TW202210418A - Method for treating liquid to be treated containing artificial musk - Google Patents

Abstract

A method for treating liquid to be treated containing artificial musk comprises: providing an adsorption member, which comprises a magnetic carrier and an adsorption layer attached to the magnetic carrier, the magnetic carrier has a magnetic stirrer and a metal mesh covering the magnetic stirrer, and the adsorption layer is selected from the polyionic liquid having the structure of formula I; and the adsorption member is placed in the liquid to be treated and then magnetically stirred, so that the artificial musk in the liquid to be treated is adsorbed by the adsorption member. The formula I is as follows, where R represents a C1 to C8 alkyl group, A- represents NTf2- or PF6-, and n represents the number of polymerized monomers ranging from 40 to 400. The method for treating the liquid to be treated containing artificial musk can effectively and simply extract the artificial musk from the liquid to be treated.

Description

Method for treating liquid to be treated containing artificial musk

The present invention relates to a treatment method, in particular to a treatment method for a liquid to be treated containing artificial musk.

As a fragrance additive, artificial musk is widely added to scented consumer products, such as cosmetics, household products and cleaning products. According to different chemical structures, artificial musks are mainly divided into three categories: aromatic nitro musks, polycyclic musks and macrocyclic musks. The extraction cost of macrocyclic musk is extremely high, and nitro musk is gradually banned or regulated due to its toxicity, so polycyclic musk is currently the main artificial musk used.

However, recent studies have shown that polycyclic musks are carcinogenic and estrogen-like. In addition, artificial musks often enter the environment with wastewater, and polycyclic musks and their metabolites are not easily biodegraded or removed in sewage treatment plants. , thus easily endangering the environment and ecology.

In view of the above, in order to avoid the environmental hazards caused by artificial musk, it is necessary to develop a method for treating artificial musk in water samples.

Therefore, the object of the present invention is to provide a method for treating the liquid to be treated containing artificial musk.

，R表示C₁ 至C₈ 的烷基，A^- 表示NTf₂ ^- 或PF₆ ^- ，n表示範圍為40至400的聚合單體數目。Therefore, the method for treating the liquid to be treated containing artificial musk of the present invention includes the following steps: (a) providing an adsorption member, which includes a magnetic carrier and an adsorption layer attached to the magnetic carrier, and the magnetic carrier has a magnetic Stirrer and a metal mesh covering the magnetic stirrer, the adsorption layer is selected from the polyionic liquid having the structure of formula I; and (b) magnetic stirring is performed after placing the adsorption member in a liquid to be treated, So that the artificial musk in the liquid to be treated is adsorbed by the adsorbent; wherein, the formula I is as follows, [Formula I]

, R represents a C ₁ to C ₈ alkyl group, A ^- represents NTf ₂ ^- or PF ₆ ^- , and n represents the number of polymerized monomers ranging from 40 to 400.

The effect of the present invention is that the method for treating the liquid to be treated containing artificial musk of the present invention can effectively and simply extract artificial musk from the liquid to be treated by using the adsorbent including the polyionic liquid.

In this article, the "synthetic musk" generally refers to musk compounds prepared by artificial synthesis, such as but not limited to aromatic nitro musks, polycyclic musk compounds, Macrocyclic musk compounds, etc. In one embodiment of the present invention, the artificial musk is selected from the group consisting of cashmidone, sali musk, powder sandalwood musk, trasmus musk, gallot musk, tona musk, xylene musk and ketone musk Group.

The method for treating the liquid to be treated containing artificial musk of the present invention comprises the following steps: placing an adsorbent in a liquid to be treated and then performing magnetic stirring, so that the artificial musk in the liquid to be treated is adsorbed by the adsorbent. In order to further know the type and content of the artificial musk in the liquid to be treated, the method for treating the liquid to be treated containing the artificial musk also comprises the following steps: after the artificial musk is removed from the adsorbent, gas chromatography-mass spectrometry is carried out. After analysis, the gas chromatography-mass spectrum of the artificial musk was obtained.

Wherein, the adsorption member includes a magnetic carrier and an adsorption layer attached to the magnetic carrier, the magnetic carrier has a magnetic stirrer and a metal mesh covering the magnetic stirrer, and the adsorption layer is selected from the group having a formula I-structured polyionic liquid.

