Polydivinylbenzene containing silicon-oxygen-silicon bonds as well as preparation method and application of polydivinylbenzene

Abstract

The invention relates to the technical field of electronic gas purification, in particular to silicon-oxygen-silicon-containing polydivinylbenzene and a preparation method and application thereof, and the silicon-oxygen-silicon-containing polydivinylbenzene comprises a polydivinylbenzene skeleton; a silicon-oxygen-silicon bond is chemically bonded on the polydivinylbenzene skeleton. The silicon-oxygen-silicon-containing polydivinylbenzene is prepared by adopting an in-situ synthesis method, the silicon-oxygen-silicon-containing polydivinylbenzene reacts with the dry hydrogen bromide gas to obtain the silicon-bromine bond-containing polydivinylbenzene, and the water content in the hydrogen bromide gas can be reduced through hydrolysis reaction. The silicon-oxygen-silicon-containing polydivinylbenzene has stable properties, is environment-friendly in the preparation and transfer processes and the use process of the silicon-oxygen-silicon-containing polydivinylbenzene as a water removal material, does not introduce metal impurities, and has a good water removal effect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic gas purification, and particularly relates to a silicon-oxygen-silicon bond-containing polydivinylbenzene and a preparation method and application thereof. BACKGROUND

[0002] Hydrogen bromide (HBr) is an electronic gas for dry etching of integrated circuits in the semiconductor and microelectronic industry. In addition, HBr can also be used for modification of photoresist and thin film deposition process, and is one of the indispensable process gases for high-end electronic manufacturing. Electronic-grade HBr has very high purity requirements. Residual moisture can cause abnormal etching rate or rough pattern sidewall, reducing device yield. At the same time, moisture is easily combined with HBr to form hydrate, causing HBr corrosion to be enhanced, accelerating the corrosion of metal pipelines and reaction cavities, shortening the service life of equipment and introducing metal contamination (such as Fe, Ni, etc.). The purification of HBr, especially the water removal technology, is the technical bottleneck and key of HBr purification process.

[0003] The trace water in HBr is removed by adsorbing water molecules by solid adsorbents such as silica gel, molecular sieve, alumina and activated carbon. This method is simple to operate and does not cause secondary pollution, but the equipment is bulky, maintenance is complex, water removal efficiency is low, and it cannot meet the requirements of 6N high-purity HBr. To obtain HBr with lower water content and higher purity, chemical reaction dehydration method can be used. A compound that does not react with HBr but reacts easily with water is added to the HBr gas, and the water content is reduced by irreversible chemical reaction with water.

[0004] Patent CN115057413A discloses a preparation method of high-purity hydrogen bromide and its application in processing of silicon carbide device trench structure. HBr containing water is introduced from the bottom of the drying tower, liquid PBr3 (or SiBr4) is introduced from the top, PBr3 (or SiBr4) and HBr are countercurrently contacted in the tower, and then secondary drying and demisting are performed to obtain HBr with water content less than 2x10 -9 Drying HBr. The disadvantage of this technology is that PBr3 and SiBr4 are highly corrosive, which can easily cause corrosion of storage containers, transportation vehicles and conveying pipelines, damage equipment, and introduce metal ion impurities to contaminate the product. The additional separation of excess PBr3, SiBr4 and by-products H3PO3, Si(OH)4 increases the complexity of the process and the energy consumption is high.

[0005] In patents CN120504779A and CN120518866A, respectively, a method for preparing polystyrene microspheres and silicone microspheres containing Si-Br bonds and their application in HBr water removal are disclosed, effectively solving the problem of separation of excess small molecule chemical water remover or hydrolysis by-product from HBr. The disadvantage of this technology is that during production, transfer or storage, the Si-Br bond reacts with water in the air to produce highly corrosive HBr gas, which corrodes the container, introduces metal impurities or pollutes the environment, and at the same time causes the water removal efficiency to decrease.

