CN115969709A - Novel liquid crystal emulsion and preparation method and application thereof - Google Patents

Novel liquid crystal emulsion and preparation method and application thereof Download PDF

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CN115969709A
CN115969709A CN202310033401.6A CN202310033401A CN115969709A CN 115969709 A CN115969709 A CN 115969709A CN 202310033401 A CN202310033401 A CN 202310033401A CN 115969709 A CN115969709 A CN 115969709A
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liquid crystal
emulsifier
novel liquid
crystal emulsion
alcohol
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李恩秀
金东寅
尹钟文
李持玟
郑弘洙
孙钟勋
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Hanfo Cosmetics Huzhou Co ltd
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Abstract

The application provides a novel liquid crystal emulsion, a preparation method and application thereof, and relates to the technical field of cosmetics. The novel liquid crystal emulsion comprises the following raw materials in percentage by weight: 10-20% of emulsifier, 5-10% of polar grease and the balance of water; the emulsifier comprises a fatty acid emulsifier or a polyglycerol ester emulsifier; the polar oil comprises one or more of olive oil, caprylic/capric triglyceride, squalane and polydimethylsiloxane. The emulsion prepared by the formula can form clear liquid crystal with large particles, and can be widely applied to the cosmetic industry.

Description

Novel liquid crystal emulsion and preparation method and application thereof
Technical Field
The application relates to the technical field of cosmetics, in particular to a novel liquid crystal emulsion and a preparation method and application thereof.
Background
As a main component of human skin, a main basic structure of a biological membrane is a lipid bilayer of phospholipid (phosphoipid) and glycolipid (glycoipid), and a drug, an active substance, or the like is trapped in an artificially prepared lipid bilayer to more easily permeate the skin, and many studies have been made. However, since the skin is covered with a certain thickness of the stratum corneum, there is a problem in that the active substances in the cosmetics are less likely to permeate into the skin. In order to overcome these limitations, various emulsion manufacturing techniques have been developed, and cosmetics having good skin absorption rate and high efficacy are actively studied. In recent years, in order to improve the stability and persistence of hydrophilic and lipophilic active ingredients, liposomes having a structure similar to that of skin lipids and capable of enhancing transdermal penetration (absorption rate) or an emulsified form containing a plurality of different compounds at once are expected to realize various effects as a main production method for cosmetic emulsification. Among them, there are many concerns and application studies particularly on liquid crystals. The definition of liquid crystal is as follows: when the temperature of an organic compound rises, the crystal structure starts to be destroyed, and above a certain temperature, the crystal structure is completely transformed into isotropy in which the crystal structure is destroyed, a phase in the process of transforming the complete crystal structure into a completely amorphous structure is called a Mesophase (Mesophase), and the organic compound in the Mesophase state is called a Liquid crystal (Liquid crystal). In the cosmetic industry, the technology of liquid crystals is being developed with the development of emulsification technology (emulsification technology) of surfactants.
Disclosure of Invention
The application aims to provide a novel liquid crystal emulsion, and liquid crystals in the novel liquid crystal emulsion are clear and large in particle size.
Another object of the present application is to provide a method for preparing a novel liquid crystal emulsion, which can make the combination of different raw materials better.
The technical problem to be solved by the application is solved by adopting the following technical scheme.
On one hand, the embodiment of the application provides a novel liquid crystal emulsion which comprises the following raw materials in percentage by weight: 10-20% of emulsifier, 5-10% of polar grease and the balance of water; the emulsifier comprises a fatty acid emulsifier or a polyglycerol ester emulsifier; the polar oil comprises one or more of olive oil, caprylic/capric triglyceride, squalane and polydimethylsiloxane.
On the other hand, the embodiment of the application provides a preparation method of a novel liquid crystal emulsion, which comprises the following steps:
respectively heating the oil phase and the water phase in the raw materials to 75-85 ℃, continuously stirring the water phase, adding the oil phase raw materials while stirring, continuously stirring, and cooling to obtain the novel liquid crystal emulsion.
