A composite odor treatment agent and its preparation method

Abstract

The present invention relates to a composite odor treatment agent and a preparation method thereof, belonging to the technical field of odor treatment agents. The present invention creatively uses ferric chloride hexahydrate as a metal iron source and 2-aminoterephthalic acid containing an amino group as an organic ligand. Then, through the coordination of the two, an NH2-metal organic framework is prepared. Next, based on the in-situ polymerization of aniline, aniline can form a bond with the amino group of the metal organic framework during the polymerization process, realizing the doping modification of polyaniline. Furthermore, a modified metal organic framework is obtained, and it is synergistically compounded with a composite plant volatile oil composed of ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil and peppermint essential oil as a deodorizing active ingredient. After simple physical blending with an auxiliary agent and deionized water, a composite odor treatment agent is obtained, which not only has a very good deodorizing effect, but also has less volatilization loss of its composite plant volatile oil after being placed for a period of time.

Description

Technical Field

[0001] The present invention belongs to the technical field of odor treatment agents, and particularly relates to a composite odor treatment agent and a preparation method thereof. Background Art

[0002] An odor treatment agent, also known as a deodorant, refers to a general term for a class of substances that can remove or reduce various unpleasant odors. At present, with the continuous improvement of people's living standards and the continuous strengthening of environmental protection awareness, the market demand for deodorants has always been high. If classified according to the deodorization principle of deodorants, the existing deodorants can be roughly divided into adsorption-type deodorants, masking-type deodorants, biological-type deodorants, plant-type deodorants, etc. Among them, plant-type deodorants have developed extremely rapidly due to many advantages such as safety, greenness, low price, and wide sources of raw materials. However, the existing plant-type deodorants still have certain drawbacks that limit their actual application effects. This is because on the one hand, most plant-type deodorants use plant essential oils as active ingredients for deodorization, and plant essential oils themselves have the characteristic of strong volatility. Based on this, how to reduce the loss of active ingredients of plant-type deodorants during daily storage is an urgent problem to be solved. The deodorization effects of many plant-type deodorants on the market are greatly reduced after a period of use. Ultimately, it is because the plant essential oils have volatilized and lost. On the other hand, the deodorization effect of a single plant essential oil for deodorization is very poor, and even after the synergistic compounding of multiple plant essential oils, its deodorization effect is still limited. Summary of the Invention

[0003] Aiming at the problems existing in the prior art, the purpose of the present invention is to provide a composite odor treatment agent and a preparation method thereof. The present invention creatively uses ferric chloride hexahydrate as a metal iron source and 2-aminoterephthalic acid containing an amino group as an organic ligand. Then, through the coordination of the two, an NH2-metal organic framework is prepared. Next, based on the in-situ polymerization of aniline, aniline can form a bond with the amino group of the metal organic framework during the polymerization process, realizing the doping modification of polyaniline, and then obtaining a modified metal organic framework. It synergistically compounds a composite plant essential oil composed of ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil, and peppermint essential oil as a deodorant active ingredient. After simple physical blending with an auxiliary agent and deionized water, a composite odor treatment agent is obtained, which not only has a very good deodorization effect, but also has less volatilization loss of its composite plant essential oil after being placed for a period of time.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A composite odor treatment agent is prepared from a composite plant essential oil, a modified metal organic framework, an auxiliary agent, and deionized water.

[0006] As a preferred technical solution of the present invention, the mass ratio of the composite plant volatile oil, the modified metal-organic framework, the auxiliary agent and the deionized water is 8-10:3:5:90-100.

[0007] As a preferred technical solution of the present invention, the composite plant volatile oil includes ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil and peppermint essential oil; the mass ratio of the ginger essential oil, the clove essential oil, the wintergreen essential oil, the linalool essential oil and the peppermint essential oil is 1:2:1-1.5:0.5:0.5.

