Hydrogel-based 3D printing adsorption rectification filler and application thereof in preparation of electronic-grade chemicals

Abstract

The application discloses a kind of preparation of adsorption rectification packing based on hydrogel 3D printing and its application in preparation of electronic grade chemicals.Different from the preparation method of traditional 3D printing hydrogel, the application uses crosslinking agent, photoinitiator, light absorber and solvent without metal ions to prepare 3D printing hydrogel ink, and adopts 3D printing photocuring technology to print and prepare adsorption rectification packing. The prepared adsorption rectification packing is loaded in the rectification tower, and through the coupling of adsorption and rectification process, the trace metal ions in N-methylpyrrolidone (NMP), propylene glycol monomethyl ether acetate (PMA) or isopropyl alcohol (IPA) and other chemicals are effectively removed, so that the metal ion content in the chemicals reaches below 1 ppb, and the preparation of G3 or above electronic grade chemicals is realized.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of 3D printing hydrogel new materials and new applications, and particularly relates to an adsorption rectification filler based on 3D printing of hydrogel and application thereof in preparation of electronic-grade chemicals. BACKGROUND

[0002] Electronic chemicals, also known as electronic chemical materials, generally refer to special chemicals and chemical materials used in the electronic industry, which have high professional requirements and high degree of distinction. Most of the electronic chemicals used in China are dependent on imports, which seriously affects the development of high-end electronic fields such as chips, integrated circuits and 5G in China. With the rapid development of integrated circuit technology, the purity requirements of electronic-grade chemicals are also increasing, among which the particle impurity content has been reduced from 1 μm to 0.5 μm and even to 0.2 μm, and the purity is at least 6N (99.9999%), and some even require a purity of more than 9N (99.9999999%), and the content of metal ion impurities has also developed from Grade 3 (≤1 ppb) to Grade 4 (≤0.1 ppb). Therefore, the removal of metal ions in electronic chemicals is one of the key problems in the development of microelectronic technology, and it is crucial to develop a functional material for removing metal ions in NMP, IPA, PMA and other organic solvents.

[0003] Wet electronic chemicals such as N-methyl pyrrolidone (NMP), isopropyl alcohol (IPA), and propylene glycol monomethyl ether acetate (PMA) are mainly used in high-end fields such as electrolytes of lithium ion batteries, cleaning agents of liquid crystal products, and stripping liquids of photoresists. At present, the purification and removal of NMP, IPA, PMA and other organic solvents are mostly carried out by continuous rectification, which can remove trace metal ions while removing organic matter, water and other impurities. However, for electronic-grade chemicals, the content of metal ions needs to be reduced from ppm level to ppb level, and the theoretical plate number required by the rectification process increases sharply, resulting in high energy consumption. Therefore, it is crucial to find a way to effectively remove metal ion impurities in the rectification process to prepare electronic-grade chemicals.

[0004] Adsorption method is one of the most promising methods for deep removal of metal ion impurities because it can be precisely designed for adsorption materials. Therefore, it is of great significance to prepare an adsorption rectification filler for the preparation of electronic-grade chemicals. SUMMARY

[0005] The purpose of the present application is to provide a preparation of an adsorption rectification filler based on 3D printing of hydrogel and its application in the preparation of electronic-grade chemicals.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] One of the purposes of the present application is to protect an adsorptive rectification packing based on hydrogel 3D printing, which is prepared by using a photoinitiator, a light absorber, a solvent and a crosslinking agent without metal ions to prepare a hydrogel ink for 3D printing, and then printing and preparing by using a 3D printing photocuring technology.

[0008] The second purpose of the present application is to protect the preparation method of the adsorptive rectification packing, which comprises the following steps:

[0009] (1) mixing L-lysine, a reaction monomer, ammonium persulfate, a crosslinking agent, a photoinitiator and a light absorber, and adding electronic grade ammonia, acrylic acid and ultrapure water under stirring to prepare a hydrogel ink for 3D printing;

[0010] (2) according to the designed three-dimensional model of the packing, using the hydrogel ink for 3D printing prepared in step (1) to perform photocuring 3D printing to obtain a photocured hydrogel adsorptive rectification packing structure;

[0011] (3) performing ion exchange on the hydrogel adsorptive rectification packing structure prepared in step (2) with a hydrochloric acid solution, and freeze-drying to obtain the adsorptive rectification packing.