式I 中，R表示C₁ 至C₈ 的烷基；較佳地，該R為C₈ 的烷基。在本發明的一實施例中，該R為C₈ 的直鏈烷基。 該A^- 表示帶負電的基團。在本發明的一實施例中，該A^- 為NTf₂ ^- 或PF₆ ^- 。 n表示範圍為40至400的聚合單體數目。The formula I is as follows: [Formula I]

In formula I, R represents a C ₁ to C ₈ alkyl group; preferably, the R is a C ₈ alkyl group. In one embodiment of the present invention, the R is a C ₈ straight-chain alkyl group. The A ^- represents a negatively charged group. In an embodiment of the present invention, the A ^- is NTf ₂ ^- or PF ₆ ^- . n represents the number of polymerized monomers ranging from 40 to 400.

The material of the metal mesh is not particularly limited. In an embodiment of the present invention, the metal mesh is made of stainless steel.

A specific way to desorb the artificial musk from the adsorbent is, for example, but not limited to, thermal desorption.

The present invention will be further described with respect to the following examples, but it should be understood that the examples are only used for illustration and should not be construed as a limitation of the implementation of the present invention.

[Preparation example] Standard solution of artificial musk (1). Dissolve 2 mg of cashmeran [Cashmeran ^® , DPMI for short, purchased from Toronto Research Chemicals (TRC)] with a small amount of isopropanol and pour it into a 2 mL quantitative bottle. Then use isopropanol to quantify to the scale line of the quantitative bottle, and prepare a standard solution with a concentration of 1000 μg/mL. Then take 200 µL of the standard solution with a concentration of 1000 μg/mL and add it to another 2 mL quantitative bottle, and quantify it with isopropanol to the scale line of the quantitative bottle, that is, prepare a standard with a concentration of 100 μg/mL. solution. And using the same method as above, Celestolide (Celestolide ^® , referred to as ADBI, purchased from TRC), powder sandalwood musk (Phantolide ^® , referred to as AHMI, purchased from TRC), Traseolide ® (Traseolide ^® , referred to as ATII, purchased from TRC), Galaxolide (HHCB for short, purchased from TRC), Tonalide ^{® (} AHTN for short, purchased from TRC), musk xylene (MX for short, purchased from Sigma-Aldrich) and ketone musk (musk ketone for short, MK, purchased from Sigma-Aldrich), respectively prepared into standard solutions with a concentration of 100 μg/mL. (2). Take 100 µL of each of the above standard solutions of DPMI, ADBI, AHMI, ATII, HHCB, AHTN, MX and MK with a concentration of 100 μg/mL and add them to a 1 mL quantitative bottle. The alcohol was quantified to the scale line of the quantitative bottle, that is, the standard solution of artificial musk with a concentration of 10 μg/mL was prepared. Among them, the main ion fragments and qualitative ion fragments of each artificial musk analyzed by gas chromatography-mass spectrometer (brand Agilent Technologies, model 7890A GC/5975C MSD) are shown in Table 1 below.

Table 1 artificial musk Residence time (RT) (unit: minutes) Major ion fragment (amu) Qualitative Ion Fragments (amu) DPMI 12.39 191 206 135 ADBI 14.77 229 244 173 AHMI 15.48 229 244 187 HHCB 15.98 243 213 258 ATII 16.31 215 173 258 AHTN 16.55 243 258 159 MX 16.81 282 297 265 MK 18.39 279 294 280

(1). 將1當量的1-乙烯基咪唑(1-vinylimidazole)及1.5當量的1-溴辛烷(1-bromooctane)用乙酸乙酯(EA)溶解後，在溫度60℃至70℃下反應48小時，反應結束後利用乙酸乙酯清洗產物3至4次以將未反應的1-乙烯基咪唑及1-溴辛烷洗掉，之後進行減壓濃縮移除乙酸乙酯，得到化合物A。該化合物A的¹ H NMR圖譜如圖1所示。 (2). 將1.1當量的KPF₆ 以二次水溶解後，逐滴加到該化合物A中並進行離子交換反應4小時，反應結束後利用二次水清洗產物3至4次以將未反應的KPF₆ 洗掉，之後進行減壓濃縮移除二次水，得到化合物B。該化合物B的¹ H NMR圖譜如圖2所示。 (3).將1當量的化合物B及0.1當量的偶氮二異丁腈(AIBN)以氯仿(CHCl₃ )溶解後，在氮氣環境且溫度60℃至70℃下進行聚合反應48小時，反應結束後將產物進行減壓濃縮，即得到式I-1所示的聚離子液體(式I-1中，n＝40~400)。該式I-1所示的聚離子液體的¹ H NMR圖譜如圖3所示。[Synthesis Example 1] Polyionic liquid

