparent glass bottles. One is blank, and 0.1 g of deodorant hydrogel is added to the other. After reacting for 24 hours, the isovaleric acid is extracted by the solid-phase microextraction method. The test conditions are a water bath at 45 °C for 2 hours of extraction, and then injection into the GC-MS. The GC-MS program is: the initial temperature is 45 °C, held for 2 minutes, the heating gradient is 20 °C / minute, heated to 280 °C, and held for 5 minutes. The removal rate of isovaleric acid is determined using the peak area as an index, and the test results are shown in Table 2.

[0122] Table 2 Removal effect of deodorant hydrogel on isovaleric acid determined by SPME-GC-MS method

[0123] Blank value After treatment Removal rate Isovaleric acid (peak area) 4208882911 67300764.89 98.40％

[0124] Deodorant effect of the deodorant hydrogel in Example 3 on ammonia

[0125] Prepare a progressive reaction type long-acting deodorant hydrogel according to the following formula:

[0126] Chondroitin sulfate: 4%, quaternary ammonium salt of chitosan: 4%, agar: 0.06%, naringin modified product: 6%, naringin essential oil: 0.1%, surfactant: 2%, deionized water: the balance.

[0127] The preparation method of this formula deodorant hydrogel is as follows:

[0128] (1) Preparation of naringin modified product:

[0129] The preparation method is the same as that in Example 1.

[0130] (2) Preparation of chondroitin sulfate hydrocolloid:

[0131] 1) Add the amino acid type anionic surfactant to 4 times the mass of deionized water, stir at a speed of 300 revolutions per minute for 2 minutes to make it evenly dispersed.

[0132] 2) Add chondroitin sulfate to 4 times the mass of deionized water, stir at a speed of 300 revolutions per minute for 5 minutes to make it fully dissolved.

[0133] 3) At a rotation speed of 300 revolutions per minute, slowly add the amino acid type anionic surfactant solution in 1) to the chondroitin sulfate solution obtained in 2), stir for 5 minutes, then seal and bottle and let stand to form a sol for standby.

[0134] (3) Preparation of Naringin-modified Agar Sol:

[0135] The preparation method is the same as that in Example 1.

[0136] (4) Preparation of Naringin-modified Agar-Chitosan Composite Hydrogel:

[0137] 1) Based on the mass of agar, weigh chitosan quaternary ammonium salt according to the mass ratio of 3:200. Add chitosan quaternary ammonium salt to 3 times its mass of deionized water, stirring while adding, and stir at a speed of 300 revolutions per minute for 3 minutes to obtain a chitosan quaternary ammonium salt solution.

[0138] 2) Add the chitosan quaternary ammonium salt solution to the naringin-modified agar sol in (3), and stir and react at a speed of 300 revolutions per minute under the condition of a constant temperature water bath at 60°C for 4 minutes, then let it stand until the sol system crosslinks to form a naringin-modified agar-chitosan hydrogel.

[0139] Basic characteristics of chitosan quaternary ammonium salt: degree of substitution is 98%, and degree of deacetylation is over 95%.

[0140] (5) Preparation of Amphoteric pH-sensitive Agar-based Chitosan-Chondroitin Sulfate Composite Hydrogel:

[0141] The operation steps are the same as those in Example 1.

[0142] Test for the effect of removing ammonia smell:

[0143] (1) Test equipment: 2 special acrylic sealed boxes, with length, width and height being 37 cm × 47 cm × 47 cm respectively, approximately 0.1 m 3 , with a sealed door, 1 deodorant hydrogel test box, and the exposed area of the deodorant hydrogel test box is approximately 130 square centimeters. Put 20 g of deodorant hydrogel and spread it evenly.

[0144] (2) Test method: Take 2 g of 1% ammonia water solution and place it in a petri dish, and put it into two test boxes respectively. Put 20 g of deodorant hydrogel (the deodorant hydrogel to be tested is placed in a box with an exposed area of 130 square centimeters) in one of the boxes. Place ammonia gas detectors in both test boxes, close the sealed door, and measure for 24 hours. The test results are shown in Table 3.