[0008] As a preferred technical solution of the present invention, the modified metal-organic framework is prepared by the following steps:

[0009] Step A: Add 1.6-2 parts by weight of ferric chloride hexahydrate and 0.5-1 part by weight of 2-aminoterephthalic acid to 80-90 parts by weight of N,N-dimethylformamide, and then stir at room temperature for 30-45 min under ultrasonic waves to obtain Component A;

[0010] Step B: Place Component A in a hydrothermal reaction kettle, then treat it at 170-180 °C for 24 h, naturally cool to room temperature, centrifuge, discard the supernatant, wash with N,N-dimethylformamide, and finally vacuum dry at 70-80 °C until constant weight to obtain Component B;

[0011] Step C: Add 8 parts by weight of absolute ethanol, 2-3 parts by weight of aniline and 3 parts by weight of Component B to 80-90 parts by weight of hydrochloric acid aqueous solution with a pH of 2-2.5 under ice bath, then stir for 10-15 min to mix, and then dropwise add 25-30 parts by weight of ammonium persulfate aqueous solution while stirring. After the addition is completed, continue to stir under ice bath for 4-6 h, let stand for 6 h, filter, take the filter residue, wash with deionized water, and finally vacuum dry at 40-60 °C until constant weight to complete the preparation.

[0012] Further, the power of the ultrasonic wave in Step A is 400-450 W.

[0013] Further, the rotation speed of the centrifuge in Step B is 10000 rpm and the time is 5 min.

[0014] Further, the dropping rate in Step C is controlled at 1-2 drops / s.

[0015] Further, the concentration of the ammonium persulfate aqueous solution in Step C is 0.5 mol / L.

[0016] As a preferred technical solution of the present invention, the auxiliary agent includes 1.5 parts by weight of polysorbate 80, 1-2 parts by weight of propylene glycol, and 1.5 parts by weight of polyethylene glycol 2000.

[0017] A preparation method of a composite odor treatment agent, the preparation method comprising the following steps:

[0018] Add composite plant volatile oil, modified metal-organic framework and auxiliary agent to deionized water, then stir and mix at a rotation speed of 300-500 rpm at room temperature for 15-30 min, and store in a sealed manner to complete the preparation.

[0019] Advantages of the present invention:

[0020] (1) The present invention creatively uses ferric chloride hexahydrate as a metal iron source and 2-aminoterephthalic acid containing an amino group as an organic ligand. Then, through the coordination of the two, an NH2-metal organic framework is prepared. Next, based on the in-situ polymerization of aniline, aniline can form a bond with the amino group of the metal organic framework during the polymerization process to achieve the doping modification of polyaniline, and then a modified metal organic framework is obtained. It synergistically combines a composite plant volatile oil composed of ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil and peppermint essential oil as a deodorant active ingredient. After simple physical blending with the auxiliary agent and deionized water, a composite odor treatment agent is obtained, which not only has a very good deodorizing effect, but also has less volatilization loss of its composite plant volatile oil after being placed for a period of time.

[0021] (2) The present invention creatively prepares a modified metal-organic framework, which synergistically combines a composite plant volatile oil composed of ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil and peppermint essential oil as a deodorant active ingredient. On the one hand, the composite plant volatile oil can remove and degrade odors through a series of complex chemical reactions such as acid-base reaction, oxidation-reduction, and addition. On the other hand, the modified metal-organic framework itself has the characteristics of a large specific surface area, rich micropores, and strong adsorption capacity. By adding a certain mass ratio of the modified metal-organic framework, the composite plant volatile oil can be "fixed" in its cavity structure, thereby improving the stability of the composite plant volatile oil and inhibiting its volatilization loss to a certain extent. At the same time, after the in-situ polymerization of aniline, the surface of the metal-organic framework is doped with a polybenzene ring rich in benzene ring groups. Polyaniline can not only combine with most aromatic compounds through π-π stacking to further reduce its volatilization, but also, as a polar polymer compound, promotes the adsorption of the composite odor treatment agent to polar odor molecules during actual use. Finally, a more excellent deodorizing effect is obtained.

[0022] (3) The present invention creatively combines a modified metal-organic framework and a composite plant volatile oil. By introducing the modified metal-organic framework, the physical adsorption of the composite odor treatment agent for malodorous gases is greatly improved, and the practicality is very good. Detailed Embodiments

[0023] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following combines examples to detail the specific embodiments, structures, features, and their effects according to the present invention as follows.

[0024] The sources of the raw materials are as follows: Ginger essential oil, clove essential oil, wintergreen essential oil, and peppermint essential oil are all purchased from Jiangxi Hairui Natural Plant Co., Ltd.; linalool essential oil is purchased from Jiangxi Jingwang Natural Flavors Co., Ltd., product number JW-87; polysorbate 80 is purchased from Shandong Kepler Biotechnology Co., Ltd., model kpl-23123.

[0025] Example 1

[0026] A composite odor treatment agent, which is prepared from a composite plant volatile oil, a modified metal-organic framework, an auxiliary agent, and deionized water.