In another aspect, the embodiments of the present application provide a novel liquid crystal emulsion for use in the preparation of cosmetics.
Compared with the prior art, the embodiment of the application has at least the following advantages or beneficial effects:
1. the novel liquid crystal emulsion is mainly prepared from fatty acid and polyglycerol ester emulsifiers and polar grease (olive oil, caprylic/capric triglyceride), wherein the polar grease can participate in the formation of liquid crystal in the emulsifiers, and higher alcohols (cetearyl alcohol, cetyl alcohol and behenyl alcohol) are added on the basis, so that liquid crystal particles can be clearer, and in a certain range, the particle size is increased along with the increase of the content of the higher alcohols.
2. The sucrose emulsifier in the application is not easy to form liquid crystal when being mixed with polar grease (olive oil, caprylic/capric triglyceride), but higher alcohols (cetearyl alcohol, cetyl alcohol and behenyl alcohol) are added into the system, so that the sample liquid crystal formation is excellent, and the higher alcohols are helpful for the formation of liquid crystal in the sucrose emulsifier series.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a photomicrograph of a polarization microscope of each experimental group in example 1 of the present application;
FIG. 2 is a photograph of a polarization microscope of each experimental group in example 2 of the present application;
FIG. 3 is a photograph of a polarization microscope of each experimental group in example 3 of the present application;
FIG. 4 is a polarization microscope photograph comparing A-4, A-5, A-6 and A-1 in example 4 of the present application;
FIG. 5 is a photograph taken by a polarizing microscope comparing A-7, A-8, A-9 and A-1 in example 4 of the present application;
FIG. 6 is a polarization microscope photograph comparing A-10, A-11, A-12 and A-1 in example 4 of the present application;
FIG. 7 is a polarization microscope photograph comparing A-13, A-14, A-15 and A-2 in example 5 of the present application;
FIG. 8 is a polarization microscope photograph comparing A-16, A-17, A-18 and A-2 in example 5 of the present application;
FIG. 9 is a polarization microscope photograph comparing A-19, A-20, A-21 and A-2 in example 5 of the present application;
FIG. 10 is a polarization microscope photograph comparing B-4, B-5, B-6 and B-7 with B-1 and B-2 in example 6 of the present application;
FIG. 11 is a polarization microscope photograph comparing C-4, C-5, C-6 and C-7 with C-1 and C-2 in example 6 of the present application;
fig. 12 is a polarization microscope photograph of each sample in example 7 of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present application will be described in detail below with reference to specific examples.
The novel liquid crystal emulsion comprises the following raw materials in percentage by weight: 10-20% of emulsifier, 5-10% of polar grease and the balance of water; wherein the water is deionized water;
the emulsifier comprises fatty acid emulsifier or polyglycerol ester emulsifier;
the polar oil comprises one or more of olive oil, caprylic/capric triglyceride, squalane and polydimethylsiloxane. The polar oil used in the present application is preferably olive oil (olive EUROPAEA fruit oil, KERFOOT (usa)), MCT (caprylic/capric triglyceride, PT Musim Mas (indonesia)), squalane (squalane, KISHIMOTO (japan)).
In some embodiments of the present application, the fatty acid based emulsifier comprises cetearyl alcohol. In the present application, the fatty acid-based emulsifier is preferably MONTANOV 68 (cetearyl alcohol/RYL GLUCETEACOSIDE, SEPPIC (France)).
In some embodiments of the present application, the above-mentioned polyglycerin ester type emulsifier includes at least one of polysorbate-60 and polyglycerin-2 stearate. In the present application, the polyglycerol ester-based emulsifier is preferably TWEEN 60V (POLYSORBATE 60, david, USA), SPAN 60-PW- (AP) (sorbitan stearate, david, USA).
In some embodiments of the present application, the emulsifier further comprises a sucrose emulsifier, and when the emulsifier is a sucrose emulsifier, the raw material further comprises 2-5% of a stabilizer.