[0145] Table 3 Effect of Deodorant Hydrogel on Removing Ammonia Gas

[0146] Dosage of deodorant hydrogel Ammonia concentration before treatment Ammonia concentration after treatment Ammonia odor removal rate 20g 46 ppm 3 ppm 93.5％

[0147] Effect of Deodorant Hydrogel in Example 4 on Removing Formaldehyde

[0148] Prepare a progressive reaction type long-acting deodorant hydrogel according to the following formula:

[0149] Chondroitin sulfate: 4%, quaternary ammonium salt of chitosan: 3.5%, agar: 0.05%, naringin modified product: 5%, naringin essential oil: 0.1%, surfactant: 1%, deionized water: the balance.

[0150] The preparation method of this formula deodorant hydrogel is as follows:

[0151] (1) Preparation of naringin modified product:

[0152] The preparation method is the same as that in Example 1.

[0153] (2) Preparation of chondroitin sulfate hydrocolloid:

[0154] 1) Add the amino acid type anionic surfactant to 3 times the mass of deionized water, and stir at a speed of 300 revolutions per minute for 2 minutes to make it evenly dispersed.

[0155] 2) Add chondroitin sulfate to 3 times the mass of deionized water, and stir at a speed of 300 revolutions per minute for 5 minutes to make it fully dissolved.

[0156] 3) Under the rotation speed of 300 revolutions per minute, slowly add the amino acid type anionic surfactant solution in 1) to the chondroitin sulfate solution obtained in 2), stir for 5 minutes, then seal the bottle and let it stand still to form a sol for standby.

[0157] (3) Preparation of agar sol loaded with naringin modified product:

[0158] The preparation method is the same as that in Example 1.

[0159] (4) Preparation of agar-chitosan composite hydrocolloid loaded with naringin modified product:

[0160] 1) Based on the mass of agar, weigh 70 times the mass of quaternary ammonium salt of chitosan, add the quaternary ammonium salt of chitosan to 2 times the mass of deionized water, stir while adding, and stir at a speed of 300 revolutions per minute for 3 minutes to obtain a quaternary ammonium salt of chitosan solution.

[0161] 2) Add the quaternary ammonium salt of chitosan solution to the agar sol loaded with naringin modified product in (3), and stir and react at a speed of 300 revolutions per minute under the condition of a constant temperature water bath at 60 °C for 4 minutes, then let it stand still until the sol system crosslinks to form an agar-chitosan hydrocolloid loaded with naringin modified product.

[0162] Basic characteristics of quaternary ammonium salt of chitosan: degree of substitution is 98%, degree of deacetylation is over 95%.

[0163] (5) Preparation of amphoteric pH-sensitive agar-based chitosan-chondroitin sulfate composite hydrogel:

[0164] The operation steps are the same as those in Example 1.

[0165] Formaldehyde removal effect test:

[0166] (1) Test equipment: 1 specially made acrylic sealed box with length, width and height of 37 cm × 47 cm × 47 cm, approximately 0.1 m 3 , with a sealed door, 1 deodorizing hydrogel test box, and the exposed area of the deodorizing hydrogel test box is approximately 130 square centimeters. Put 20 g of deodorizing hydrogel and spread it evenly.

[0167] (2) Test method: First step, use a pipette to transfer 1000 microliters (about 1 g) of 0.13% formaldehyde aqueous solution into a petri dish, then put the sealed deodorizing hydrogel test box into the test chamber, close the test chamber door, turn on the fan at level 1 for 30 minutes, then turn off the fan, and the formaldehyde concentration measured by the air formaldehyde detector is the initial formaldehyde concentration. Take away or seal the petri dish containing formaldehyde, open the prepared deodorizing hydrogel test box, place it in the middle of the test chamber, turn on the fan at level 1 for 30 minutes, then turn off the fan, and the measured formaldehyde concentration is the formaldehyde removal effect after 30 minutes. After 24 hours, turn on the fan at level 1 again for 30 minutes, then turn off the fan, and the measured formaldehyde concentration is the formaldehyde removal effect after 24 hours.