[0006] Therefore, there is an urgent need in the art for a non-corrosive and environmentally friendly material and water removal method that does not react with water during storage, transportation and transfer, does not corrode equipment and introduce metal impurities. Before use, it is chemically stable and does not react with moisture; when used, it reacts with HBr to convert into a compound that can react with water, effectively removing trace amounts of moisture in HBr gas while avoiding the introduction of impurities and pollution of the environment. In addition, the separation is simple, the energy consumption is low, and it meets the stringent requirements for the preparation of high-purity HBr. SUMMARY

[0007] The present application is to overcome the main problems of using small molecules or polymers to load chemical water removers in the prior art, which are highly corrosive, sensitive to water vapor during transfer, transportation or storage, and easily pollute the environment. At the same time, the separation of excess small molecule chemical water remover or hydrolysis by-product from hydrogen bromide is difficult, which requires additional process steps and increases energy consumption. The physical adsorption method is simple but the purification degree is limited, which cannot meet the demand of high-purity electronic gas. The present application provides a polydivinylbenzene containing Si-O-Si bond and its preparation method and application to overcome the above shortcomings.

[0008] To achieve the above-mentioned application purposes, the present application realizes the following technical solutions: In a first aspect, the present application provides a polydivinylbenzene containing Si-O-Si bond, which comprises a polydivinylbenzene skeleton. The polydivinylbenzene skeleton contains Si-O-Si bonds, The Si-O-Si bond structure is as follows:

[0009] In the formula, R1 is methyl, R2 is methyl, and R2 is phenyl.

[0010] The application provides a polydivinylbenzene containing Si-O-Si bond, and the core innovation is that the Si-O-Si bond is introduced into the polydivinylbenzene skeleton by an in-situ synthesis method. In the specific technical solution, divinylbenzene and hydrogen-containing disiloxane (such as HMe2SiOSiMe2H, HMePhSiOSiMePhH) are used as raw materials, and a silicon-hydrogen addition reaction is carried out under the action of a Karstedt catalyst to generate bis (vinylbenzene ethyl) disiloxane, which is then polymerized together with divinylbenzene by precipitation to generate the polydivinylbenzene containing Si-O-Si bond. This method can ensure that the Si-O-Si bond is uniformly distributed in the polydivinylbenzene and the content is controllable by accurately controlling the monomer ratio and reaction conditions. The cross-linked structure of the polydivinylbenzene not only enhances the chemical stability, but also fixes the Si-O-Si bond on the cross-linked polydivinylbenzene skeleton through ethylene (CH2CH2), thereby avoiding the problem of free Si-Br bond conversion. In the application stage, the polydivinylbenzene containing Si-O-Si bond and a Lewis acid catalyst (such as zinc bromide or magnesium bromide) are filled into a reaction tower, dry HBr gas is introduced, and the Si-O-Si bond reacts with HBr under heating conditions, so that the polydivinylbenzene containing Si-O-Si bond is converted into polydivinylbenzene containing Si-Br bond. After the conversion reaction is completed, water-containing HBr is introduced, the Si-Br bond is hydrolyzed to generate a silicon hydroxyl group (Si-OH) and HBr, so that the water content in the HBr gas is reduced from 1×10 6 to 1×10 -5 to 1×10 -8 to 1×10 -7 The polydivinylbenzene containing Si-O-Si bond has good temperature resistance and toughness, is stable to water vapor, is non-corrosive, is convenient to produce, transfer, transport or store, does not corrode equipment, introduce impurities or pollute the environment. When used as a water removal agent, the Si-O-Si bond in the polydivinylbenzene is first converted into a Si-Br bond by reacting with dry HBr, and then water-containing HBr is introduced to reduce the water content through a hydrolysis reaction. Since the conversion of the Si-O-Si bond into the Si-Br bond and the hydrolysis of the Si-Br bond are completed in the same equipment, the polydivinylbenzene containing Si-Br bond does not need to be transferred and stored, avoiding contact with air, effectively solving the defects of low water removal efficiency, environmental pollution and introduction of metal impurities in the prior art. At the same time, dry HBr gas is used as the raw material, and the by-product is a solid polymer with stable structure, which is easy to separate from the gas, and the water removal process does not increase impurities, reducing the difficulty of subsequent purification.

[0011] As a preferred, the polydivinylbenzene skeleton is connected with the Si-O-Si bond through a CH2CH2 bond.

[0012] As a preferred, the Si-O-Si bond structure is as follows:

[0013] wherein R1 is methyl, and R2 is methyl, phenyl.

[0014] In a second aspect, the present application also provides a method for preparing the Si-O-Si bond-containing polydivinylbenzene, comprising the following steps: (1) in the presence of a platinum catalyst, silicon hydride addition reaction occurs between an excess of divinylbenzene and a hydrogen-containing disiloxane to obtain a mixture of bis (vinylbenzyl) disiloxane and divinylbenzene; (2) adding an organic solvent and an initiator to the mixture of bis (vinylbenzyl) disiloxane and divinylbenzene obtained in step (1), and performing precipitation polymerization to obtain the Si-O-Si bond-containing polydivinylbenzene.

