Method for storing and delivering electronic special gas by using fluorine-containing porous organic polymer

Abstract

The invention discloses a method for storing and delivering electronic special gas by using a fluorine-containing porous organic polymer, the mass content of fluorine in the fluorine-containing porous organic polymer is 20-30%, the specific surface area of the fluorine-containing porous organic polymer is 500-2500m < 2 > g <-1 >, and the pore volume is 0.3-3cm < 3 > g <-1 >; the deliverable amount of the fluorine-containing porous organic polymer to the electronic special gas at the pressure of 650 torr and the temperature of 21 DEG C is at least 140 g L <-1 >, and the desorption rate of the adsorbed electronic special gas at the pressure of 5 torr to 650 torr is greater than 70%. According to the invention, the problems of low delivery amount, low desorption rate, low desorbed electronic special gas quality and the like of the existing adsorbent for storing and delivering the electronic special gas in the field can be solved.

Description

Technical Field

[0001] The present invention relates to the field of gas storage technology, and in particular to a method for storing and delivering electronic special gases by using fluorine-containing porous organic polymers. Background Art

[0002] As a key basic raw material for industries such as integrated circuits and semiconductors, electronic special gases play a key role in multiple process flows such as ion implantation, etching, doping, and packaging in the production of semiconductor chips. Fluorine-containing electronic special gases used for ion implantation such as boron trifluoride and germanium tetrafluoride are highly toxic and corrosive. Traditional high-pressure cylinder storage methods have serious leakage risks. The industry generally uses negative pressure storage and transportation methods to use electronic special gases. The common negative pressure storage method for special gases is to use an adsorbent filled in a gas cylinder to reversibly adsorb the electronic special gas. The gas in the cylinder is in a negative pressure state. When the electronic special gas is needed, it will be desorbed from the adsorbent and delivered.

[0003] The patent specification with publication number CN115770548A provides the application of all-silicon molecular sieve adsorbent in the storage of special gases, and the all-silicon molecular sieve adsorbent has a multi-level pore structure, and the multi-level pore structure includes mesopores. The porous adsorbent has the problems of low delivery capacity and low desorption rate for the negative pressure adsorption storage of electronic special gases. The development of efficient adsorbent materials to improve the negative pressure storage capacity and desorption rate of electronic special gases is the key. Metal organic framework materials (Metal Organic Frameworks, MOFs), activated carbon and other materials have received widespread attention in the field of gas storage. The metal organic framework material in the embodiment of patent application CN105813711A has a desorption rate of about 50% for electronic special gases, and still has the disadvantage of low desorption rate of electronic special gases. Therefore, it is urgent to develop a technical solution to improve the delivery capacity and desorption rate of fluorine-containing electronic special gases. Summary of the invention

[0004] In view of the above-mentioned technical problems and the shortcomings in the art, the present invention provides a method for storing and delivering electronic special gases using fluorine-containing porous organic polymers. The fluorine-containing porous organic polymer of the present invention can be used as a medium for storing and delivering electronic special gases, especially fluorine-containing electronic special gases. It has a relatively weak interaction with electronic special gases, especially fluorine-containing electronic special gases, and can thereby improve the desorption rate of electronic special gases, especially fluorine-containing electronic special gases in the material, thereby achieving effective storage and delivery of electronic special gases, especially fluorine-containing electronic special gases. The present invention can solve the problems of low deliverable amount, low desorption rate, and low quality of desorbed electronic special gases in existing adsorbents for storage and delivery of electronic special gases in the art.

[0005] The specific technical solutions are as follows:

[0006] A method for storing and delivering electronic special gases using a fluorine-containing porous organic polymer, wherein the mass content of fluorine in the fluorine-containing porous organic polymer is between 20% and 30%, and the specific surface area of ​​the fluorine-containing porous organic polymer is 500-2500m 2 g -1 (For example, 650m 2 g -1 、1200m 2 g -1 etc.), pore volume is 0.3-3cm 3 g -1 (For example 0.4m 2 g -1 、1.1m 2 g -1 wait);

[0007] The fluorine-containing porous organic polymer can deliver at least 140 g L of the electronic special gas at a pressure of 650 Torr and 21° C. -1 , further at least 300 g L -1 , and the desorption rate of the electronic special gas adsorbed at a pressure of 5 torr to 650 torr is greater than 70%, and can further be greater than 85%.