[0168] Second step, test the persistence of the formaldehyde removal ability of the deodorizing hydrogel. Place the deodorizing hydrogel box in an open space and let it volatilize naturally. Test its formaldehyde removal ability when it volatilizes from 20 g to 5 g. The test method is the same as above.

[0169] The test results are as follows. From the following data, it can be concluded that the formaldehyde removal rate of the deodorizing hydrogel and its persistence are very good.

[0170] Table 4 Formaldehyde removal effect of deodorizing hydrogel

[0171]

[0172]

[0173] Comparative test of the formaldehyde removal effect between the deodorizing hydrogel in Comparative Example 1 and market products

[0174] In Comparative Example 1, the preparation method of the deodorizing hydrogel is the same as that in Example 4, and the formaldehyde removal effect test method is the same as the first step in Example 4.

[0175] Conduct a comparative test on the 24-hour formaldehyde removal effects of the invented deodorizing hydrogel, commercially available German deodorant (A30 from Evonik Industries AG in Germany) and British deodorant (FORSTALL from Croda International Plc in the UK), as shown in Table 5.

[0176] Table 5 Comparative test of the formaldehyde removal effects between the deodorizing hydrogel and market products

[0177] Deodorant hydrogel German deodorant British deodorant Formaldehyde removal rate / % 95％ 61.9％ 66.7％

[0178] The above data shows that the formaldehyde-removing effect of the deodorant hydrogel is much higher than that of the commonly used deodorants in the market.

[0179] Effect of agar content on the forming state of hydrogel in Comparative Example 2

[0180] During the preparation of the deodorant hydrogel, the content of agar has a great influence on the formability and strength of the hydrogel. In addition, the content of naringin modified product has a great influence on the formaldehyde removal rate. Therefore, in order to make the deodorant hydrogel have good formability, strength and good formaldehyde removal effect, it is necessary to explore the addition amounts of agar and naringin modified product during the preparation of the deodorant hydrogel.

[0181] The preparation method of the deodorant hydrogel in Comparative Example 2 is the same as that in Example 4.

[0182] Table 6 Effect of agar content on the forming state of hydrogel

[0183]

[0184]

[0185] In the deodorant hydrogel prepared in Example 4, with the addition amounts of other components being the same, the addition amount of agar is optimized based on that in Comparative Example 2. The deodorant hydrogels prepared in Example 4 and the other three examples have good forming, smooth surfaces, almost no solution in the system and no fluidity. Only a hydrogel with good formability can achieve the purpose of progressive reaction deodorization when it plays a role. Therefore, in the present invention, the addition amount of agar needs to reach at least 0.05%.

[0186] Effect of naringin modified product content on formaldehyde removal rate and hydrogel forming state in Comparative Example 3

[0187] During the preparation of the deodorant hydrogel, the content of naringin modified product has a great influence on the formability and strength of the hydrogel. In addition, the content of naringin modified product has a great influence on the formaldehyde removal rate. Therefore, in order to make the deodorant hydrogel have good formability, strength and good formaldehyde removal effect, it is necessary to explore the addition amount of naringin modified product during the preparation of the deodorant hydrogel.

[0188] The preparation method of the deodorant hydrogel in Comparative Example 3 is the same as that in Example 4, and the test method for the formaldehyde removal effect is the same as the first step in Example 4.

[0189] When testing the formaldehyde removal effect of the hydrogel, as the content of the naringin modifier increased, the formaldehyde removal rate also increased. When the addition amount of the naringin modifier increased to 5% or more, the formaldehyde removal rate exceeded 90%. However, when the addition amount of the naringin modifier continued to increase thereafter, the growth rate of the formaldehyde removal rate of the hydrogel gradually slowed down. When the addition amount of the naringin modifier exceeded 8%, the formaldehyde removal rate of the hydrogel reached the peak value of 98%. Moreover, from the appearance, compared with the examples, the formability of the hydrogel was significantly worse at this time. It may be that too much naringin modifier affected the cross-linking and recombination of the gel system, thus affecting the formation of the hydrogel. Therefore, while ensuring the formaldehyde removal effect, the addition amount of the naringin modifier should not exceed 8%.