[0015] The preparation method provided by the present application combines silicon hydride addition reaction and precipitation polymerization process, introduces Si-O-Si bond into polydivinylbenzene by in-situ synthesis based on the preparation of bis (vinylbenzyl) disiloxane, thereby improving the temperature resistance and toughness of polydivinylbenzene, increasing the reactivity of polydivinylbenzene, and providing a new technical route for synthesizing Si-O-Si bond-modified polydivinylbenzene.

[0016] Preferably, the hydrogen-containing disiloxane in step (1) is 1,3-dihydro-1,1,3,3-tetramethyldisiloxane (HMe2SiOSiMe2H) or 1,3-dihydro-1,3-dimethyl-1,3-diphenyldisiloxane (HMePhSiOSiMePhH).

[0017] Preferably, the molar ratio of divinylbenzene to hydrogen-containing disiloxane in step (1) is 2.2-3.0:1.

[0018] When the molar ratio of divinylbenzene to hydrogen-containing disiloxane is 1:1, a linear polymer with a non-crosslinked structure is obtained when silicon hydride addition reaction occurs, and the reaction schematic formula is as follows:

[0019] The polymer reacts with dry HBr, the Si-O-Si bond is cleaved into Si-Br bond, and bis (bromosilylethylbenzene) is obtained, and the reaction schematic formula is as follows:

[0020] When bis (bromosilylethylbenzene) is used as a HBr water removal agent, although its boiling point is high, it will still volatilize into HBr gas, increasing the difficulty of HBr purification.

[0021] When the molar ratio of divinylbenzene to hydrogen-containing disiloxane is 2:1, the reaction product is bis (vinylbenzyl) disiloxane, and the reaction schematic formula is as follows:

[0022] When the molar ratio of divinylbenzene to hydrogen-containing disiloxane is greater than 2, divinylbenzene is in excess, and the yield of bis (vinylbenzene ethyl) disiloxane is increased. Excessive divinylbenzene copolymerizes with bis (vinylbenzene ethyl) disiloxane under the action of an initiator, and Si-O-Si bonds are combined on the cross-linked polydivinylbenzene skeleton through CH2CH2. When reacting with dry HBr, the generated Si-Br bonds are also combined on the cross-linked polydivinylbenzene skeleton through CH2CH2, avoiding pollution to HBr gas. If the amount of divinylbenzene is too large, the content of Si-O-Si bonds in polydivinylbenzene is low.

[0023] As a preferred, the platinum catalyst in step (1) is a Karstedt catalyst, which is a complex of chloroplatinic acid and divinyltetramethyldisiloxane, and is a highly efficient catalyst for hydrosilylation reaction. The mass content of platinum in the commonly used Karstedt catalyst is 0.1%, 0.3%, 0.5%, etc.

[0024] As a preferred, the amount of Karstedt catalyst (based on the mass content of platinum) is 0.001% to 0.005% of the total mass of divinylbenzene and hydrogen-containing disiloxane.

[0025] The hydrosilylation reaction can be carried out at room temperature or by heating. The reaction speed is fast when heated, but side reactions such as thermal polymerization of divinylbenzene and dehydrogenation of hydrogen-containing disiloxane are prone to occur. As a preferred, in step (1), the hydrosilylation reaction is carried out at room temperature.

[0026] As a preferred, in step (1), infrared spectroscopy is used to track the reaction process. The Si-H bond of hydrogen-containing disiloxane has strong absorption at 2160 cm -1 -1, and when the absorption peak at 2160 cm -1 -1 disappears, it indicates that the hydrosilylation reaction is complete.

[0027] As a preferred, in step (1), the hydrosilylation reaction is carried out under stirring, and the stirring speed is 450 r / min to 850 r / min.

[0028] As a preferred, in step (1), divinylbenzene and platinum catalyst are added to the reaction bottle at one time, and after being mixed uniformly, hydrogen-containing disiloxane is added dropwise into the mixture of divinylbenzene and platinum catalyst, and the dropwise time is 2 h to 4 h.

[0029] As a preferred, the reaction scheme of step (1) is as follows:

[0030] In the formula, R1 is methyl, and R2 is methyl or phenyl.