[0012] Further, the reaction monomer in step (1) is cellulose or sodium lignosulfonate.

[0013] Further, the crosslinking agent in step (1) is N,N-methylene bisacrylamide or polyethylene glycol diacrylate.

[0014] Further, the photoinitiator in step (1) is (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (TPO) or 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester (TPO-L).

[0015] Further, the light absorber in step (1) is lemon yellow, riboflavin or ultraviolet absorber UV-P.

[0016] Further, the mass ratio of L-lysine, the reaction monomer, ammonium persulfate, the crosslinking agent, the photoinitiator and the light absorber used in step (1) is 1:(1~3):5:1:(0.4~1):(0.1~0.5).

[0017] Further, the amount of electronic grade ammonia, acrylic acid and ultrapure water used in step (1) accounts for 21~30%, 38~49% and 20~30% of the mass of the obtained hydrogel ink for 3D printing, respectively.

[0018] Further, the electronic grade ammonia does not contain metal ions. The conductivity of the ultrapure water is 18.2 MΩ, and the TOC value is less than 5 ppb.

[0019] Further, the three-dimensional model of the filler designed in step (2) includes a foam structure, a corrugated structure, a columnar structure, and the like.

[0020] Further, the designed filler includes an open hole, a non-open hole, a window, a thread, and the like.

[0021] Further, the light source wavelength used in the light-cured 3D printing in step (2) is 320-500 nm, the light source intensity is 300-500 mW, the exposure time of each layer is 10-30 s, and the slice thickness is 0.1-0.2 mm.

[0022] Further, the concentration of the hydrochloric acid solution used in step (3) is 1-5 M.

[0023] Further, the ion exchange time in step (3) is 2-12 h.

[0024] Further, the temperature of the freeze-drying in step (3) is -40-50 DEG C.

[0025] The third object of the present application is to protect the application of the adsorption rectification filler in removing trace metal ions in adsorption rectification of chemicals and preparing electronic-grade chemicals.

[0026] Specifically, the application method is to load the adsorption rectification filler into a rectification tower for adsorption rectification removal of trace metal ions in chemicals to obtain electronic-grade chemicals of G3 or above.

[0027] Further, the chemicals include N-methyl pyrrolidone (NMP), isopropyl alcohol (IPA), propylene glycol monomethyl ether acetate (PMA), and the like.

[0028] Further, the theoretical plate number of the rectification tower is 30-50, and the reflux ratio is 2-20.

[0029] Further, the rectification tower is subjected to multiple acid pickling and alkaline repeated passivation.

[0030] Further, a single or multiple rectification towers can be used in series.

[0031] Further, the content of metal ions in the obtained electronic-grade chemicals is below 1 ppb.

[0032] The present application has the following beneficial effects:

[0033] The present application prepares a hydrogel ink for 3D printing by using a photoinitiator, a light absorber, a solvent and a crosslinking agent without metal ions, and uses a 3D printing light curing technology to print and prepare an adsorption rectification filler, and then loads the prepared adsorption rectification filler in a rectification tower, so that through the coupling of adsorption and rectification process, trace metal ions in chemicals are removed, which can effectively reduce the rectification tower plate, avoid the cost of additional construction of an adsorption tower, and remove metal ions in NMP, IPA and PMA to below 1 ppb, realize the preparation of G3 or above electronic grade chemicals, and provide a reference for the separation and purification of industrial grade chemicals to prepare electronic grade chemicals. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 A schematic diagram of the device for preparing G3 grade NMP in Example 1.

[0035] Figure 2 A SEM image of the adsorption rectification filler prepared in Example 1.

[0036] Figure 3 The infrared spectra of lysine (M-L), sodium lignosulfonate (M-S) used in Example 1, the prepared adsorption rectification filler (SLH-2) and the adsorbed NMP containing Cu metal ions (SLH-2-Cu).

[0037] Figure 4 The X-ray diffraction patterns of the adsorption rectification filler (SLH-2) prepared in Example 1 and the adsorbed NMP containing Cu metal ions (SLH-2-Cu).