(1). After dissolving 1 equivalent of 1-vinylimidazole (1-vinylimidazole) and 1.5 equivalents of 1-bromooctane (1-bromooctane) in ethyl acetate (EA), at a temperature of 60°C to 70°C The reaction was performed for 48 hours. After the reaction, the product was washed with ethyl acetate 3 to 4 times to wash off the unreacted 1-vinylimidazole and 1-bromooctane, and then concentrated under reduced pressure to remove ethyl acetate to obtain compound A. . The ¹ H NMR spectrum of this compound A is shown in FIG. 1 . (2). After dissolving 1.1 equivalents of KPF ₆ in secondary water, dropwise added to the compound A and subjected to ion exchange reaction for 4 hours. After the reaction, the product was washed with secondary water 3 to 4 times to remove the unreacted The KPF ₆ was washed off, and then concentrated under reduced pressure to remove secondary water to obtain compound B. The ¹ H NMR spectrum of this compound B is shown in FIG. 2 . (3). After dissolving 1 equivalent of compound B and 0.1 equivalent of azobisisobutyronitrile (AIBN) in chloroform (CHCl ₃ ), a polymerization reaction was carried out in a nitrogen atmosphere at a temperature of 60°C to 70°C for 48 hours. After the end, the product is concentrated under reduced pressure to obtain the polyionic liquid represented by formula I-1 (in formula I-1, n=40~400). The ¹ H NMR spectrum of the polyionic liquid represented by the formula I-1 is shown in FIG. 3 .

(1). 化合物A的的合成方式是如上所述，於此不再贅述。 (2). 將1當量的LiNTf₂ 以二次水溶解後，逐滴加到該化合物A中並進行離子交換反應4小時，反應結束後利用二次水清洗產物3至4次以將未反應的LiNTf₂ 洗掉，之後進行減壓濃縮移除二次水，得到化合物C。 (3).將1當量的化合物C及0.1當量的偶氮二異丁腈(AIBN)以氯仿(CHCl₃ )溶解後，在氮氣環境且溫度60℃至70℃下進行聚合反應48小時，反應結束後將產物進行減壓濃縮，即得到式I-2所示的聚離子液體(式I-2中，n＝40~400)。該式I-2所示的聚離子液體的¹ H NMR圖譜如圖4所示。[Synthesis Example 2] Polyionic liquid

(1). The synthesis method of compound A is as described above and will not be repeated here. (2). After dissolving 1 equivalent of LiNTf ₂ with secondary water, add dropwise to the compound A and carry out ion exchange reaction for 4 hours. After the reaction is completed, use secondary water to wash the product 3 to 4 times to remove unreacted The LiNTf ₂ was washed off, and then concentrated under reduced pressure to remove secondary water to obtain compound C. (3). After dissolving 1 equivalent of Compound C and 0.1 equivalent of azobisisobutyronitrile (AIBN) in chloroform (CHCl ₃ ), a polymerization reaction was carried out in a nitrogen atmosphere at a temperature of 60°C to 70°C for 48 hours. After the end, the product is concentrated under reduced pressure to obtain the polyionic liquid represented by formula I-2 (in formula I-2, n=40~400). The ¹ H NMR spectrum of the polyionic liquid represented by the formula I-2 is shown in FIG. 4 .