[0031] Both bis (vinylphenylethyl) disiloxane and divinylbenzene contain vinyl groups, which can be precipitated polymerized in the presence of a free radical initiator in a suitable organic solvent to obtain polydivinylbenzene containing Si-O-Si bond, which is precipitated from the solution. Before polymerization, bis (vinylphenylethyl) disiloxane and divinylbenzene are dissolved in the organic solvent, and as the polymerization proceeds and the degree of polymerization reaches a certain value, the product is phase separated from the organic solvent and precipitated from the system.

[0032] Preferably, in step (2), the temperature of the precipitation polymerization reaction is 65-80℃, and the reaction time is 8-12h.

[0033] Preferably, in step (2), the organic solvent is any one or a combination of ethanol, acetonitrile, petroleum ether, and toluene, and the mass of the organic solvent is 1.5-2.5 times the total mass of divinylbenzene and hydrogen-containing disiloxane.

[0034] Preferably, in step (2), the initiator is azobisisobutyronitrile (AIBN) or dicumyl peroxide (DCP), and the amount of the initiator is 1.0%-3.0% of the total mass of divinylbenzene and hydrogen-containing disiloxane.

[0035] Preferably, in step (2), the precipitation polymerization reaction is carried out under stirring at a stirring speed of 750-950r / min.

[0036] Preferably, in step (2), after the precipitation polymerization reaction is completed, the organic solvent is removed by suction filtration and vacuum drying.

[0037] Preferably, in step (2), the preparation reaction of polydivinylbenzene containing Si-O-Si bond is shown in the following schematic formula:

[0038] In the formula, R1 is methyl, and R2 is methyl or phenyl.

[0039] In a third aspect, the application further provides an application of the polydivinylbenzene containing Si-O-Si bond in reducing the water content of electronic gas hydrogen bromide, characterized in that it comprises the following steps: (3) The polydivinylbenzene containing Si-O-Si bond and a Lewis acid catalyst are mixed uniformly and then filled into a reaction tower, dry HBr gas is introduced into the reaction tower under reduced pressure to make the HBr gas contact with the polydivinylbenzene containing Si-O-Si bond, and the Si-O-Si bond is converted into a Si-Br bond through heating reaction to obtain polydivinylbenzene containing Si-Br bond; (4) After the reaction in step (3) is completed, water-containing HBr gas is introduced into the reaction tower so that the HBr gas comes into contact with the polyvinylbenzene containing Si-Br bonds. The water content in the HBr gas is reduced through the hydrolysis reaction of Si-Br bonds.

[0040] The electronegativity of silicon (Si) is 1.8, and that of oxygen (O) is 3.0. The Si-O-Si bond exhibits strong polarity and readily reacts with nucleophiles (such as HBr) to form Si-X bonds. This invention uses ZnBr2 or MgBr2 as a catalyst to react the aforementioned Si-O-Si bond-containing polyvinylbenzene with dry HBr to obtain Si-Br bond-containing polyvinylbenzene.

[0041] Preferably, in step (3), the Lewis acid catalyst is ZnBr2 or MgBr2. ZnBr2 and MgBr2 have moderate catalytic activity, which can efficiently catalyze the Si-O-Si nucleophilic reaction while avoiding the Si-C cleavage reaction, ensuring that the generated Si-Br bonds are firmly bound in the cross-linked polyvinylbenzene structure. Both ZnBr2 and MgBr2 are solid bromides with stable structures and will not introduce new impurities into HBr.

[0042] Preferably, in step (3), the mass ratio of Lewis acid catalyst to Si-O-Si bonded polyvinylbenzene is 3 to 5:100.

[0043] Preferably, in step (3), the volume content of moisture in the dried HBr is not higher than 1.0 × 10⁻⁶. -9 .

[0044] Preferably, in step (3), the flow rate of the dried HBr is 0.5 L / min to 5.0 L / min; more preferably, the flow rate of the dried HBr gradually increases with the reaction time. A high flow rate of dried HBr facilitates the rapid discharge of H2O and the conversion of Si-O-Si to Si-Br. However, an excessively high flow rate results in significant energy loss.

[0045] Preferably, in step (3), the Si-O-Si bonded polyvinylbenzene reacts with dry HBr under reduced pressure, with a reaction pressure of 10 kPa to 80 kPa; more preferably, the reaction pressure gradually decreases with increasing reaction time. Reducing the reaction pressure facilitates the rapid discharge of the generated H2O with the HBr gas from the reaction tower, promoting the conversion of Si-O-Si to Si-Br.