[0038] Figure 5 A comparison chart of the adsorption rectification filler prepared in Example 1 and the adsorbed NMP containing Cu metal ions.

[0039] Figure 6 A schematic diagram of the device for preparing G3 grade IPA in Example 2.

[0040] Figure 7 A schematic diagram of the device for preparing G3 grade PMA in Example 3. DETAILED DESCRIPTION

[0041] An adsorption rectification filler based on 3D printing of hydrogel, the preparation thereof comprises the following steps:

[0042] (1) Take appropriate amounts of L-lysine, reaction monomer, ammonium persulfate, crosslinking agent, photoinitiator and light absorber according to the mass ratio of 1: (1-3): 5: 1: (0.4-1): (0.1-0.5) and add them to a beaker. Add electronic grade ammonia water without metal ions, acrylic acid and ultrapure water under stirring to prepare a 3D printing hydrogel ink; the amounts of electronic grade ammonia water, acrylic acid and ultrapure water account for 21-30%, 38-49% and 20-30% of the mass of the obtained 3D printing hydrogel ink, respectively;

[0043] (2) Use computer-aided modeling software to design a three-dimensional model of the filler structure of foam structure, corrugated structure, columnar structure, etc., then use slicing software to process the three-dimensional model, and then use the 3D printing hydrogel ink prepared in step (1) to place in the printer cartridge for photocuring 3D printing to obtain a photocured hydrogel adsorption rectification filler structure; the wavelength of the light source used in photocuring 3D printing is 320-500 nm, the light source intensity is 300-500 mW, the exposure time of each layer is 10-30 s, and the slice thickness is 0.1-0.2 mm;

[0044] (3) The hydrogel adsorption rectification filler structure prepared in step (2) is ion exchanged with a hydrochloric acid solution with a concentration of 1-5 M for 2-12 h, and then freeze-dried at -40-50℃ to obtain the adsorption rectification filler, which is placed in a drying box for standby.

[0045] In step (1), the reaction monomer is cellulose or sodium lignosulfonate. The crosslinking agent is N,N-methylene bisacrylamide or polyethylene glycol diacrylate. The photoinitiator is (2,4,6-trimethylbenzoyl) diphenyl phosphine oxide (TPO) or 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester (TPO-L). The light absorber is lemon yellow, riboflavin or ultraviolet absorber UV-P.

[0046] In order to make the content of the application more convenient to understand, the technical solutions of the application will be further described in combination with specific embodiments, but the application is not limited to this.

[0047] In the experiment, the reagents used to prepare the hydrogel are analytical pure, all of which are commercially available. The conductivity of the ultrapure water used is 18.2 MΩ, and the TOC value is less than 5 ppb.

[0048] The concentration of metal ions in the experiment was tested by ICP (ICPE-9000) and ICP-MS (ICAP RQ, ThermoFisher Scientific, Germany). The purity of the solvent after adsorption was tested by gas chromatography (Agilent 8890 GC System). The real adsorption experiment was carried out in a clean laboratory of 100,000 level. The instruments used in the experiment were made of PFA material.

[0049] Example 1

[0050] 0.03 g of lysine, 0.06 g of sodium lignosulfonate, 0.15 g of ammonium persulfate, 0.03 g of N,N-methylenebisacrylamide, 0.018 g of TPO, and 0.005 g of tartrazine were weighed into a 250 mL beaker, and then 7.5 g of acrylic acid, 5 g of ultrapure water, and 4.5 g of electronic grade ammonia water were slowly added. After stirring for 1 h, a hydrogel ink for 3D printing was obtained. Then the obtained hydrogel ink was placed in a smooth 3D printing cartridge, and a light-cured 3D printer was used to print according to the model program (the wavelength of the light source of the 3D printer was 350 nm, the intensity was 380 mW, the slice thickness was 0.1 nm, and the exposure time of each layer was 20 s) to obtain a light-cured hydrogel adsorption rectification packing. The obtained hydrogel adsorption rectification packing was ion exchanged with 1 M hydrochloric acid solution for 2 h, and then freeze-dried at -45°C to obtain an adsorption rectification packing.