[0008] The mass content of fluorine in the fluorine-containing porous organic polymer of the present invention is not less than 20%. The fluorine element in the fluorine-containing porous organic polymer can be derived from synthetic monomers or introduced through post-treatment.

[0009] In some embodiments, in the method of storing and delivering electronic special gases using fluorine-containing porous organic polymers, the electronic special gases may include at least one of boron trifluoride, germanium tetrafluoride, and arsine.

[0010] In some embodiments, in the method of storing and delivering electronic special gases using fluorine-containing porous organic polymers, the average pore size of the fluorine-containing porous organic polymers can be distributed in the range of 0.5-3 nm.

[0011] The method of storing and delivering electronic special gases using fluorine-containing porous organic polymers, the shape of the fluorine-containing porous organic polymers may include at least one of powder, granular, spherical, strip, block, cylindrical, cubic, and disc-like.

[0012] In some embodiments, in the method of storing and delivering electronic special gases using a fluorine-containing porous organic polymer, the fluorine-containing porous organic polymer may have an average diameter between 0.05 mm and 10.0 mm.

[0013] In some embodiments, the method of storing and delivering electronic special gases using a fluorinated porous organic polymer can have a volume packing density of 0.5-2.0 g cm-1 between.

[0014] The method of storing and delivering electronic special gases using fluorinated porous organic polymers, the fluorinated porous organic polymers may include at least one of hyper-crosslinked organic polymers (Hyper-Crosslinked Polymers, HCPs), conjugated organic microporous polymers (Conjugated Microporous Polymers, CMPs), and porous aromatic frameworks (Porous Aromatic Frameworks, PAFs).

[0015] In some embodiments, in the method of storing and delivering electronic special gases using fluorine-containing porous organic polymers, the fluorine-containing porous organic polymers do not contain metal ions, and therefore, no metal impurities are introduced during the storage and delivery of the electronic special gases.

[0016] In some embodiments, in the method of storing and delivering electronic special gases using fluorine-containing porous organic polymers, the polymerized monomers of the fluorine-containing porous organic polymers contain at least tetrafluorobenzene, and the fluorine mass content can be controlled by regulating the structure of other polymerized monomers.

[0017] Furthermore, the fluorine-containing porous organic polymer can be formed by reacting raw materials including organic monomer 1 and organic monomer 2. The organic monomer 1 can be selected from at least one of 1,3,5-tribromobenzene and tri(4-bromophenyl)amine. The organic monomer 2 can be 1,2,4,5-tetrafluorobenzene. The organic monomer 1 and the organic monomer 2 can be connected by polycondensation to remove HBr to form the fluorine-containing porous organic polymer.

[0018] The fluorine-containing porous organic polymer of the present invention can be prepared by referring to the prior art. Furthermore, no metal is involved in the preparation process of the fluorine-containing porous organic polymer.

[0019] The method for storing and delivering electronic special gases using fluorine-containing porous organic polymers can bring the electronic special gases into contact with the fluorine-containing porous organic polymers to achieve adsorption, storage and delivery of the electronic special gases under the drive of adsorption and desorption pressures.

[0020] The present invention can regulate the pore size and surface microenvironment of the polymer material by introducing high-quality fluorine elements into the adsorbent framework, and the negatively charged adsorption surface is conducive to the desorption of electronic special gases, especially fluorine-containing electronic special gases. Fluorine-containing porous organic polymers are used as the medium for the storage and delivery of electronic special gases, especially fluorine-containing electronic special gases. They have relatively weak interactions with electronic special gases, especially fluorine-containing electronic special gases, and can thus improve the desorption rate of electronic special gases, especially fluorine-containing electronic special gases, in the material, and achieve efficient storage and delivery of electronic special gases, especially fluorine-containing electronic special gases.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1) When the fluorine-containing porous organic polymer adsorbent proposed in the present invention is used for the adsorption, storage and delivery of electronic special gases, especially fluorine-containing electronic special gases, the negatively charged pore microenvironment provided on the surface of the material weakens the interaction between the adsorbent and the electronic special gases, especially fluorine-containing electronic special gases, thereby improving the desorption rate of electronic special gases, especially fluorine-containing electronic special gases.