[0046] Preferably, in step (3), the heating reaction temperature is 80℃~105℃. Increasing the reaction temperature accelerates the reaction rate between Si-O-Si and HBr, and also facilitates the removal of generated H2O from the system with HBr; if the reaction temperature is too high, side reactions increase, leading to the breakage of Si-C bonds.

[0047] Preferably, in step (3), the H2O content in the exhaust gas is measured using a moisture analyzer to track the reaction progress. As the Si-O-Si bonds are broken down by HBr into Si-Br bonds and H2O, the H2O content in the exhaust gas gradually increases; when the Si-O-Si bond reaction is complete, the residual H2O in the reaction tower decreases with the continuous introduction of dry HBr. When the H2O volume content drops to 1.0 × 10⁻⁶, the H2O content decreases. -8 If the reaction proceeds as follows, the reaction is considered complete, yielding a polyvinylbenzene containing Si-Br bonds.

[0048] Preferably, in step (3), the water-containing HBr gas discharged from the reaction tower is reused after being dried by molecular sieve adsorption and chemical dehydration.

[0049] Preferably, in step (3), the reaction scheme for converting Si-O-Si bonded polyvinylbenzene into Si-Br bonded polyvinylbenzene is as follows: .

[0050] Preferably, in step (4), the initial H2O volume content in the aqueous HBr gas is 1×10⁻⁶. -6 ~1×10 -5 .

[0051] Preferably, in step (4), the flow rate of the water-containing HBr gas is 0.5 L / min to 2.0 L / min.

[0052] Preferably, in step (4), the Si-Br bond hydrolysis reaction temperature is -10℃ to 10℃. A low hydrolysis temperature results in incomplete hydrolysis; a high reaction temperature leads to the formation of the byproduct H2O, weakening the dehydration effect.

[0053] Preferably, in step (4), the volume content of water in the HBr gas after water removal is 1.0 × 10⁻⁶. -8 ~1×10 -7 .

[0054] Preferably, in step (4), the dehydration mechanism of Si-Br bonded polyvinylbenzene is as follows:

[0055] Therefore, the present invention has the following beneficial effects: (1) This invention combines hydrosilylation and precipitation polymerization to prepare polydivinylbenzene containing Si-O-Si bonds through in-situ synthesis. This method efficiently introduces Si-O-Si bonds into the polydivinylbenzene skeleton, improving its high-temperature resistance and toughness, while also providing new reactivity.

[0056] (2) This invention innovatively utilizes a Lewis acid catalyst and heating conditions to induce a nucleophilic reaction between Si-O-Si bonded polyvinylbenzene and HBr to obtain Si-Br bonded polyvinylbenzene, which is then used as an HBr electronic gas dehydrating agent. Compared with existing HBr gas dehydration methods, this method avoids the hydrolysis reaction of chemical dehydrating agents during production, transfer, and storage, is environmentally friendly, does not introduce metal impurities, and has a good dehydration effect. Attached Figure Description

[0057] Figure 1 Infrared spectrum of a mixture of bis(vinylphenylethyl)tetramethyldisiloxane and divinylbenzene.

[0058] Figure 2 Infrared spectrum of divinylbenzene containing silicon-oxygen-silicon bonds. Detailed Implementation

[0059] The present invention will be further described below with reference to specific embodiments. Those skilled in the art will be able to implement the present invention based on these descriptions. Furthermore, the embodiments of the present invention described below are generally only some, not all, of the embodiments of the present invention. Therefore, all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0060] Example 1 100.0 g of divinylbenzene and 0.30 g of Castells catalyst (platinum content 0.5%) were added to a reaction flask and mixed thoroughly with stirring at 450 rpm. Then, 46.8 g of HMe₂SiOSiMe₂H was added dropwise over 2 hours. After the addition was complete, the reaction was continued at room temperature for 6 hours. Infrared spectroscopy analysis showed that the chromatogram was positive at 2160 cm⁻¹. -1 The disappearance of the Si-H absorption peak indicates that the HMe2SiOSiMe2H reaction is complete. 367.0 g of ethanol and 1.5 g of AIBN were added to the reaction flask, stirred at 750 r / min until homogeneous, heated to 65 °C, and reacted for 8 h. The mixture was then filtered and dried under vacuum to obtain 102.0 g of polyvinylbenzene containing Si-O-Si bonds.