[0051] The prepared adsorption rectification packing was loaded into a rectification tower, and G3 grade NMP was prepared by using a single rectification tower. The schematic diagram of the device is shown in Figure 1 The theoretical plate number of the rectification tower 1 used was 40, and the reflux ratio was 8. The product indicators are shown in Table 1.

[0052] Table 1 Adsorption effect of the prepared adsorption rectification packing on different metal ions in NMP

[0053]

[0054] Figure 2 The SEM image of the prepared adsorption rectification packing. As can be seen from the figure, the surface contains a rich porous structure, which can make the material surface exhibit more active sites, which may be the key to its better adsorption performance.

[0055] Figure 3 The infrared spectra of the lysine (M-L), sodium lignosulfonate (M-S), the prepared adsorption rectification packing (SLH-2), and the packing after adsorbing Cu metal ions in NMP (SLH-2-Cu) are shown in the figure. As can be seen from the figure, in the infrared spectrum of lysine, ~3440 cm -1 is the stretching vibration peak of -OH or -COOH; 1580 cm-1 The tooth-shaped absorption peak at 1570 cm -1 The C=C skeleton vibration peak in benzene ring at 1120 cm -1 The -O- stretching vibration peak at 1040, 657 and 532 cm -1 The sulfonate stretching vibration peak at 1040, 657 and 532 cm -1 and 549 cm -1 The peaks at 1564 cm

[0056] Figure 4 The XRD patterns of the prepared adsorption rectification filler (SLH-2) and the adsorption NMP Cu metal ion (SLH-2-Cu) after the adsorption. As can be seen from the figure, the filler sample itself has no XRD diffraction peak, and after adsorbing Cu metal ion, there is an obvious XRD diffraction peak, which corresponds to a copper ammonium complex, indicating that the filler has successfully adsorbed copper ions.

[0057] Figure 5 The real object comparison diagram of the prepared adsorption rectification and its adsorption of Cu metal ion in NMP. As can be seen from the figure, the filler is yellow before adsorption and blue after adsorption, which indicates that the filler surface is covered with a layer of copper ions.

[0058] Example 2

[0059] 0.03 g of lysine, 0.03 g of cellulose, 0.15 g of ammonium persulfate, 0.03 g of N,N-methylene bisacrylamide, 0.012 g of TPO, and 0.005 g of lemon yellow were weighed into a 250 mL beaker, and then 15.7 g of acrylic acid, 10 g of ultrapure water, and 8.9 g of electronic grade ammonia water were slowly added. After stirring for 1 h, a 3D printing hydrogel ink was obtained. Then the obtained hydrogel ink was placed in a smooth 3D printing cartridge, and a light curing 3D printer was used to print according to the model program (the wavelength of the light source of the 3D printer was 350 nm, the intensity was 380 mW, the slice thickness was 0.1 nm, and the exposure time of each layer was 20 s) to form a light-cured hydrogel adsorption rectification filler. The obtained hydrogel adsorption rectification filler was ion exchanged with 1 M hydrochloric acid solution for 2 h, and then freeze-dried at -45°C to obtain an adsorption rectification filler.

[0060] The prepared adsorption rectification filler was packed in a rectification tower, and two rectification towers were used in series to prepare G3 grade IPA, and the device schematic diagram is asFigure 6 The theoretical plate number of the rectification tower 2 used was 40, and the reflux ratio was 10; the theoretical plate number of the rectification tower 3 was 45, and the reflux ratio was 10. The product indicators are shown in Table 2.

[0061] Table 2 Adsorption effect of the prepared adsorption rectification packing on different metal ions in IPA

[0062]

[0063] Example 3

[0064] 0.03 g of lysine, 0.09 g of cellulose, 0.15 g of ammonium persulfate, 0.03 g of N, N-methylenebisacrylamide, 0.024 g of TPO, and 0.005 g of lemon yellow were weighed into a 250 mL beaker, and then 15.7 g of acrylic acid, 10 g of ultrapure water, and 8.9 g of electronic-grade ammonia water were slowly added, and stirred for 1 h to obtain a hydrogel ink for 3D printing. Then the obtained hydrogel ink was placed in a smooth 3D printing cartridge, and a light-cured 3D printer was used to print according to a model program (the wavelength of the light source of the 3D printer was 350 nm, the intensity was 380 mW, the slice thickness was 0.1 nm, and the exposure time of each layer was 20 s) to obtain a light-cured hydrogel adsorption rectification packing. Then the obtained hydrogel adsorption rectification packing was ion exchanged with a 1 M hydrochloric acid solution for 2 h, and then freeze-dried at -45 °C to obtain an adsorption rectification packing.