[0023] 2) The fluorine-containing porous organic polymer described in the present invention has a suitable pore size distribution and a large specific surface area, which can achieve high-capacity adsorption, storage and delivery of electronic special gases, especially fluorine-containing electronic special gases, and the fluorine-containing porous organic polymer material does not contain metal ions and will not introduce metal impurities.

[0024] 3) The fluorine-containing porous organic polymer described in the present invention is easy to process and has extremely high air stability and thermal stability, and has great application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is the adsorption-desorption isotherm diagram of germanium tetrafluoride by the fluorine-containing porous organic polymer FPOP-1 of Example 1 at 294K;

[0026] Figure 2 The bar graphs are the mass contents of carbon and fluorine in Example 1 and Example 2;

[0027] Figure 3 The non-local density functional theory (NLDFT) pore size distribution diagram obtained by calculating the nitrogen adsorption isotherm at 77K of the fluorine-containing porous organic polymer FPOP-1 of Example 1;

[0028] Figure 4 77K nitrogen adsorption isotherm diagram of the fluorine-containing porous organic polymer FPOP-1 of Example 1 before and after being placed in air for 3 months;

[0029] Figure 5 This is a thermogravimetric curve of the fluorine-containing porous organic polymer FPOP-1 of Example 1;

[0030] Figure 6 is the adsorption-desorption isotherm diagram of germanium tetrafluoride by the fluorine-containing porous organic polymer FPOP-2 of Example 2 at 294K;

[0031] Figure 7 is the adsorption-desorption isotherm diagram of arsine by the fluorine-containing porous organic polymer FPOP-2 of Example 2 at 294K;

[0032] Figure 8is the adsorption-desorption isotherm diagram of germanium tetrafluoride by the fluorine-free porous organic polymer HCP-TPB of Example 3 at 294K;

[0033] Fig. 9 This is the adsorption-desorption isotherm diagram of germanium tetrafluoride on the fluorine-containing porous organic polymer FPOP-3 of Example 4 at 294K. DETAILED DESCRIPTION

[0034] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0035] The operating methods in the following examples without specifying specific conditions are usually carried out under conventional conditions or under conditions recommended by the manufacturers.

[0036] Example 1

[0037] Preparation of fluorinated porous organic polymer adsorbent: Di-tert-butyl methylphosphine tetrafluoroborate (31 mg, 0.13 mmol), 1,3,5-tribromobenzene (271 mg, 0.83 mmol), 1,2,4,5-tetrafluorobenzene (133 μL, 1.25 mmol), potassium carbonate (345 mg, 2.5 mmol) were dissolved in N,N-dimethylacetamide (DMAc, 2.5 mL). Palladium acetate (14 mg, 0.06 mmol) was added to the mixture, and three freeze-pump-thaw cycles were added under nitrogen atmosphere. The reaction solution was stirred overnight at 120 ° C under nitrogen atmosphere. After cooling to room temperature, the mixture was poured into 100 ml of water. The precipitate was collected after filtration and washing with water, methanol and tetrahydrofuran. Using a Soxhlet extractor, methanol solvent was treated for 24 hours, and then tetrahydrofuran was treated for 24 hours to obtain a black solid which was dried in a vacuum oven at 110°C overnight to obtain a product. The material was named FPOP-1 and can be used as an adsorbent.

[0038] The mass content of fluorine in the fluorine-containing porous organic polymer material FPOP-1 determined by EDX elemental analysis is 27.56%, and the deliverable amount of germanium tetrafluoride calculated from the pressure range of 5 to 650 torr is 275 g L -1 The gas desorption rate calculated from 5 to 650 torr pressure is 76.3%. The NLDFT pore size distribution of FPOP-1 material is 0.5-3 nm and the specific surface area is 1145 m 2 g -1 , pore volume is 1.09cm 3 g -1 .

[0039] Example 1 The adsorption and desorption isotherms of germanium tetrafluoride on the adsorbent at 294K are as follows Figure 1As shown; the mass contents of carbon and fluorine in the adsorbent of Example 1 are as shown Figure 2 The NLDFT pore size distribution of the adsorbent of Example 1 calculated from the 77K nitrogen adsorption isotherm is shown in Figure 3 As shown, the 77K nitrogen adsorption isotherm of the adsorbent in Example 1 before and after being placed in air for 3 months is as follows Figure 4 As shown, it shows that the adsorbent has good air stability. The thermogravimetric adsorption curve of the adsorbent in Example 1 is shown in Figure 5 As shown, it shows that the adsorbent has good thermal stability. Good air and thermal stability make the adsorbent suitable for the storage of corrosive and reactive electronic special gases.

