SOLID COMPOSITE STABILIZER FOR PERCHLOROETHYLENE (PCE) AND PREPARATION METHOD

Abstract

The solid composite stabilizer for PCE includes the following components in parts by weight: 10 to 30 parts of a phenol-substituted ion-exchange resin, 50 to 80 parts of a basic anion-exchange resin, and 50 to 100 parts of a desiccating agent. The phenol-substituted ion-exchange resin is chloromethylated macroporous polystyrene-divinylbenzene (PS-DVB) substituted by a phenolic compound; and the basic anion-exchange resin is chloromethylated macroporous PS-DVB substituted by an amine compound. The preparation method includes the following step: thoroughly mixing the phenol-substituted ion-exchange resin, the basic anion-exchange resin, and the desiccating agent in a specified ratio to obtain the solid composite stabilizer for PCE. The solid composite stabilizer for PCE is packaged in a glass fiber bag and placed in PCE for storage and use.

Claims

1. A solid composite stabilizer for perchloroethylene (PCE), comprising the following components in parts by weight: 10 to 30 parts of a phenol-substituted ion-exchange resin, 50 to 80 parts of a basic anion-exchange resin, and 50 to 100 parts of a desiccating agent.

2. The solid composite stabilizer for PCE according to claim 1, wherein the phenol-substituted ion-exchange resin is a first substitution product from a reaction of a phenolic compound with chloromethylated macroporous polystyrene-divinylbenzene (PS-DVB); and the chloromethylated macroporous PS-DVB has a benzyl chloride content of 12 wt % to 15 wt %.

3. The solid composite stabilizer for PCE according to claim 2, wherein the first substitution product is obtained by washing with water, methanol, and absolute methanol and drying, and the first substitution product has a moisture content of ≤50 ppm and methanol residues are not detected in the first substitution product.

4. The solid composite stabilizer for PCE according to claim 2, wherein the phenolic compound is a hydroquinone monosodium salt.

5. The solid composite stabilizer for PCE according to claim 1, wherein the basic anion-exchange resin is a second substitution product from a reaction of an amine compound with chloromethylated macroporous PS-DVB; and the chloromethylated macroporous PS-DVB has a benzyl chloride content of 12 wt % to 15 wt %.

6. The solid composite stabilizer for PCE according to claim 5, wherein the second substitution product is obtained by washing with water, methanol, and absolute methanol and drying, and the second substitution product has a moisture content of ≤50 ppm and methanol residues are not detected in the second substitution product.

7. The solid composite stabilizer for PCE according to claim 5, wherein the amine compound is ethylenediamine (EDA).

8. The solid composite stabilizer for PCE according to claim 1, wherein the desiccating agent is a 4A molecular sieve.

9. A preparation method of the solid composite stabilizer for PCE according to claim 1, comprising the following step: thoroughly mixing the phenol-substituted ion-exchange resin, the basic anion-exchange resin, and the desiccating agent in a specified ratio to obtain the solid composite stabilizer, wherein the solid composite stabilizer is packaged in a glass fiber bag and placed in PCE for storage and use.

10. The preparation method according to claim 9, wherein the solid composite stabilizer used in the PCE has an amount of 0.5 wt % to 1.0 wt %.

11. The preparation method according to claim 9, wherein the phenol-substituted ion-exchange resin is a first substitution product from a reaction of a phenolic compound with chloromethylated macroporous polystyrene-divinylbenzene (PS-DVB); and the chloromethylated macroporous PS-DVB has a benzyl chloride content of 12 wt % to 15 wt %.

12. The preparation method according to claim 11, wherein the first substitution product is obtained by washing with water, methanol, and absolute methanol and drying, and the first substitution product has a moisture content of ≤50 ppm and methanol residues are not detected in the first substitution product.

13. The preparation method according to claim 11, wherein the phenolic compound is a hydroquinone monosodium salt.

14. The preparation method according to claim 9, wherein the basic anion-exchange resin is a second substitution product from a reaction of an amine compound with chloromethylated macroporous PS-DVB; and the chloromethylated macroporous PS-DVB has a benzyl chloride content of 12 wt % to 15 wt %.

15. The preparation method according to claim 14, wherein the second substitution product is obtained by washing with water, methanol, and absolute methanol and drying, and the second substitution product has a moisture content of ≤50 ppm and methanol residues are not detected in the second substitution product.

16. The preparation method according to claim 14, wherein the amine compound is ethylenediamine (EDA).

17. The preparation method according to claim 9, wherein the desiccating agent is a 4A molecular sieve.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG. 1 shows a synthesis route of a first substitution product from a reaction of a hydroquinone monosodium salt with chloromethylated macroporous PS-DVB.