[0061] The 102.0 g of Si-O-Si bonded polyvinylbenzene and 3.1 g of ZnBr2 prepared above were mixed evenly and then loaded into a reaction tower equipped with a vacuum system. A water content of 1.0 × 10⁻⁶ g was introduced from the bottom of the reaction tower. -9Dry HBr gas was introduced at a flow rate of 0.5 L / min to 3.0 L / min to contact the HBr gas with divinylbenzene containing Si-O-Si bonds. The reaction temperature was maintained at 105 °C, and the reaction pressure was controlled at 10 kPa to 40 kPa. After 6.0 h of reaction, the volume content of moisture in the HBr gas discharged from the reaction tower was 9.5 × 10⁻⁶ m³ / h, as measured by a trace moisture gas analyzer. -9 This indicates that the Si-O-Si bonded polyvinylbenzene has been converted to the Si-Br bonded polyvinylbenzene, and the introduction of dry HBr gas is stopped. The water content introduced from the bottom of the reaction tower is 1.0 × 10⁻⁶. -5 HBr gas at a flow rate of 0.5 L / min was introduced into contact with divinylbenzene containing Si-Br bonds, and the reaction temperature was maintained at -10℃. After 3.0 h of reaction, the volume content of moisture in the discharged HBr gas was measured to be 9.8 × 10⁻⁶ m³ / h using a trace moisture gas analyzer. -8 .

[0062] Figure 1 This is the infrared spectrum of a mixture of bis(vinylphenethyl)tetramethyldisiloxane and divinylbenzene. The value at 2955.31 cm⁻¹ is shown in the figure. -1 These are absorption peaks from the stretching vibrations of the CH bond, at 1601.64 and 1494.25 cm⁻¹. -1 It is the absorption peak of the stretching vibration of the benzene ring and the C=C in CH2=CH-, at 1450.50 cm⁻¹. -1 It is the absorption peak of the -CH2- bending vibration, at 1252.19 cm⁻¹. -1 It is the absorption peak of the Si-CH3 symmetric deformation vibration, at 1053.34 cm⁻¹. -1 It is the absorption peak of the stretching vibration of the Si-O-Si bond, at 905.89 cm⁻¹. -1 It is the absorption peak of the deformation vibration of the Si-C bond, 774.07 cm⁻¹. -1 This is the absorption peak due to the CH bond bending vibration. 2160 cm⁻¹ -1 The absorption peak of the Si-H bond stretching vibration disappeared. Infrared spectroscopy results indicate that the structure of the reaction product is as expected.

[0063] Figure 2 This is the infrared spectrum of divinylbenzene containing Si-O-Si bonds. The image shows a peak length of 2920.83 cm⁻¹. -1 It is the absorption peak of the stretching vibration of the CH bond, at 1601.78 cm⁻¹. -1 It is the absorption peak of the C=C stretching vibration in the benzene ring, at 1444.07 cm⁻¹. -1 It is the absorption peak of the -CH2- group bending vibration, at 1251.00 cm⁻¹. -1 It is the absorption peak of the Si-CH3 symmetric deformation vibration, at 1047.34 cm⁻¹. -1It is the absorption peak of the stretching vibration of the Si-O-Si bond, at 834.25 cm⁻¹. -1 It is the absorption peak of the Si-C bond deformation vibration, 785.10 cm⁻¹. -1 The peak is an absorption peak due to the bending vibration of the CH bond. Infrared spectroscopy results indicate that the structure of the reaction product is as expected.

[0064] Table 1 shows the change in the volume content of moisture in the HBr gas discharged from the reaction tower with reaction time during the reaction of Si-O-Si bonded polyvinylbenzene with dry HBr.

[0065] Table 1. Changes in water volume content with reaction time Reaction time (h) Dry HBr gas flow rate (L / min) Reaction pressure (kPa) Moisture volume content 1.0 0.5 40 1.3 x 10 -6 ]]> 2.0 1.0 40 2.9 x 10 -6 ]] 3.0 2.0 20 1.8 x 10 -6 ]]> 4.0 2.5 20 9.5 x 10 -7 ]]> 5.0 3.0 10 1.5 x 10 -7 ]]> 6.0 3.0 10 9.5 x 10 -9 ]]> As shown in Table 1, the volume content of water in the HBr gas discharged from the reaction tower first increases and then decreases with increasing reaction time. When the reaction time is 6.0 h, the volume content of water is 9.5 × 10⁻⁶. -9 less than 1×10 -8 This indicates that the polyvinylbenzene containing Si-O-Si bonds has been completely converted into polyvinylbenzene containing Si-Br bonds.