[0040] Example 2

[0041] Preparation of fluorinated porous organic polymer adsorbent: Tri(4-bromophenyl)amine (482.0 mg, 1.0 mmol), 1,2,4,5-tetrafluorobenzene (160.8 μL, 1.5 mmol), di-tert-butylmethylphosphine tetrafluoroborate (37.05 mg, 0.15 mmol), potassium carbonate (414.62 mg, 3.0 mmol) were mixed and added to anhydrous N,N-dimethylacetamide (DMAc, 2.5 mL). Palladium acetate (16.84 mg, 0.075 mmol) was added to the mixture under nitrogen atmosphere, and three freeze-pump-thaw cycles were performed. The reaction solution was stirred at 120 °C for 24 hours under nitrogen atmosphere. After cooling to room temperature, the mixture was poured into 200 mL of deionized water. The precipitate was washed with water, methanol and tetrahydrofuran, collected by filtration, extracted with a Soxhlet extractor and methanol solvent for 24 hours, and then treated with tetrahydrofuran for 24 hours to obtain a black solid, which was dried in a vacuum oven at 100°C overnight to obtain a product. The material was named FPOP-2 and can be used as an adsorbent.

[0042] The mass content of fluorine in the fluorine-containing porous organic polymer material FPOP-2 determined by EDX elemental analysis is 22.95%, and the deliverable amount of germanium tetrafluoride calculated from the pressure range of 5 to 650 torr is 205 g L -1 The gas desorption rate calculated from 5 to 650 torr pressure is 73.2%; the specific surface area of ​​FPOP-2 is 693m 2 g -1 , pore volume is 0.42cm 3 g -1 The adsorption capacity of arsine is 165 g L -1 The gas desorption rate calculated from 5 to 650 torr pressure is 87.1%, and the deliverable amount is 144 g L -1 .

[0043] Example 2 The adsorption and desorption isotherms of germanium tetrafluoride on the adsorbent at 294K are as follows Figure 6As shown; the adsorption and desorption isotherms of the adsorbent of Example 2 for arsine at 294K are as follows Figure 7 As shown; the mass content of carbon and fluorine in the adsorbent of Example 2 is as shown Figure 2 shown.

[0044] Example 3

[0045] Preparation of a fluorine-free porous organic polymer adsorbent for comparison: Under a nitrogen atmosphere, anhydrous aluminum chloride (4.9 g, 36.8 mmol) was added to a solution of 1,3,5-triphenylbenzene (1.51 g, 4.9 mmol) in a dichloromethane DCM solvent (60 mL) and refluxed, and stirred under reflux for 18-24 hours. The brown precipitate was collected by filtration and rinsed with water and ethanol. The polymer was then dispersed in the following solvents in turn and refluxed for six hours: ethanol, chloroform, tetrahydrofuran, acetone and methanol. The brown product was ground into a fine powder and dried in a vacuum oven at 80°C for 18 hours to obtain a product, which was named HCP-TPB and can be used as an adsorbent.

[0046] The fluorine-free porous organic polymer material HCP-TPB has a calculated deliverable amount of germanium tetrafluoride of 225 g L at a pressure range of 5 to 650 torr. -1 The desorption rate calculated from 5 to 650 torr pressure is 39.3%, which is significantly lower than 70%. The above results show that the introduction of fluorine sites can improve the desorption rate of fluorine-containing gases.

[0047] Example 3 The adsorption and desorption isotherms of germanium tetrafluoride on the adsorbent at 294K are as follows: Figure 8 shown.