[0027] The mass ratio of the composite plant volatile oil, the modified metal-organic framework, the auxiliary agent, and the deionized water is 8:3:5:90.

[0028] The composite plant volatile oil includes ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil, and peppermint essential oil; the mass ratio of the ginger essential oil, the clove essential oil, the wintergreen essential oil, the linalool essential oil, and the peppermint essential oil is 1:2:1:0.5:0.5.

[0029] The modified metal-organic framework is prepared through the following steps:

[0030] Step A: Add 1.6 parts by weight of ferric chloride hexahydrate and 0.5 parts by weight of 2-aminoterephthalic acid to 80 parts by weight of N,N-dimethylformamide, and then stir at room temperature for 30 min under ultrasonic conditions to obtain Component A;

[0031] Step B: Place Component A in a hydrothermal reaction kettle, then treat it at 170 °C for 24 h, naturally cool to room temperature, centrifuge, discard the supernatant, wash with N,N-dimethylformamide, and finally vacuum dry at 70 °C until constant weight to obtain Component B;

[0032] Step C: Add 8 parts by weight of absolute ethanol, 2 parts by weight of aniline, and 3 parts by weight of component B to 80 parts by weight of an aqueous hydrochloric acid solution with a pH of 2 under an ice bath. Then stir for 10 min to mix. Next, while stirring, dropwise add 25 parts by weight of an aqueous ammonium persulfate solution. After the addition is complete, continue to stir under the ice bath for 4 h, let stand for 6 h, filter, collect the filter residue, wash it with deionized water, and finally dry it under vacuum at 40 °C until a constant weight is achieved, thus completing the preparation.

[0033] The power of the ultrasonic wave in Step A is 400 W.

[0034] The rotation speed of the centrifugation in Step B is 10,000 rpm, and the time is 5 min.

[0035] The dropping rate in Step C is controlled at 1 drop / s.

[0036] The concentration of the aqueous ammonium persulfate solution in Step C is 0.5 mol / L.

[0037] The auxiliary agent includes 1.5 parts by weight of polysorbate 80, 1 part by weight of propylene glycol, and 1.5 parts by weight of polyethylene glycol 2000.

[0038] A preparation method of a composite odor treatment agent, the preparation method comprising the following steps:

[0039] Add composite plant volatile oil, modified metal-organic framework, and auxiliary agent to deionized water, then stir and mix at a rotation speed of 300 rpm at room temperature for 15 min, and store it sealed, thus completing the preparation.

[0040] Example 2

[0041] A composite odor treatment agent, the composite odor treatment agent is prepared from composite plant volatile oil, modified metal-organic framework, auxiliary agent, and deionized water.

[0042] The mass ratio of the composite plant volatile oil, the modified metal-organic framework, the auxiliary agent, and the deionized water is 10:3:5:100.

[0043] The composite plant volatile oil includes ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil, and peppermint essential oil; the mass ratio of the ginger essential oil, the clove essential oil, the wintergreen essential oil, the linalool essential oil, and the peppermint essential oil is 1:2:1.5:0.5:0.5.

[0044] The modified metal-organic framework is prepared through the following steps:

[0045] Step A: Add 2 parts by weight of ferric chloride hexahydrate and 1 part by weight of 2-aminoterephthalic acid to 90 parts by weight of N,N-dimethylformamide, then stir and mix at room temperature in ultrasonic waves for 45 min to obtain component A;

[0046] Step B: Place the component A in a hydrothermal reactor, then treat it at 180 °C for 24 h, naturally cool it to room temperature, centrifuge it, discard the supernatant, wash it with N,N-dimethylformamide, and finally dry it under vacuum at 80 °C until a constant weight is obtained to get component B;

[0047] Step C: Add 8 parts by weight of absolute ethanol, 3 parts by weight of aniline, and 3 parts by weight of component B to 90 parts by weight of an aqueous hydrochloric acid solution with a pH of 2.5 under an ice bath, then stir for 15 min to mix. Next, while stirring, dropwise add 30 parts by weight of an aqueous ammonium persulfate solution. After the addition is completed, continue to stir under the ice bath for 6 h, let it stand for 6 h, filter, take the filter residue, wash it with deionized water, and finally dry it under vacuum at 60 °C until a constant weight is obtained, thus completing the preparation.

[0048] The power of the ultrasonic wave in Step A is 450 W.

[0049] The rotation speed of the centrifuge in Step B is 10,000 rpm and the time is 5 min.