[Example 1] (a). A metal mesh (material is stainless steel, size is 2×2 cm ² ) is coated with a magnetic stirring bar to obtain a magnetic carrier. The magnetic carrier was baked at 300° C. for 60 minutes to ensure that no artificial musk was attached to the magnetic carrier. After the magnetic carrier was cooled, the magnetic carrier was washed with hexane, acetone and methanol in sequence with an ultrasonic cleaner. After 30 minutes, the magnetic carrier was dried. In addition, 0.4996 mg of the polyionic liquid of Synthesis Example 2 was dissolved in 2 mL of acetone to obtain a polyionic liquid mixed solution. Drop 1 mL of the polyionic liquid mixture on the magnetic carrier, and after the acetone is volatilized, an adsorption member is obtained. (b). Provide a sample bottle containing a solution to be treated, which is composed of 8 mL of ultrapure water and 1 μL of a standard solution of artificial musk with a concentration of 10 μg/mL. After placing the adsorbent in the sample bottle, the sample bottle was placed on a magnetic stirring plate (brand GERSTEL) and magnetically stirred at 340 rpm for 30 to 40 minutes, so that the liquid to be treated was immersed in the sample bottle. of artificial musk is adsorbed by the adsorbent. (c). Next, after the adsorbent is taken out from the sample bottle and dried, a thermal desorption unit (TDU for short, brand GERSTEL) is used to remove the artificial musk from the adsorbent After that, the artificial musk was injected into a gas chromatography mass spectrometer (brand Agilent Technologies, model 7890A GC/5975C MSD) using a cooled injection system (CIS for short, brand GERSTEL). The gas chromatography-mass spectrometry chromatogram of the artificial musk of Example 1 was obtained by phase chromatography-mass spectrometry, and the results are shown in Figure 5 and Table 2. Among them, the thermal desorber adopts the split flow mode, the initial temperature is 30 °C and the temperature is maintained for 0.2 minutes, the end temperature is 280 °C and the temperature is maintained for 10 minutes, and the heating rate is 120 °C/min. The initial temperature of the cooling sample introduction system was -30°C and the temperature was maintained for 0.2 minutes, the end temperature was 250°C and the temperature was maintained for 10 minutes, and the heating rate was 6°C/min. In this gas chromatography-mass spectrometer, the carrier gas was helium and the flow rate was 1.8 mL/min; the brand of the GC column was Agilent Technologies, model DB-1701; the initial temperature of the oven was 60 °C and the Warm for 1 minute, then heat up to 190°C at a heating rate of 10°C/min and hold the temperature for 1 minute, then heat up to 220°C at a heating rate of 20°C/min and hold the temperature for 1 minute, and finally heat up at a heating rate of 30°C/min to The temperature was kept at 250°C for 1 minute; the mass spectrometry detection mode was selected ion monitoring (SIM).

[Comparative Example 1]

The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses a magnetic carrier to adsorb the artificial musk in the liquid to be treated, and the structure and preparation method of the magnetic carrier are the same as those described in step (a) of Example 1. are the same, and will not be repeated here. The chromatogram results of the gas chromatography-mass spectrometer of the artificial musk of Comparative Example 1 are shown in FIG. 6 and Table 2.

[Standard example]

After the artificial musk standard solution with a concentration of 10 μg/mL was diluted to a concentration of 10 ng/mL, it was analyzed by gas chromatography-mass spectrometer, and the results of the obtained chromatogram were shown in Figure 7 and Table 2.

Subsequently, the extraction rate of Example 1 and Comparative Example 1 can be calculated according to the ionic strength of the chromatographic peak of the standard example, and the DPMI extraction rate of Example 1 is used as an example to illustrate the calculation method, DPMI extraction rate of Example 1=DPMI of Example 1 The ionic strength ÷ the ionic strength of the standard example of DPMI × 100%.

Table 2 Example 1 Comparative Example 1 Standard example ionic strength DPMI 863033 × 729653 ADBI 700816 131718 970342 AHMI 710803 131179 713426 ATII 895576 286906 910369 HHCB 633470 229854 720550 AHTN 1308080 484595 1436912 MX 130396 × 121995 MK 182195 × 159165 Residence time (min) DPMI 12.39 × 12.39 ADBI 14.77 14.79 14.77 AHMI 15.48 15.43 15.48 ATII 16.31 16.29 15.98 HHCB 15.99 16.04 16.31 AHTN 16.55 16.50 16.55 MX 16.82 × 16.81 MK 18.40 × 18.39 Chromatographic peak area relative standard deviation (%) DPMI 6.92 --- --- ADBI 3.89 --- --- AHMI 0.08 --- --- ATII 5.77 --- --- HHCB 2.12 --- --- AHTN 6.95 --- --- MX 8.90 --- --- MK 6.07 --- --- Extraction rate (%) DPMI 118 × --- ADBI 72 14 --- AHMI 100 18 --- ATII 98 32 --- HHCB 88 32 --- AHTN 91 34 --- MX 107 × --- MK 114 × --- Note: "×" indicates that the chromatographic peak could not be measured; "---" indicates that no measurement was performed; "Relative Standard Deviation (RSD)" is the relative standard deviation of the chromatographic peak area of the chromatographic peak area repeated three times under the same conditions , RSD less than 10% represents good reproducibility.