[0065] The prepared adsorption rectification packing was packed in a rectification tower, and G3-grade PMA was prepared by using three rectification towers in series, and the schematic diagram of the device is shown in Figure 7 The theoretical plate number of the rectification tower 4 used was 20, and the reflux ratio was 5; the theoretical plate number of the rectification tower 5 was 25, and the reflux ratio was 10; the theoretical plate number of the rectification tower 6 was 20, and the reflux ratio was 8. The product indicators are shown in Table 3.

[0066] Table 3 Adsorption effect of the prepared adsorption rectification packing on different metal ions in PMA

[0067]

[0068] As can be seen from the above, after the adsorption rectification of Examples 1-3, the metal ions in IPA, NMP, and PMA can be well removed, so that the concentration of the metal ions is all below 1 ppb, which meets the requirements of G3-grade electronic-grade chemicals.

[0069] The above only describes the preferred embodiments of the present application, and any equivalent changes and modifications made within the scope of the patent application of the present application shall be included in the scope of the present application.

Claims

1. An adsorption and distillation filler based on hydrogel 3D printing, characterized in that: The preparation method comprises the following steps: (1) L-lysine, a reactive monomer, ammonium persulfate, a crosslinker, a photoinitiator, and a light absorber were mixed, and electronic grade ammonia, acrylic acid, and ultrapure water were added under stirring to prepare a 3D printing hydrogel ink; (2) According to the designed filler three-dimensional model, the 3D printing hydrogel ink prepared in step (1) is used for photocuring 3D printing to obtain a photocured hydrogel adsorption distillation filler structure; (3) subjecting the hydrogel adsorption distillation filler structure obtained in step (2) to ion exchange with a hydrochloric acid solution, and freeze-drying to obtain the adsorption distillation filler; In step (1), the reaction monomer is cellulose or sodium lignin sulfonate; the cross-linking agent is N,N-methylenebisacrylamide or polyethylene glycol diacrylate; the photoinitiator is (2,4,6-trimethylbenzoyl)diphenylphosphine oxide or ethyl 2,4,6-trimethylbenzoylphenylphosphonate; and the light absorber is tartrazine, riboflavin or ultraviolet absorber UV-P.

2. The adsorption distillation packing according to claim 1, characterized in that: The mass ratio of L-lysine, reactive monomer, ammonium persulfate, crosslinking agent, photoinitiator and light absorber used in step (1) is 1:(1-3):5:1:(0.4-1):(0.1-0.5).

3. The adsorption distillation packing according to claim 1, characterized in that: In step (1), the amounts of electronic grade ammonia, acrylic acid and ultrapure water used account for 21-30%, 38-49% and 20-30% of the mass of the obtained 3D printing hydrogel ink, respectively.

4. The adsorption distillation packing according to claim 1, characterized in that: The light source wavelength used in the light-curing 3D printing in step (2) is 320~500nm, the light source intensity is 300~500mW, the exposure time of each layer is 10~30s, and the slice thickness is 0.1~0.2mm.

5. The adsorption distillation packing according to claim 1, characterized in that: The concentration of the hydrochloric acid solution used in step (3) is 1-5 M; the time of the ion exchange is 2-12 h; and the temperature of the freeze-drying is -40~50°C.

6. Use of the adsorption distillation filler according to claim 1 in removing trace metal ions from chemicals by adsorption distillation, characterized in that: The adsorption distillation filler is loaded into a distillation tower for removing trace metal ions in chemicals by adsorption distillation to obtain electronic grade chemicals above G3 grade.

7. The use according to claim 6, characterized in that: The chemicals include N-methylpyrrolidone, isopropyl alcohol, and propylene glycol monomethyl ether acetate.

8. The use according to claim 6, characterized in that: The number of theoretical plates of the distillation tower is 30-50, and the reflux ratio is 2-20.

9. The use according to claim 6, characterized in that: The metal ion content in the obtained electronic-grade chemicals is below 1 ppb.

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