[0050] The dropping rate in Step C is controlled at 2 drops / s.

[0051] The concentration of the aqueous ammonium persulfate solution in Step C is 0.5 mol / L.

[0052] The auxiliary agent includes 1.5 parts by weight of polysorbate 80, 2 parts by weight of propylene glycol, and 1.5 parts by weight of polyethylene glycol 2000.

[0053] A preparation method of a composite odor treatment agent, the preparation method comprising the following steps:

[0054] Add composite plant volatile oil, modified metal-organic framework, and auxiliary agent to deionized water, then stir and mix at a rotation speed of 500 rpm at room temperature for 30 min, and store it sealed, thus completing the preparation.

[0055] Example 3

[0056] A composite odor treatment agent, the composite odor treatment agent is prepared from composite plant volatile oil, modified metal-organic framework, auxiliary agent, and deionized water.

[0057] The mass ratio of the composite plant volatile oil, the modified metal-organic framework, the auxiliary agent, and the deionized water is 9:3:5:95.

[0058] The composite plant volatile oil includes ginger essential oil, clove essential oil, wintergreen essential oil, linalool essential oil, and peppermint essential oil; the mass ratio of the ginger essential oil, the clove essential oil, the wintergreen essential oil, the linalool essential oil, and the peppermint essential oil is 1:2:1.3:0.5:0.5.

[0059] The modified metal-organic framework is prepared through the following steps:

[0060] Step A: Add 1.8 parts by weight of ferric chloride hexahydrate and 0.8 parts by weight of 2-aminoterephthalic acid to 85 parts by weight of N,N-dimethylformamide, and then stir the mixture at room temperature for 40 min under ultrasonic treatment to obtain Component A;

[0061] Step B: Place Component A in a hydrothermal reaction kettle, then treat it at 175 °C for 24 h, naturally cool it to room temperature, centrifuge it, discard the supernatant, wash it with N,N-dimethylformamide, and finally dry it under vacuum at 75 °C until a constant weight is obtained to obtain Component B;

[0062] Step C: Add 8 parts by weight of absolute ethanol, 2.5 parts by weight of aniline, and 3 parts by weight of Component B to 85 parts by weight of hydrochloric acid aqueous solution with a pH of 2.2 under an ice bath, then stir the mixture for 13 min to mix, and then dropwise add 28 parts by weight of ammonium persulfate aqueous solution while stirring. After the addition is completed, continue to stir under the ice bath for 5 h, let it stand for 6 h, filter it, take the filter residue, wash it with deionized water, and finally dry it under vacuum at 50 °C until a constant weight is obtained, thus completing the preparation.

[0063] The power of the ultrasonic treatment in Step A is 400 W.

[0064] The rotation speed of the centrifuge in Step B is 10,000 rpm, and the time is 5 min.

[0065] The dropping rate in Step C is controlled at 1.5 drops / s.

[0066] The concentration of the ammonium persulfate aqueous solution in Step C is 0.5 mol / L.

[0067] The auxiliary agent includes 1.5 parts by weight of polysorbate 80, 1.5 parts by weight of propylene glycol, and 1.5 parts by weight of polyethylene glycol 2000.

[0068] A preparation method of a composite odor treatment agent, the preparation method includes the following steps:

[0069] Add composite plant volatile oil, modified metal-organic framework, and auxiliary agent to deionized water, and then stir the mixture at a rotation speed of 400 rpm at room temperature for 20 min to mix, and store it sealed, thus completing the preparation.

[0070] Comparative Example 1

[0071] On the basis of Example 3, the modified metal-organic framework is changed to an equal weight of composite plant volatile oil, and the rest remains unchanged.

[0072] Comparative Example 2

[0073] On the basis of Example 3, 2.5 parts by weight of aniline in Step C is changed to 1 part by weight of aniline, and the rest remains unchanged.

[0074] Comparative Example 3

[0075] On the basis of Example 3, the mass ratio of the composite plant volatile oil, the modified metal-organic framework, the auxiliary agent, and the deionized water is changed from 9:3:5:95 to 9:1.5:5:95, and the rest remains unchanged.

[0076] Test Example 1

[0077] Deodorization effect test:

[0078] The composite odor treatment agents prepared in Example 3 and Comparative Examples 1-3 were respectively subjected to a deodorization effect test with reference to the standard QB / T 2761-2006. Among them, when preparing the test samples (spray materials), they were not dried, and the subsequent operations could be directly skipped. Using ammonia as the evaluation standard, the removal rate was obtained.