It can be seen from Fig. 5 (Example 1), Fig. 6() and Table 2 that by using the adsorbent (containing the polyionic liquid of Synthesis Example 2) in Example 1, all 8 kinds of artificial musk in the liquid to be treated have Very high extraction rate. In contrast, in Comparative Example 1, because the magnetic carrier (without ionic liquid) was used, the artificial musk extracted from the liquid to be treated only had ADBI, AHMI, ATII, HHCB and AHTN, and the extraction rate was extremely low. It was proved that in Example 1, artificial musk can be effectively extracted from the liquid to be treated by using the adsorbent including the polyionic liquid.

In addition, from the ionic strength and retention time of Example 1, it is proved that the treatment method of Example 1 can identify the kind of artificial musk. From the relative standard deviation of the chromatographic peak area of Example 1, it is proved that the processing method of Example 1 has high reproducibility.

To sum up, the method for treating the liquid to be treated containing artificial musk of the present invention can effectively extract artificial musk from the liquid to be treated by using the adsorbent including the polyionic liquid, and cooperate with the subsequent gas chromatography- Mass spectrometry analysis can know the type of artificial musk. In addition, the adsorbent used in the method for treating the artificial musk-containing liquid to be treated can be reused, and extraction can be performed only by matching the adsorbent with a magnetic stirring plate. The new treatment method not only requires low equipment, but also does not need to use organic solvents in the extraction process. Therefore, the object of the present invention can indeed be achieved.

However, the above are only examples of the present invention, and should not limit the scope of implementation of the present invention. Any simple equivalent changes and modifications made according to the scope of the patent application of the present invention and the contents of the patent specification are still included in the scope of the present invention. within the scope of the invention patent.

Other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, wherein: Fig. 1 is the ¹ H NMR spectrum of Compound A of Synthesis Example 1 of the present invention; Fig. 2 is the Synthesis Example of the present invention The ¹ H NMR spectrum of compound B of 1; Fig. 3 is the ¹ H NMR spectrum of the polyionic liquid of formula I-1 of synthesis example 1 of the present invention; Fig. 4 is the polyionic liquid of formula I-2 of synthesis example 2 of the present invention Fig. 5 is the chromatogram of the gas chromatography-mass spectrometer of the artificial musk of Example ¹ of the present invention; Fig. 6 is the layer of the gas chromatography-mass spectrometer of the artificial musk of the comparative example 1 and FIG. 7 is the chromatogram of the standard example of artificial musk by gas chromatography-mass spectrometer.

Claims (6)

A method for treating a liquid to be treated containing artificial musk, comprising the following steps: (a) providing an adsorption member comprising a magnetic carrier and an adsorption layer attached to the magnetic carrier, the magnetic carrier having a magnetic stirrer and a metal mesh covering the magnetic stirrer, the adsorption layer is selected from the polyionic liquid having the structure of formula I; and (b) the adsorption member is placed in a liquid to be treated and then magnetically stirred, so that the The artificial musk in the liquid to be treated is adsorbed by the adsorbent; wherein, the formula I is as follows, [Formula I]

, R represents a C ₁ to C ₈ alkyl group, A ^- represents NTf ₂ ^- or PF ₆ ^- , and n represents the number of polymerized monomers ranging from 40 to 400. The method for treating a liquid to be treated containing artificial musk according to claim ₁ , wherein the R is a C8 alkyl group. The method for treating the artificial musk-containing liquid to be treated according to claim 2, wherein the R is a C ₈ straight-chain alkyl group. The method for treating a liquid to be treated containing artificial musk according to claim 1, wherein the artificial musk is selected from the group consisting of cashmidone, sali musk, powder sandalwood musk, truss musk, kale musk, and tona musk , musk xylene and musk ketone. The method for treating a liquid to be treated containing artificial musk according to claim 1, wherein the metal mesh is made of stainless steel. The method for treating a liquid to be treated containing artificial musk as claimed in claim 1, further comprising a step (c) after the step (b): (c) carrying out gas chromatography-mass spectrometry analysis after removing the artificial musk from the adsorbent to obtain a gas chromatography-mass spectrometry spectrum of the artificial musk.

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