In some embodiments herein, the sucrose-based emulsifier comprises sorbitan stearate and the stabilizer is a higher alcohol.
In some embodiments of the present application, the higher alcohol is one or more of cetearyl alcohol, cetyl alcohol, and behenyl alcohol.
A preparation method of a novel liquid crystal emulsion comprises the following steps:
respectively heating the oil phase and the water phase in the raw materials to 75-85 ℃, continuously stirring the water phase, adding the oil phase raw materials while stirring, continuously stirring, and cooling to obtain the novel liquid crystal emulsion.
In the present application, the aqueous phase is water and the oil phase is an emulsifier, a polar oil and a stabilizer.
In view of stability, immediately after the production, the state of emulsified particles was confirmed using a microscope (Model CP15U, mitsubishi, japan) equipped with a polarizer, and the presence or absence of liquid crystal generation was confirmed.
In some embodiments of the present application, the stirring speed is 1500-3000rpm, the stirring time is 10-20min, and the temperature after cooling is 28-35 ℃.
Use of the novel liquid-crystal emulsions according to claim for the preparation of cosmetics.
In some embodiments of the present application, the cosmetic comprises one or more of facial cleanser, facial mask, lotion, milky lotion, cream, essence, and the novel liquid crystal emulsion is added in an amount of 0.1-4%.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
This example uses cetearyl alcohol (MONTANOV 68) in the series of fatty acids as an emulsifier, which was reacted with different kinds of polar oils (olive oil, caprylic/capric triglyceride, and squalane) to prepare liquid crystal emulsions, the addition ratios (weight ratios) of which are shown in table 1.
TABLE 1
Figure BDA0004048227540000061
Figure BDA0004048227540000071
The preparation method comprises the following steps: heating the water phase and oil phase to 80 deg.C, respectively, stirring the water phase at 2000rpm, adding dissolved oil phase while stirring, stirring at 2000rpm for 10min, and cooling the stirred emulsion to 30 deg.C under the same cooling condition.
The results of observation with a microscope equipped with a polarizing plate after cooling are shown in FIG. 1, and it can be seen from FIG. 1 that the emulsion particle and liquid crystal formation state of each sample were observed immediately after production using an emulsifier of fatty acid series MONTANOV 68 (CETEARYL alcohol/CETEARYL alcohol), and it was found that the A-1 and A-2 samples using olive oil and caprylic/capric triglyceride having high polarity in the oil phase exhibited good liquid crystal formation and liquid crystal particle formation was more clear and stable.
Example 2
In this example, sorbitan stearate (ARLACEL 2121-FL- (MV)) in sucrose emulsifier series was used as an emulsifier, and this was reacted with different kinds of polar oils and fats (olive oil, caprylic/capric triglyceride, and squalane) to prepare liquid crystal emulsions, and the addition ratio (weight ratio) thereof was as shown in table 2.
TABLE 2
Figure BDA0004048227540000072
The preparation method comprises the following steps: heating water phase and oil phase to 82 deg.C respectively, stirring water phase at 2500rpm, adding dissolved oil phase while stirring, stirring at 2500rpm for 15min, and cooling the stirred emulsion to 30 deg.C under the same cooling condition.
The results of observation of the liquid crystal after cooling with a microscope equipped with a polarizer are shown in FIG. 2, and it can be seen from FIG. 2 that the liquid crystal was not well formed in the samples produced using the SUCROSE series ARLACEL 2121-FL- (MV) (sorbitan stearate/SUCROSE COCOATE) emulsifier and using oils of different polarities (olive oil, caprylic/capric triglyceride, squalane).
Example 3
In this example, a polyglycerol ester emulsifier glyceryl stearate (POLYAQUOL-2W) was used as an emulsifier, and the emulsifier was reacted with different kinds of polar oils (olive oil, caprylic/capric triglyceride, and polydimethylsiloxane) to prepare a liquid crystal emulsion, and the addition ratio (weight ratio) thereof was as shown in Table 3.