[0048] Example 4

[0049] Preparation of fluorine-containing porous organic polymer adsorbent using low-fluorine monomers: Di-tert-butyl methylphosphine tetrafluoroborate (31 mg, 0.13 mmol), 1,3,5-tribromobenzene (271 mg, 0.83 mmol), p-difluorobenzene (105 μL, 1.25 mmol), potassium carbonate (345 mg, 2.5 mmol) were dissolved in N,N-dimethylacetamide (DMAc, 2.5 mL). Palladium acetate (14 mg, 0.06 mmol) was added to the mixture, and three freeze-pump-thaw cycles were performed under a nitrogen atmosphere. The reaction solution was stirred overnight at 120 ° C in a nitrogen atmosphere. After cooling to room temperature, the mixture was poured into 100 ml of water. The precipitate was collected after filtration and washing with water and ethanol. Using a Soxhlet extractor, a brown solid was obtained and dried overnight at 110 ° C in a vacuum oven to obtain a product, which was named FPOP-3 and can be used as an adsorbent. Since only part of the hydrogen in the monomer is replaced by fluorine, the fluorine mass content is low, and the mass content of fluorine element determined by EDX elemental analysis is 15.25%. The desorption rate of germanium tetrafluoride gas of FPOP-3 is 61.9%, which is lower than that of FPOP-1, because the interaction between part of the hydrogen and germanium tetrafluoride is strong.

[0050] Example 4 The adsorption and desorption isotherms of germanium tetrafluoride on the adsorbent at 294K are as follows: Fig. 9 shown.

[0051] Example 5

[0052] Preparation of fluorinated polymer F-CTF-1: Tetrafluoroterephthalonitrile (TFPN, 1 mmol, 0.2 g) and Lewis superacid Zn(NTf2)2 (1 mmol, 0.626 g) were added to a Pyrex tube and flame-sealed under vacuum. Then, the tube was heated at 250°C in a muffle furnace for 24 hours. After the reaction, the Pyrex tube was cooled to room temperature. After removing the catalyst, the unreacted monomers and low-polymerization products were treated with tetrahydrofuran (THF), dilute HCl, H2O and acetone, and the product F-CTF-1 was a black powder. The mass content of fluorine element obtained by EDX elemental analysis of FCTF-1 was 30%, and the specific surface area was 312 m 2 g -1 , pore volume is 0.16cm 3 g -1 The deliverable amount of arsenic is 102 g L -1 , the deliverable amount of germanium tetrafluoride is 125 g L -1 .

[0053] In addition, it should be understood that after reading the above description of the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application.

Claims

1. A method for storing and delivering electronic special gases using fluorinated porous organic polymers, characterized in that: The mass content of fluorine in the fluorine-containing porous organic polymer is between 20% and 30%, and the specific surface area of ​​the fluorine-containing porous organic polymer is 500-2500m 2 g -1 , pore volume is 0.3-3cm 3 g -1 ; The fluorine-containing porous organic polymer can deliver at least 140 g L of the electronic special gas at a pressure of 650 Torr and 21° C. -1 , and the desorption rate of the adsorbed electronic special gas under the pressure of 5 torr to 650 torr is greater than 70%.

2. The method according to claim 1, characterized in that The electronic special gas includes at least one of boron trifluoride, germanium tetrafluoride and arsine.

3. The method according to claim 1, characterized in that The average pore size of the fluorine-containing porous organic polymer is distributed in the range of 0.5-3 nm.

4. The method according to claim 1, characterized in that: The shape of the fluorine-containing porous organic polymer includes at least one of powder, granule, sphere, strip, block, cylinder, cube and disk.

5. The method according to claim 1, characterized in that The fluorine-containing porous organic polymer has an average diameter between 0.05 mm and 10.0 mm.

6. The method according to claim 1, characterized in that The bulk density of the fluorinated porous organic polymer is 0.5-2.0 g cm -1 between.

7. The method according to claim 1, characterized in that The fluorine-containing porous organic polymer comprises at least one of a hyper-crosslinked organic polymer, a conjugated organic microporous polymer, and a porous aromatic framework.

8. The method according to claim 1, characterized in that The fluorine-containing porous organic polymer does not contain metal ions.

9. The method according to claim 1, characterized in that: The fluorine-containing porous organic polymer is formed by reacting raw materials including organic monomer 1 and organic monomer 2; The organic monomer 1 is selected from at least one of 1,3,5-tribromobenzene and tri(4-bromophenyl)amine; The organic monomer 2 is 1,2,4,5-tetrafluorobenzene; The organic monomer 1 and the organic monomer 2 are connected by polycondensation to remove HBr to form the fluorine-containing porous organic polymer.

10. The method according to claim 1, characterized in that The electronic special gas is brought into contact with the fluorine-containing porous organic polymer, and the adsorption, storage and delivery of the electronic special gas are achieved under the driving force of adsorption and desorption pressure.

Images