[0025] FIG. 2 shows a synthesis route of a second substitution product from a reaction of EDA with chloromethylated macroporous PS-DVB.

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0026] The technical solutions in the examples of the present disclosure are clearly and completely described below with reference to the examples of the present disclosure. Apparently, the described examples are merely some rather than all of the examples of the present disclosure. The following description of at least one exemplary example is merely illustrative, and not intended to limit the present disclosure and application or use thereof in any way. All other examples obtained by a person of ordinary skill in the art based on the examples of the present disclosure without creative efforts shall fall within the protection scope of the present disclosure.

[0027] Unless otherwise specified, the numerical values set forth in these examples do not limit the scope of the present disclosure. The techniques and methods known to those of ordinary skill in the relevant arts may not be discussed in detail, but where appropriate, the techniques and methods should be regarded as part of the description. In all examples shown and discussed herein, any specific value should be interpreted as merely exemplary, rather than restrictive. Therefore, other examples of the exemplary examples may have different values.

[0028] In addition, it should be noted that the use of the terms “first” and “second” to define a substitution product is merely for the convenience of distinguishing and naming the substitution products obtained from a reaction of chloromethylated macroporous PS-DVB with a phenolic compound and a reaction of chloromethylated macroporous PS-DVB with an amine compound. The first substitution product is obtained from the reaction of chloromethylated macroporous PS-DVB with a phenolic compound, and the second substitution product is obtained from the reaction of chloromethylated macroporous PS-DVB with an amine compound. Unless otherwise stated, the above-mentioned terms “first” and “second” have no special meaning and thus cannot be understood as limiting the protection scope of the present disclosure.

[0029] The macroporous PS-DVB used in the following examples is an ion-exchange resin intermediate chloromethylated bead produced by Shanghai Resin Factory (chloromethylated macroporous PS-DVB), which has a benzyl chloride content of 12 wt % to 15 wt % and a particle size of 60 to 100 mesh.

[0030] In the following examples, 6 m, 9 m, and 18 m in Tables 1, 2, and 3 represent 6 months, 9 months, and 18 months, respectively; and a blank indicates PCE without the solid composite stabilizer of the present disclosure.

EXAMPLE 1

[0031] A solid composite stabilizer for PCE was provided, including the following components in parts by weight: 10 parts of a phenol-substituted ion-exchange resin, 80 parts of a basic anion-exchange resin, and 50 parts of a 4A molecular sieve.

[0032] The phenol-substituted ion-exchange resin was a first substitution product of a reaction of a hydroquinone monosodium salt with chloromethylated macroporous PS-DVB, and this reaction was a substitution reaction conducted according to the synthesis route shown in FIG. 1. A specific preparation method refers to the synthesis method of “Wang Resin” in “Encyclopedia of Reagents for Organic Synthesis” (author: Paquette, Leo A.). The first substitution product obtained was called 4-hydroxyphenol resin (HP) for short. The first substitution product was washed with water, methanol, and absolute methanol and then vacuum-dried, such that the first substitution product had a moisture content of ≤50 ppm and an undetectable methanol residue.

[0033] The basic anion-exchange resin was a second substitution product of a reaction of EDA with chloromethylated macroporous PS-DVB, and this reaction was a substitution reaction conducted according to the synthesis route shown in FIG. 2. A specific preparation method refers to the “Amination Reaction” in “Preparation and Properties of Macroporous Anion-Exchange Resin” (Su Yuqin, Zhang Zuoguang, “Journal of Beijing University of Aeronautics and Astronautics”, 2003, Volume 29 (6): 493-496). The second substitution product obtained was called EDA resin (EAP) for short. The second substitution product was washed with water, methanol, and absolute methanol and then vacuum-dried, such that the second substitution product had a moisture content of ≤50 ppm and an undetectable methanol residue.

[0034] A preparation method of the above solid composite stabilizer for PCE included the following step: the above-mentioned phenol-substituted ion-exchange resin (the first substitution product), the basic anion-exchange resin (the second substitution product), and the 4A molecular sieve were thoroughly mixed in a specified ratio to obtain the solid composite stabilizer for PCE. The solid composite stabilizer for PCE was packaged in a glass fiber bag and placed in PCE for storage and use.

[0035] Usage: 500 mL (about 815 g) of fresh environmentally-friendly PCE was taken and placed in a brown bottle, 4.1 g (0.50 wt %) of the solid composite stabilizer was added, and then the brown bottle was sealed and packaged.

[0036] Results of the quality assurance experiment were shown in Table 1.