TABLE 3
Figure BDA0004048227540000081
/>
The preparation method comprises the following steps: heating the water phase and oil phase to 75 deg.C, respectively, stirring the water phase at 2000rpm, adding dissolved oil phase while stirring, stirring at 2000rpm for 20min, and cooling the stirred emulsion to 30 deg.C under the same cooling condition.
The observation of the resulting liquid crystal layer after cooling was carried out by a microscope equipped with a polarizer, and the results are shown in FIG. 3. As can be seen from FIG. 3, the formation of C-1 and C-2 liquid crystals was confirmed in the sample using the polyglycerol ester series POLYAQUOL-2W emulsifier.
From the combination of examples 1 to 3, it can be seen that 2 emulsifiers other than the sucrose-series emulsifier ARLACEL 21211-FL- (MV) among the 3 emulsifiers were able to confirm that olive oil and caprylic/capric triglyceride having high polarity intervene in the formation of liquid crystals.
Example 4
In this example, higher alcohols (cetearyl alcohol, cetyl alcohol and behenyl alcohol) were added in different proportions (2%, 3% and 4%) based on example 1A-1, and the addition proportions (weight ratio) are shown in Table 4.
TABLE 4
Figure BDA0004048227540000091
The preparation method is the same as example 1.
The emulsion was observed by a microscope equipped with a polarizer after cooling, and the results and comparison with A-1 in example 1 are shown in FIGS. 4-6. From FIG. 4, it can be seen that the A-4, A-5 and A-6 samples in which cetearyl alcohol was added at a content of 2.00%, 3.00% and 4.00% each showed larger particle formation than CONTROL, and the liquid crystal particle formation was also clearer and more constant. As can be seen from FIG. 5, the A-7, A-8, and A-9 samples, in which cetyl alcohol was added at a content of 2.00%, 3.00%, and 4.00%, were all seen to have larger particles than the control group, and the liquid crystal particle formation was also clearer and more constant. As can be seen from FIG. 6, the samples A-10, A-11, and A-12, in which behenyl alcohol was added at 2.00%, 3.00%, and 4.00%, all showed larger particles than the control, and the liquid crystal particle formation was more clear and constant.
In summary, A-4, A-5, A-6, A-7, A-8, A-9, A-10, A-11, and A-12 all had good liquid crystal particle formation, with the longer the chain of the hydrophobic group of the higher alcohol, the larger the particle size formation.
Example 5
In this example, higher alcohols (cetearyl alcohol, cetyl alcohol and behenyl alcohol) were added in different proportions (2%, 3% and 4%) on the basis of examples 1A-2, and the addition proportions (weight ratio) are shown in table 5.
TABLE 5
Figure BDA0004048227540000101
The preparation method is the same as example 1.
The emulsion was observed by a microscope equipped with a polarizer after cooling, and the results and comparison with A-2 in example 1 are shown in FIGS. 7-9, and it can be seen from FIG. 7 that the samples A-13, A-14 and A-15 in which cetearyl alcohol was added at a content of 2.00%, 3.00% and 4.00% each had larger particles than the control group and the liquid crystal particle formation was more distinct and constant. As can be seen from FIG. 8, the samples A-16, A-17, and A-18, in which cetyl alcohol was added at levels of 2.00%, 3.00%, and 4.00%, all showed larger particle formation than the CONTROL, and the liquid crystal particle formation was also clearer and more constant. As can be seen in FIG. 9, the A-18, A-20, A-21 samples, to which behenyl alcohol was added at levels of 2.00%, 3.00%, 4.00%, all were seen to have larger grain formation than CONTROL, and the liquid crystal grain formation was also more distinct and constant.
In summary, A-13, A-14, A-15, A-16, A-17, A-18, A-19, A-20, and A-21 all had good liquid crystal particle formation, with the longer the chain of the hydrophobic group of the higher alcohol, the larger the particle size formation.