[0190] Table 7 Influence of the content of the naringin modifier on the formaldehyde removal rate and the forming state of the hydrogel

[0191]

[0192] The above embodiments are the preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A progressive reaction type long-acting deodorant hydrogel, characterized in that, It comprises raw material components with the following mass percentages: Chondroitin sulfate: 4% - 5.5% Quaternary ammonium salt of chitosan: 3.5% - 4.5% Agar: 0.05% - 0.1% Naringin modified product: 5% - 8% Naringin essential oil: 0.1 - 0.2% Surfactant: 1% - 3% Deionized water: the balance The sum of the above raw material components is 100%; The preparation method of the progressive reaction type long - acting deodorant hydrogel comprises the following steps: (1) Preparation of chondroitin sulfate hydrocolloid: Add the surfactant into 3 - 5 times the mass of deionized water and stir to obtain a surfactant solution; Add chondroitin sulfate into 3 - 6 times the mass of deionized water and stir to obtain a chondroitin sulfate solution; Slowly add the surfactant solution to the chondroitin sulfate solution under stirring, continue stirring, seal and let it stand for shaping to obtain chondroitin sulfate hydrocolloid; (2) Preparation of agar sol loaded with naringin modified product: Based on the mass of the naringin modified product, add 3 - 4 times the mass of deionized water and stir to obtain a naringin modified product solution; Based on the mass of agar, first heat 30 - 40 times the mass of deionized water to boiling, immediately add agar while it is boiling, stir, add the naringin modified product solution, stir evenly and then place it in a 60°C constant temperature water bath to stand to obtain agar sol loaded with naringin modified product; (3) Preparation of agar - chitosan composite hydrocolloid loaded with naringin modified product: Based on the mass of agar, weigh 45 - 90 times the mass of quaternary ammonium salt of chitosan, add the quaternary ammonium salt of chitosan into 2 - 5 times the mass of deionized water of the quaternary ammonium salt of chitosan and stir while adding to obtain a quaternary ammonium salt of chitosan solution; Add the quaternary ammonium salt of chitosan solution to the agar sol loaded with naringin modified product in step (2), and carry out stirring reaction at 60 - 70°C in a constant temperature water bath for 4 - 5 minutes, then let it stand to form agar - chitosan composite hydrocolloid loaded with naringin modified product; (4) Preparation of amphoteric pH - sensitive agar - based chitosan - chondroitin sulfate composite hydrogel: Add the chondroitin sulfate hydrocolloid in step (1) into deionized water, carry out the first stirring, add it to the agar - chitosan composite hydrocolloid loaded with naringin modified product in step (3), carry out the second stirring, stop the 60 - 70°C constant temperature water bath, and place the whole sol system in a 35 - 40°C constant temperature water bath to stand for 3 - 5 h to obtain the progressive reaction type long - acting deodorant hydrogel.

2. The progressive reaction type long-acting deodorant hydrogel according to claim 1, characterized in that, The naringin modified product is prepared by the following method: Mix naringin active ingredient, neohesperidin and water, heat under oil bath reflux, and after cooling to room temperature, freeze - dry to obtain the naringin modified product; The mass ratio of the naringin active ingredient, neohesperidin and water is 1 - 3:2 - 5:3 - 6.

3. The progressive reaction type long-acting deodorant hydrogel according to claim 2, characterized in that, The mass ratio of the naringin active ingredient, neohesperidin and water is 1:2:3; The oil bath heating reflux is at 70 - 90°C for 1 - 3 h.