TABLE-US-00001 TABLE 1 Test results of the solid composite stabilizer of Example 1 Example 1 Standards for environmentally-friendly Test results of the solid composite stabilizer (measured) PCE HJ637-2018 (Ministry of After After Environmental Protection) Blank Blank stabilization stabilization Test item Test standard Blank (6 m) (9 m) (6 m) (18 m) Content, % ≥ 99.5 99.9 99.9 99.9 99.9 99.9 Moisture (H.sub.2O), % ≤ 0.05 0.04 0.04 0.04 0.03 0.03 Density (20° C.), g/cm.sup.3 1.63 Qualified Qualified Qualified Qualified Qualified Refractive index, % 1.5 Qualified Qualified Qualified Qualified Qualified Outer packaging 500 mL/4 L Absorbance (IR, with a 4 mm empty cuvette as reference), nm 2,930 cm.sup.−1 0.34 0.28 0.31 0.35 0.28 0.28 2,960 cm.sup.−1 0.07 0.04 0.05 0.08 0.04 0.05 3,030 cm.sup.−1 0.00 0.00 0.00 0.01 0.00 0.00

EXAMPLE 2

[0037] A solid composite stabilizer for PCE was provided, including the following components in parts by weight: 30 parts of a phenol-substituted ion-exchange resin, 50 parts of a basic anion-exchange resin, and 100 parts of a 4A molecular sieve.

[0038] The phenol-substituted ion-exchange resin was a first substitution product of a reaction of a hydroquinone monosodium salt with chloromethylated macroporous PS-DVB, and this reaction was a substitution reaction conducted according to the synthesis route shown in FIG. 1. A specific preparation method refers to the synthesis method of “Wang Resin” in “Encyclopedia of Reagents for Organic Synthesis” (author: Paquette, Leo A.). The first substitution product obtained was called 4-hydroxyphenol resin (HP) for short. The first substitution product was washed with water, methanol, and absolute methanol and then vacuum-dried, such that the first substitution product had a moisture content of ≤50 ppm and an undetectable methanol residue.

[0039] The basic anion-exchange resin was a second substitution product of a reaction of EDA with chloromethylated macroporous PS-DVB, and this reaction was a substitution reaction conducted according to the synthesis route shown in FIG. 2. A specific preparation method refers to the “Amination Reaction” in “Preparation and Properties of Macroporous Anion-Exchange Resin” (Su Yuqin, Zhang Zuoguang, “Journal of Beijing University of Aeronautics and Astronautics”, 2003, Volume 29 (6): 493-496). The second substitution product obtained was called EDA resin (EAP) for short. The second substitution product was washed with water, methanol, and absolute methanol and then vacuum-dried, such that the second substitution product had a moisture content of ≤50 ppm and an undetectable methanol residue.

[0040] A preparation method of the above solid composite stabilizer for PCE included the following step: the above-mentioned phenol-substituted ion-exchange resin, the basic anion-exchange resin, and a desiccating agent were thoroughly mixed in a specified ratio to obtain the solid composite stabilizer for PCE. The solid composite stabilizer for PCE was packaged in a glass fiber bag and placed in PCE for storage and use.

[0041] Usage: 500 mL (about 815 g) of fresh environmentally-friendly PCE was taken and placed in a brown bottle, 8.2 g (1.0 wt %) of the solid composite stabilizer was added, and then the brown bottle was sealed and packaged.

[0042] Results of the quality assurance experiment were shown in Table 2.

TABLE-US-00002 TABLE 2 Test results of the solid composite stabilizer of Example 2 Standards for environmentally-friendly Example 2 PCE HJ637-2018 (Ministry of Test results of the solid composite stabilizer (measured) Environmental Protection) Blank Blank Stabilization Stabilization Test item Test standard Blank (6 m) (9 m) (6 m) (18 m) Content, % ≥ 99.5 99.9 99.9 99.9 99.9 99.9 Moisture (H.sub.2O), % ≤ 0.05 0.04 0.04 0.04 0.02 0.02 Density (20° C.), g/cm.sup.3 1.63 Qualified Qualified Qualified Qualified Qualified Refractive index, % 1.5 Qualified Qualified Qualified Qualified Qualified Outer packaging 500 mL/4 L Absorbance (IR, with a 4 mm empty cuvette as reference), nm 2,930 cm.sup.−1 0.34 0.28 0.31 0.35 0.27 0.28 2,960 cm.sup.−1 0.07 0.04 0.05 0.08 0.04 0.04 3,030 cm.sup.−1 0.00 0.00 0.00 0.01 0.00 0.00

EXAMPLE 3

[0043] A solid composite stabilizer for PCE was provided, including the following components in parts by weight: 20 parts of a phenol-substituted ion-exchange resin, 65 parts of a basic anion-exchange resin, and 70 parts of a 4A molecular sieve.