Example 6
This example added different proportions (2%, 3% and 4%) of higher alcohols (cetearyl alcohol, cetyl alcohol and behenyl alcohol) as shown in Table 6, based on B-1 and B-2 in example 2 and C-1 and C-2 in example 3, respectively.
TABLE 6
Figure BDA0004048227540000111
/>
Wherein the preparation methods of B-4, B-5, B-6 and B-7 are the same as example 2; the preparation of C-4, C-5, C-6 and C-7 was carried out as in example 3.
The emulsion was observed by a microscope equipped with a polarizer after cooling, and the results are shown in FIGS. 10 and 11, and it can be seen from FIG. 10 that the B-4, B-5, B-6, B-7 samples prepared by using higher alcohols (cetearyl alcohol, cetyl alcohol) at a content of 4.00% formed liquid crystals well in the B-1, B-2 samples using olive oil, caprylic/capric triglyceride using sucrose series ARLAEL 21211-FL- (MV) emulsifier, although liquid crystals were not formed. As can be seen from FIG. 11, the C-1, C-2 sample using olive oil and caprylic/capric triglyceride using the polyglycerol ester series POLYAQUOL-2W emulsifier formed liquid crystals, but the C-4, C-5, C-6, C-7 sample manufactured at a content of 4.00% of higher alcohols (cetearyl alcohol, cetyl alcohol) formed more excellently. The longer the hydrophobic group in the higher alcohol, the longer the carbon chain length surrounding the oil particles, and it was judged that it could affect the particle size and the formation of liquid crystal. In addition, higher alcohols with higher melting points are more favorable for the formation of stable liquid crystals.
Example 7
This example judges whether or not a liquid crystal is formed by adding a higher alcohol to an emulsion system of polysorbate-60 and sorbitol consisting of 20 moles of ethylene oxide (C2H 3O) and sorbitan fatty acid ester-sorbitan stearate obtained by reacting sorbitan with stearic acid. The ratio is shown in Table 7.
TABLE 7
Figure BDA0004048227540000121
The preparation method is the same as that of example 2.
The emulsion obtained was observed by cooling it with a microscope equipped with a polarizer, and the results are shown in FIG. 12, using a TWEEN 60V 15.0%/SPAN 60-PW- (AP) 5.00% emulsification system, olive oil, caprylic/capric triglyceride, cetearyl alcohol 4.00%, and the emulsified particles and liquid crystal formation of each sample were observed immediately after the manufacture, and the results show that the formation of D-4 sample of cetearyl alcohol on the liquid crystal particles was also clearer and more constant using caprylic/capric triglyceride. Although olive oil has high polarity and contains hydrophobic groups such as oleic acid, palmitic acid, linoleic acid and the like, which may affect the formation of liquid crystals, caprylic acid with 8 carbon atoms and capric acid with 10 carbon atoms are combined with 3 glycerides, and the hydrophobic groups have 3 chains, which is more effective for the formation of liquid crystals, compared to the caprylic/capric triglyceride structure.
In summary, the novel liquid crystal emulsion, the preparation method and the application thereof provided by the embodiments of the present application have the following advantages:
1. the novel liquid crystal emulsion is mainly prepared from fatty acid and polyglycerol ester emulsifiers and polar grease (olive oil, caprylic/capric triglyceride), wherein the polar grease can participate in the formation of liquid crystal in the emulsifiers, and higher alcohols (cetearyl alcohol, cetyl alcohol and behenyl alcohol) are added on the basis, so that liquid crystal particles can be clearer, and in a certain range, the particle size is increased along with the increase of the content of the higher alcohols.
2. The sucrose emulsifier in the application is not easy to form liquid crystal when being mixed with polar grease (olive oil, caprylic/capric triglyceride), but higher alcohols (cetearyl alcohol, cetyl alcohol and behenyl alcohol) are added into the system, so that the sample liquid crystal formation is excellent, and the higher alcohols are helpful for the formation of liquid crystal in the sucrose emulsifier series.