4. The progressive reaction type long-acting deodorant hydrogel according to claim 2, characterized in that, The naringin active ingredient is prepared by the following method: Cut the pomelo peel, separate the essential oil cortex and the albedo layer. After pulverizing the albedo layer, add 22 - 25 times the mass of water and soak it at a constant temperature of 100 - 120 °C for 1 - 2 hours. Filter the extract, and rotate and evaporate the obtained filtrate to concentrate it by 2.5 - 4.5 times the mass, then seal it and let it stand and freeze at -4 °C for 21 - 25 h. After separating into two layers, take the lower layer, which is the active ingredient of naringin. The pomelo essential oil is prepared by physically cold pressing the essential oil cortex.

5. A method for preparing the progressive reaction type long-acting deodorant hydrogel according to claim 1, characterized in that, It includes the following steps: Prepare chondroitin sulfate hydrogel, agar hydrogel loaded with naringin modified product, and agar - chitosan composite hydrogel loaded with naringin modified product in sequence. Under stirring conditions, add the chondroitin sulfate hydrogel to the agar - chitosan composite hydrogel loaded with naringin modified product, and let it stand in a constant temperature water bath at 35 - 40 °C to obtain a progressive reaction - type long - acting deodorant hydrogel.

6. A method for preparing a progressive reaction type long-acting deodorant hydrogel according to claim 5, characterized in that, The specific steps are as follows: (1) Preparation of chondroitin sulfate hydrogel: Add a surfactant to 3 - 5 times the mass of deionized water and stir to obtain a surfactant solution; Add chondroitin sulfate to 3 - 6 times the mass of deionized water and stir to obtain a chondroitin sulfate solution; Under stirring conditions, slowly add the surfactant solution to the chondroitin sulfate solution, continue stirring, seal and let it stand and form to obtain chondroitin sulfate hydrogel; (2) Preparation of agar hydrogel loaded with naringin modified product: Based on the mass of the naringin modified product, add 3 - 4 times the mass of deionized water and stir to obtain a naringin modified product solution; Based on the mass of agar, first heat 30 - 40 times the mass of deionized water to boiling, then immediately add agar while it is boiling, stir, add the naringin modified product solution, stir evenly and then let it stand in a 60 °C constant temperature water bath to obtain agar hydrogel loaded with naringin modified product; (3) Preparation of agar - chitosan composite hydrogel loaded with naringin modified product: Based on the mass of agar, weigh 45 - 90 times the mass of chitosan quaternary ammonium salt of it. Add the chitosan quaternary ammonium salt to 2 - 5 times the mass of deionized water of the chitosan quaternary ammonium salt and stir while adding to obtain a chitosan quaternary ammonium salt solution; Add the chitosan quaternary ammonium salt solution to the agar hydrogel loaded with naringin modified product in step (2), and stir and react together in a constant temperature water bath at 60 - 70 °C for 4 - 5 minutes, then let it stand to form an agar - chitosan composite hydrogel loaded with naringin modified product; (4) Preparation of amphoteric pH - sensitive agar - based chitosan - chondroitin sulfate composite hydrogel: Add the chondroitin sulfate hydrogel in step (1) to deionized water, conduct the first stirring, add it to the agar - chitosan composite hydrogel loaded with naringin modified product in step (3), conduct the second stirring, stop the 60 - 70 °C constant temperature water bath, and let the whole sol system stand in a 35 - 40 °C constant temperature water bath for 3 - 5 h to obtain a progressive reaction - type long - acting deodorant hydrogel.

7. A method for preparing a progressive reaction type long-acting deodorant hydrogel according to claim 6, characterized in that, The stirring speed in steps (1), (2), and (3) is 300 - 400 rpm, and the stirring speed in step (4) is 100 - 200 rpm. Each stirring time is 20 - 30 minutes.

8. A method for preparing a progressive reaction type long-acting deodorant hydrogel according to claim 6, characterized in that, The surfactant is an amino acid - type anionic surfactant.

9. Use of the progressive reaction type long-acting deodorant hydrogel according to any one of claims 1 to 4 in air purification.

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