[0066] Table 2 shows the change in the volume content of water in the HBr gas discharged from the reaction tower with reaction time during the hydrolysis reaction of polydivinylbenzene containing Si-Br bonds.

[0067] Table 2. Changes in the volumetric water content of HBr with reaction time. Reaction time (h) Moisture volume content 0.5 6.7 x 10 -6 ]]> 1.0 4.1 x 10 -6 ]]> 1.5 2.1 x 10 -6 ]]> 2.0 8.7 x 10 -7 ]] 2.5 2.5 x 10 -7 ]]> 3.0 9.8 x 10 -8 ]] Table 2 shows that the water content in HBr gas decreases with increasing hydrolysis reaction time. When the reaction time is 3.0 h, the water volume content in HBr gas is 9.8 × 10⁻⁶. -8 .

[0068] Example 2 100.0 g of divinylbenzene and 1.65 g of Castrol catalyst (platinum content 0.5%) were added to a reaction flask and mixed thoroughly with stirring at 850 rpm. Then, 67.0 g of HMePhSiOSiMePhH was added dropwise over 4 hours. After the addition was complete, the reaction was continued at room temperature for 2 hours. Infrared spectroscopy revealed a result at 2160 cm⁻¹. -1 The disappearance of the Si-H absorption peak indicates that the HMePhSiOSiMePhH reaction is complete. 255g of acetonitrile and 5.0g of DCP were added to the reaction flask, stirred at 950r / min until homogeneous, heated to 70℃, and reacted for 12h. The mixture was then filtered and dried under vacuum to obtain 141.5g of Si-O-Si bonded polyvinylbenzene.

[0069] The 141.5g of Si-O-Si bonded polyvinylbenzene and 7.0g of MgBr2 prepared above were mixed evenly and then loaded into a reaction tower equipped with a vacuum system. A water content of 1.0 × 10⁻⁶ g was introduced from the bottom of the reaction tower. -9 Dry HBr gas was introduced at a flow rate of 0.5 L / min to 5.0 L / min, and then brought into contact with divinylbenzene containing Si-O-Si bonds. The reaction temperature was maintained at 80 °C, and the reaction pressure was controlled at 40 kPa to 80 kPa. After 5.0 h of reaction, the volume content of moisture in the HBr gas discharged from the reaction tower was 9.3 × 10⁻⁶ m³ / h, as measured by a trace moisture gas analyzer. -9 This indicates that the Si-O-Si bonded polyvinylbenzene has been converted to the Si-Br bonded polyvinylbenzene, and the introduction of dry HBr gas is stopped. The water content introduced from the bottom of the reaction tower is 1.0 × 10⁻⁶. -6 HBr gas was introduced at a flow rate of 1.0 L / min to contact Si-Br bonded polyvinylbenzene, and the reaction temperature was maintained at 10 °C. After 2.0 h of reaction, the water content in the HBr gas discharged from the reaction tower was measured by a trace moisture gas analyzer to be 1.0 × 10⁻⁶ m³ / h. -8 .

[0070] Infrared absorption peaks of a mixture of bis(vinylphenethyl)dimethyldiphenyldisiloxane and divinylbenzene: 2972.41, 1603.25, 1498.36, 1452.23, 1256.31, 1055.72, 906.75, 785.04 cm⁻¹ -1 .

[0071] Infrared absorption peaks of polyvinylbenzene containing Si-O-Si bonds: 2925.32, 1600.51, 1492.39, 1442.54, 1253.76, 1040.29, 856.68, 787.13 cm⁻¹ -1 .

[0072] Table 3 shows the change in the volume content of moisture in the HBr gas discharged from the reaction tower with reaction time during the reaction of Si-O-Si bonded polyvinylbenzene with dry HBr.

[0073] Table 3. Changes in water volume content with reaction time. Reaction time (h) Dry HBr gas flow rate (L / min) Reaction pressure (kPa) Moisture volume content 1.0 0.5 80 3.5 x 10 -7 ]]> 2.0 1.5 60 4.1 x 10 -6 ]]> 3.0 3.5 60 1.9 x 10 -6 ]] 4.0 4.5 40 2.1 x 10 -7 ]]> 5.0 5.0 40 9.3 x 10 -9 ]]> Table 4 shows the change in the volume content of water in the HBr gas discharged from the reaction tower with reaction time during the hydrolysis reaction of polydivinylbenzene containing Si-Br bonds.