The embodiments described above are some, but not all embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

Claims (10)

1. The novel liquid crystal emulsion is characterized by comprising the following raw materials in percentage by weight: 10-20% of emulsifier, 5-10% of polar grease and the balance of water;
the emulsifier comprises a fatty acid emulsifier or a polyglycerol ester emulsifier;
the polar oil comprises one or more of olive oil, caprylic/capric triglyceride, squalane and polydimethylsiloxane.
2. A novel liquid crystal emulsion according to claim 1 wherein said emulsifier fatty acid emulsifier comprises cetearyl alcohol.
3. The novel liquid crystal emulsion according to claim 1, wherein said polyglycerol-based emulsifier comprises at least one of polysorbate-60 and polyglycerol-2 stearate.
4. The novel liquid crystal emulsion according to claim 1, wherein the emulsifier further comprises a sucrose emulsifier, and when the emulsifier is a sucrose emulsifier, the raw material further comprises 2-5% of a stabilizer.
5. The novel liquid crystal emulsion according to claim 4, wherein the sucrose-based emulsifier comprises sorbitan stearate and the stabilizer is a higher alcohol.
6. A novel liquid crystal emulsion according to claim 5, characterized in that said higher alcohol is one or more of cetearyl alcohol, cetyl alcohol and behenyl alcohol.
7. A method for preparing a novel liquid crystal emulsion according to any one of claims 1 to 6, characterized in that it comprises the following steps:
respectively heating the oil phase and the water phase in the raw materials to 75-85 ℃, continuously stirring the water phase, adding the oil phase raw materials while stirring, continuously stirring, and cooling to obtain the novel liquid crystal emulsion.
8. The method for preparing a novel liquid crystal emulsion according to claim 7, wherein the stirring speed is 1500-3000rpm, the stirring time is 10-20min, and the temperature after cooling is 28-35 ℃.
9. Use of a novel liquid-crystalline emulsion as claimed in any of claims 1 to 6 for the preparation of cosmetics.
10. The use of the novel liquid crystal emulsion according to claim 9 for the preparation of cosmetics comprising one or more of face toilet, face pack, lotion, milky lotion, cream and essence, wherein the novel liquid crystal emulsion is added in an amount of 0.1-4%.
CN202310033401.6A 2023-01-10 2023-01-10 Novel liquid crystal emulsion and preparation method and application thereof Pending CN115969709A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109431866A (en) * 2018-11-28 2019-03-08 澳宝化妆品(惠州)有限公司 A kind of skin care compositions of the system containing liquid crystal and preparation method thereof
CN109528503A (en) * 2018-12-29 2019-03-29 花安堂生物科技集团有限公司 A kind of emulsifier combination and the preparation method and application thereof forming liquid crystal structure
CN110123655A (en) * 2015-03-31 2019-08-16 爱茉莉太平洋股份有限公司 The cosmetic composition of multiple emulsion dosage form with layered liquid crystal structure
CN113616556A (en) * 2020-05-08 2021-11-09 (株)伊思韩佛 Cosmetic composition with ferroelectric and piezoelectric properties
CN113730288A (en) * 2021-08-13 2021-12-03 广州暨大美塑生物科技有限公司 Liquid crystal composition and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110123655A (en) * 2015-03-31 2019-08-16 爱茉莉太平洋股份有限公司 The cosmetic composition of multiple emulsion dosage form with layered liquid crystal structure
CN109431866A (en) * 2018-11-28 2019-03-08 澳宝化妆品(惠州)有限公司 A kind of skin care compositions of the system containing liquid crystal and preparation method thereof
CN109528503A (en) * 2018-12-29 2019-03-29 花安堂生物科技集团有限公司 A kind of emulsifier combination and the preparation method and application thereof forming liquid crystal structure
CN113616556A (en) * 2020-05-08 2021-11-09 (株)伊思韩佛 Cosmetic composition with ferroelectric and piezoelectric properties
CN113730288A (en) * 2021-08-13 2021-12-03 广州暨大美塑生物科技有限公司 Liquid crystal composition and preparation method and application thereof

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