[0079] Table 1. Deodorization effect test results

[0080] Removal rate of ammonia / % Example 3 95.2 Comparative Example 1 80.4 Comparative Example 2 89.9 Comparative Example 3 92.8

[0081] Test Example 2

[0082] Volatile loss test:

[0083] The composite odor treatment agents prepared in Example 3 and Comparative Examples 1-3 were respectively placed naturally for 6 h (not sealed, placed openly) at normal temperature and a relative humidity of 50%, and then the deodorization effect test was carried out again according to the requirements of Test Example 1.

[0084] Table 2. Volatile loss test results

[0085] Removal rate of ammonia / % Example 3 91.9 Comparative Example 1 58.5 Comparative Example 2 81.8 Comparative Example 3 76.4

[0086] From Test Examples 1-2, by comparing Example 3 with Comparative Examples 1-3, it can be seen that the composite odor treatment agent prepared by the present invention not only has a good deodorization effect, but also can still maintain a good deodorization performance after being placed for a period of time, which indirectly shows that the volatile loss of its composite plant volatile oil is less.

[0087] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments of equivalent changes within the scope of the technical solution of the present invention by using the above-disclosed technical content. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A composite odor treatment agent, characterized in that: The composite odor treatment agent is prepared from composite plant volatile oil, modified metal organic framework, auxiliary agent and deionized water; The modified metal organic framework is prepared by the following steps: Step A: adding 1.6-2 parts by weight of ferric chloride hexahydrate and 0.5-1 parts by weight of 2-aminoterephthalic acid to 80-90 parts by weight of N,N-dimethylformamide, and then stirring and mixing at room temperature for 30-45 minutes in an ultrasonic manner to obtain component A; Step B: placing the component A in a hydrothermal reaction kettle, and then treating at 170-180° C. for 24 hours, naturally cooling to room temperature, centrifuging, discarding the supernatant, washing with N,N-dimethylformamide, and finally vacuum drying at 70-80° C. until constant weight, to obtain component B; Step C: Add 8 parts by weight of anhydrous ethanol, 2-3 parts by weight of aniline and 3 parts by weight of component B to 80-90 parts by weight of a hydrochloric acid aqueous solution with a pH of 2-2.5 under an ice bath, and then stir for 10-15 minutes to mix, then dropwise add 25-30 parts by weight of an ammonium persulfate aqueous solution while stirring, and continue to stir for 4-6 hours under an ice bath after the dropwise addition is completed, let stand for 6 hours, filter, take the filter residue, wash with deionized water, and finally vacuum dry at 40-60° C. until constant weight, and the preparation is completed.

2. A composite odor treatment agent according to claim 1, characterized in that: The mass ratio of the composite plant volatile oil, the modified metal organic framework, the auxiliary agent and the deionized water is 8-10:3:5:90-100.

3. A composite odor treatment agent according to claim 1, characterized in that: The composite plant volatile oil comprises ginger essential oil, clove essential oil, wintergreen essential oil, camphor essential oil and peppermint essential oil; the mass ratio of the ginger essential oil, the clove essential oil, the wintergreen essential oil, the camphor essential oil and the peppermint essential oil is 1:2:1-1.5:0.5:0.

5.

4. The composite odor treatment agent according to claim 1, characterized in that: The power of the ultrasound in step A is 400-450W.

5. The composite odor treatment agent according to claim 1, characterized in that: The centrifugation speed in step B is 10000 rpm and the time is 5 min.

6. The composite odor treatment agent according to claim 1, characterized in that: The dripping rate in step C is controlled at 1-2 drops / s.

7. The composite odor treatment agent according to claim 1, characterized in that: The concentration of the ammonium persulfate aqueous solution in step C is 0.5 mol / L.

8. The composite odor treatment agent according to claim 1, characterized in that: The auxiliary agent includes 1.5 parts by weight of polysorbate 80, 1-2 parts by weight of propylene glycol and 1.5 parts by weight of polyethylene glycol 2000.

9. A method for preparing the composite odor treatment agent according to any one of claims 1 to 8, characterized in that: The preparation method comprises the following steps: The composite plant volatile oil, the modified metal organic framework and the additive are added into the deionized water, and then stirred at a speed of 300-500 rpm for 15-30 minutes at room temperature for mixing, and sealed for storage, and the preparation is completed.