[0044] The phenol-substituted ion-exchange resin was a first substitution product of a reaction of a hydroquinone monosodium salt with chloromethylated macroporous PS-DVB, and this reaction was a substitution reaction conducted according to the synthesis route shown in FIG. 1. A specific preparation method refers to the synthesis method of “Wang Resin” in “Encyclopedia of Reagents for Organic Synthesis” (author: Paquette, Leo A.). The first substitution product obtained was called 4-hydroxyphenol resin (HP) for short. The first substitution product was washed with water, methanol, and absolute methanol and then vacuum-dried, such that the first substitution product had a moisture content of ≤50 ppm and an undetectable methanol residue.

[0045] The basic anion-exchange resin was a second substitution product of a reaction of EDA with chloromethylated macroporous PS-DVB, and this reaction was a substitution reaction conducted according to the synthesis route shown in FIG. 2. A specific preparation method refers to the “Amination Reaction” in “Preparation and Properties of Macroporous Anion-Exchange Resin” (Su Yuqin, Zhang Zuoguang, “Journal of Beijing University of Aeronautics and Astronautics”, 2003, Volume 29 (6): 493-496). The second substitution product obtained was called EDA resin (EAP) for short. The second substitution product was washed with water, methanol, and absolute methanol and then vacuum-dried, such that the second substitution product had a moisture content of ≤50 ppm and an undetectable methanol residue.

[0046] A preparation method of the above solid composite stabilizer for PCE included the following step: the above-mentioned phenol-substituted ion-exchange resin, the basic anion-exchange resin, and a desiccating agent were thoroughly mixed in a specified ratio to obtain the solid composite stabilizer for PCE. The solid composite stabilizer for PCE was packaged in a glass fiber bag and placed in PCE for storage and use.

[0047] Usage: 500 mL (about 815 g) of fresh environmentally-friendly PCE was taken and placed in a brown bottle, 6.4 g (0.75 wt %) of the solid composite stabilizer was added, and then the brown bottle was sealed and packaged.

[0048] Results of the quality assurance experiment were shown in Table 3.

TABLE-US-00003 TABLE 3 Test results of the solid composite stabilizer of Example 3 Standards for environmentally-friendly Example 3 PCE HJ637-2018 (Ministry of Test results of the stabilizer (measured) Environmental Protection) Blank Blank Stabilization Stabilization Test item Test standard Blank (6 m) (9 m) (6 m) (18 m) Content, % ≥ 99.5 99.9 99.9 99.9 99.9 99.9 Moisture (H.sub.2O), % ≤ 0.05 0.04 0.04 0.04 0.02 0.03 Density (20° C.), g/cm.sup.3 1.63 Qualified Qualified Qualified Qualified Qualified Refractive index, % 1.5 Qualified Qualified Qualified Qualified Qualified Outer packaging 500 ml/4 L Absorbance (IR, with a 4 mm empty cuvette as reference), nm 2,930 cm.sup.−1 0.34 0.28 0.31 0.35 0.27 0.29 2,960 cm.sup.−1 0.07 0.04 0.05 0.08 0.04 0.04 3,030 cm.sup.−1 0.00 0.00 0.00 0.01 0.00 0.00

[0049] It can be seen from the above Tables 1, 2, and 3 that, on month 9, the IR absorbance indexes of the blank sample (9 m) without the solid composite stabilizer of the present disclosure at 2,930 cm.sup.−1, 2,960 cm.sup.−1, and 3,030 cm.sup.−1 were higher than the test standards, indicating that the PCE had deteriorated on month 9; after 0.50 wt % to 1 wt % of the solid composite stabilizer of the present disclosure was added to PCE for stabilization, the IR absorbance indexes of the PCE (18 m) at 2,930 cm.sup.−1, 2,960 cm.sup.−1, and 3,030 cm.sup.−1 were all lower than the test standards, indicating that the solid composite stabilizer of the present disclosure exhibited a prominent stabilization effect for PCE, which lasted for 18 months; and the addition of the solid composite stabilizer of the present disclosure did not affect the density of PCE, and during the stabilization process, the solid composite stabilizer of the present disclosure floated in the PCE liquid.

[0050] The foregoing description only provides preferred specific implementations of the present disclosure, and the protection scope of the present disclosure is not limited thereto. Any equivalent replacement or modification made according to the technical solution and inventive concept by a person skilled in the art within a technical scope of the present disclosure shall fall within the protection scope of the present disclosure.