Composite peculiar smell treatment agent and preparation method thereof

Abstract

The invention relates to a composite peculiar smell treating agent and a preparation method thereof, and belongs to the technical field of peculiar smell treating agents. Iron chloride hexahydrate is creatively used as a metal iron source, 2-aminoterephthalic acid containing an amino group is used as an organic ligand, then an NH2-metal organic framework is prepared through the coordination effect of the iron chloride hexahydrate and the 2-aminoterephthalic acid, then in-situ polymerization based on aniline is carried out, and the composite material is obtained. According to the invention, aniline is added into a metal organic framework, so that aniline can be bonded with amino groups of the metal organic framework in a polymerization process, doping modification of polyaniline is realized, and then a modified metal organic framework is obtained and is synergistically compounded with composite plant volatile oil consisting of ginger essential oil, clove essential oil, holly essential oil, cinnamomum camphora essential oil and mint essential oil as a deodorization active component; according to the present invention, the composite plant volatile oil is subjected to simple physical blending with the auxiliary agent and the deionized water to obtain the composite odor treatment agent, such that the deodorization effect is good, and the volatilization loss of the composite plant volatile oil is less after the storage for a period of time.

Description

Technical Field

[0001] The 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] Odor treatment agent is also called deodorant, which is 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 awareness, the market demand for deodorants has remained high. If classified according to the deodorization principle of deodorants, the existing deodorants can be roughly divided into adsorption deodorants, masking deodorants, biological deodorants, plant deodorants, etc. Among them, plant deodorants have developed extremely rapidly due to their safety, green, low price, and wide sources of raw materials. However, the existing plant deodorants still have certain disadvantages that limit their practical application. This is because, on the one hand, most plant-based deodorants use plant volatile oils as active ingredients for deodorization, and plant volatile oils themselves are highly volatile. Based on this, how to reduce the loss of active ingredients in plant-based deodorants during daily storage is an urgent problem to be solved. The deodorization effect of many plant-based deodorants on the market has been greatly reduced after a period of use. In the final analysis, the deodorization effect of plant volatile oils has been greatly reduced. On the other hand, the deodorization effect of a single plant volatile oil is very poor. Even after the synergistic compounding of multiple plant volatile oils, the deodorization effect is still limited. Summary of the invention

[0003] In view of 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 metallic iron source and 2-aminoterephthalic acid containing an amino group as an organic ligand, and then prepares an NH2-metal organic skeleton through the coordination effect of the two, and then based on the in-situ polymerization of aniline, the aniline can be bonded with the amino group of the metal organic skeleton during the polymerization process, so as to achieve the doping modification of polyaniline, and then obtain a modified metal organic skeleton, and the composite plant volatile oil composed of ginger essential oil, clove essential oil, wintergreen essential oil, camphor essential oil and peppermint essential oil is synergistically compounded as a deodorizing active ingredient, and a composite odor treatment agent is obtained after simple physical blending with an auxiliary agent and deionized water. Not only does the deodorizing effect of the composite plant volatile oil very good, but also after being placed for a period of time, the volatilization loss of the composite plant volatile oil is still small.

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

[0005] A composite odor treatment agent is prepared from composite plant volatile oil, a modified metal organic skeleton, 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, 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.

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

[0009] 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;

[0010] 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;

[0011] 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.

[0012] Furthermore, the power of the ultrasound in step A is 400-450W.

[0013] Furthermore, the centrifugation speed in step B is 10000 rpm and the time is 5 min.

[0014] Furthermore, the dripping rate in step C is controlled at 1-2 drops / s.

[0015] Furthermore, 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 method for preparing a composite odor treatment agent, the method comprising the following steps:

[0018] 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.

[0019] Beneficial effects of the present invention:

[0020] (1) The present invention creatively uses ferric chloride hexahydrate as a metallic iron source and 2-aminoterephthalic acid containing an amino group as an organic ligand, and then prepares an NH2-metal organic framework through the coordination effect of the two. Then, based on the in-situ polymerization of aniline, aniline can be bonded with the amino group of the metal organic framework during the polymerization process to achieve the doping modification of polyaniline, thereby obtaining a modified metal organic framework, which is synergistically compounded with a composite plant volatile oil composed of ginger essential oil, clove essential oil, wintergreen essential oil, camphor essential oil and peppermint essential oil as a deodorizing active ingredient, and is simply physically blended with an auxiliary agent and deionized water to obtain a composite odor treatment agent, which not only has a very good deodorizing effect, but also has a relatively low volatilization loss of the composite plant volatile oil after being placed for a period of time.

[0021] (2) The present invention creatively prepares a modified metal organic framework, and makes it synergistically compounded with a composite plant volatile oil composed of ginger essential oil, clove essential oil, wintergreen essential oil, camphor essential oil and peppermint essential oil as a deodorizing active ingredient. On the one hand, the composite plant volatile oil can remove and degrade odor 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 large specific surface area, rich micropores and strong adsorption capacity. By adding a certain mass proportion of the modified metal organic framework, the composite plant volatile oil can remove and degrade odor. The composite plant volatile oil is "fixed" in its cavity structure, thereby improving the stability of the composite plant volatile oil and inhibiting its volatility 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 polyphenyl rings rich in benzene ring groups, and polyaniline can not only combine with most aromatic compounds through π-π stacking to further reduce their volatility, but also polyaniline, as a polar polymer compound, also promotes the adsorption of polar odor molecules by the composite odor treatment agent during actual use, ultimately obtaining a more excellent deodorization effect.

[0022] (3) The present invention creatively combines the modified metal organic framework and the composite plant volatile oil for synergistic compounding. By introducing the modified metal organic framework, the physical adsorption effect of the composite odor treatment agent on odor is greatly improved, and the practicality is very good. DETAILED DESCRIPTION

[0023] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

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

[0025] Example 1

[0026] A composite odor treatment agent is prepared from composite plant volatile oil, a modified metal organic skeleton, 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 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 1:2:1:0.5:0.5.

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

[0030] Step A: adding 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 stirring and mixing at room temperature for 30 minutes under ultrasound to obtain component A;

[0031] Step B: placing the component A in a hydrothermal reactor, and then treating at 170° C. for 24 hours, naturally cooling to room temperature, centrifuging, discarding the supernatant, washing with N,N-dimethylformamide, and finally vacuum drying at 70° C. until constant weight, to obtain component B;

[0032] Step C: Add 8 parts by weight of anhydrous ethanol, 2 parts by weight of aniline and 3 parts by weight of component B to 80 parts by weight of hydrochloric acid aqueous solution with a pH of 2 under ice bath, then stir for 10 minutes to mix, then dropwise add 25 parts by weight of ammonium persulfate aqueous solution while stirring, continue stirring under ice bath for 4 hours 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° C. until constant weight, and the preparation is completed.

[0033] The power of the ultrasound in step A is 400W.

[0034] The centrifugation speed in step B is 10000 rpm and the time is 5 min.

[0035] The dripping rate in step C is controlled at 1 drop / s.

[0036] The concentration of the ammonium persulfate aqueous 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 method for preparing a composite odor treatment agent, the method comprising the following steps:

[0039] 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 rpm for 15 minutes at room temperature for mixing, and sealed for storage, and the preparation is completed.

[0040] Example 2

[0041] A composite odor treatment agent is prepared from composite plant volatile oil, a modified metal organic skeleton, an 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 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 1:2:1.5:0.5:0.5.

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

[0045] Step A: adding 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, and then stirring and mixing at room temperature for 45 minutes under ultrasound to obtain component A;

[0046] Step B: placing the component A in a hydrothermal reactor, and then treating at 180° C. for 24 hours, naturally cooling to room temperature, centrifuging, discarding the supernatant, washing with N,N-dimethylformamide, and finally vacuum drying at 80° C. until constant weight, to obtain component B;

[0047] Step C: Add 8 parts by weight of anhydrous ethanol, 3 parts by weight of aniline and 3 parts by weight of component B to 90 parts by weight of hydrochloric acid aqueous solution with a pH of 2.5 under an ice bath, and then stir for 15 minutes to mix, then dropwise add 30 parts by weight of ammonium persulfate aqueous solution while stirring, and continue to stir for 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 60° C. until constant weight, and the preparation is completed.

[0048] The power of the ultrasound in step A is 450W.

[0049] The centrifugation speed in step B is 10000 rpm and the time is 5 min.

[0050] The rate of the dripping in step C is controlled at 2 drops / s.

[0051] The concentration of the ammonium persulfate aqueous 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 method for preparing a composite odor treatment agent, the method comprising the following steps:

[0054] 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 500 rpm for 30 minutes at room temperature for mixing, and sealed for storage, and the preparation is completed.

[0055] Example 3

[0056] A composite odor treatment agent is prepared from composite plant volatile oil, a modified metal organic skeleton, an 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 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 1:2:1.3:0.5:0.5.

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

[0060] Step A: adding 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 stirring and mixing at room temperature for 40 minutes under ultrasound to obtain component A;

[0061] Step B: placing the component A in a hydrothermal reactor, and then treating at 175° C. for 24 hours, naturally cooling to room temperature, centrifuging, discarding the supernatant, washing with N,N-dimethylformamide, and finally vacuum drying at 75° C. until constant weight, to obtain component B;

[0062] Step C: Add 8 parts by weight of anhydrous ethanol, 2.5 parts by weight of aniline and 3 parts by weight of component B to 85 parts by weight of a hydrochloric acid aqueous solution with a pH of 2.2 under an ice bath, and then stir for 13 minutes to mix, then dropwise add 28 parts by weight of an ammonium persulfate aqueous solution while stirring, and continue to stir for 5 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 50° C. until constant weight, and the preparation is completed.

[0063] The power of the ultrasound in step A is 400W.

[0064] The centrifugation speed in step B is 10000 rpm and the time is 5 min.

[0065] The dripping 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 method for preparing a composite odor treatment agent, the method comprising the following steps:

[0069] 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 400 rpm for 20 minutes at room temperature for mixing, and sealed for storage, and the preparation is completed.

[0070] Comparative Example 1

[0071] On the basis of Example 3, the modified metal organic framework was replaced with an equal weight of composite plant volatile oil, and the rest remained unchanged.

[0072] Comparative Example 2

[0073] On the basis of Example 3, the 2.5 parts by weight of aniline in step C was changed to 1 part by weight of aniline, and the rest remained 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 remain 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 tested for deodorization effect according to standard QB / T 2761-2006, wherein the test samples were prepared (spray-type materials) without drying and subsequent operations were skipped directly, and ammonia was used as the evaluation standard to obtain the removal rate.

[0079] Table 1. Deodorization effect test results

[0080] Ammonia removal rate / % 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 placed naturally for 6 hours at room temperature and a relative humidity of 50% (not sealed, but left open), and then the deodorization effect test was performed again according to the requirements of Test Example 1.

[0084] Table 2. Volatile loss test results

[0085] Ammonia removal rate / % Example 3 91.9 Comparative Example 1 58.5 Comparative Example 2 81.8 Comparative Example 3 76.4

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

[0087] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still 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 skeleton, auxiliary agent and deionized water.

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 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.

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

6. A composite odor treatment agent according to claim 4, characterized in that: The centrifugation speed in step B is 10000 rpm and the time is 5 min.

7. A composite odor treatment agent according to claim 4, characterized in that: The dripping rate in step C is controlled at 1-2 drops / s.

8. The composite odor treatment agent according to claim 4, characterized in that: The concentration of the ammonium persulfate aqueous solution in step C is 0.5 mol / L.

9. 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.

10. A method for preparing the composite odor treatment agent according to any one of claims 1 to 9, 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.