[0074] Table 4. Changes in water volume content with hydrolysis reaction time. Reaction time (h) Moisture volume content 0.5 6.1 x 10 -7 ]]> 1.0 1.6 x 10 -7 ]]> 1.5 5.6 x 10 -8 ]]> 2.0 1.0 x 10 -8 ]]> Example 3 100.0 g of divinylbenzene and 0.85 g of Castells catalyst (platinum content 0.5%) were added to a reaction flask and mixed thoroughly with stirring at 600 rpm. Then, 41.0 g of HMe₂SiOSiMe₂H was added dropwise over 2.5 h. After the addition was complete, the reaction was continued at room temperature for 3 hours. Infrared spectroscopy analysis showed that the chromatogram was positive at 2160 cm⁻¹. -1 The disappearance of the Si-H absorption peak indicates that the HMe2SiOSiMe2H reaction is complete. 280g of petroleum ether and 2.8g of AIBN were added to the reaction flask, stirred at 800r / min until homogeneous, heated to 75℃, and reacted for 10h. The mixture was then filtered and dried under vacuum to obtain 113.6g of polyvinylbenzene containing Si-O-Si bonds.

[0075] The 113.6 g of Si-O-Si bonded polyvinylbenzene and 4.6 g of ZnBr2 prepared above were mixed evenly and then loaded into a reaction tower equipped with a vacuum system. A water content of 1.0 × 10⁻⁶ g was introduced from the bottom of the reaction tower. -9 Dry HBr gas was introduced at a flow rate of 2.0 L / min to contact the HBr gas with divinylbenzene containing Si-O-Si bonds. The reaction temperature was maintained at 90℃, and the reaction pressure was controlled at 10 kPa to 80 kPa. After 5.0 h of reaction, the volume content of moisture in the gas discharged from the reaction tower was 9.6 × 10⁻⁶ m³ / h, as measured by a trace moisture gas analyzer. -8 This indicates that the Si-O-Si bonded polyvinylbenzene has been converted to the Si-Br bonded polyvinylbenzene, and the introduction of dry HBr gas should be stopped. The water content introduced from the bottom of the reaction tower is 3.5 × 10⁻⁶. -6 HBr gas at a flow rate of 2.0 L / min was introduced into contact with Si-Br bonded polyvinylbenzene, and the reaction temperature was maintained at 0 °C. After 2.0 h of hydrolysis, the water content in the HBr gas discharged from the reaction tower was 3.0 × 10⁻⁶ by volume analysis using a trace moisture gas analyzer. -8 .

[0076] Infrared absorption peaks of a mixture of bis(vinylphenethyl)tetramethyldisiloxane and divinylbenzene: 2962.51, 1600.75, 1496.58, 1450.47, 1254.63, 1038.92, 908.30, 780.86 cm⁻¹ -1 .

[0077] Infrared absorption peaks of poly(divinylbenzene) containing Si-O-Si bonds: 2943.18, 1602.63, 1495.21, 1446.38, 1254.68, 1035.41, 859.42, 782.06 cm⁻¹ -1 .

[0078] Table 5 shows the change in the volume content of moisture in the HBr gas discharged from the reaction tower with reaction time during the reaction of Si-O-Si bonded polyvinylbenzene with dry HBr.

[0079] Table 5. Changes in water volume content with reaction time. Reaction time (h) Dry HBr gas flow rate (L / min) Reaction pressure (kPa) Moisture volume content 1.0 2.0 80 1.8 x 10 -6 ]]> 2.0 2.0 60 4.2 x 10 -6 ]]> 3.0 2.0 40 1.1 x 10 -6 ]]> 4.0 2.0 20 1.3 x 10 -7 ]]> 5.0 2.0 10 9.6 x 10 -9 ]]> Table 6 shows the change in the volume content of water in the HBr gas discharged from the reaction tower with reaction time during the hydrolysis reaction of polydivinylbenzene containing Si-Br bonds.

[0080] Table 6. Changes in water volume content with reaction time. Reaction time (h) Moisture volume content 0.5 1.8 x 10 -6 ]]> 1.0 9.2 x 10 -7 ]]> 1.5 1.4 x 10 -7 ]]> 2.0 3.0 x 10 -8 ]]> Example 4 100.0 g of divinylbenzene and 1.37 g of Castells catalyst (platinum content 0.5%) were added to a reaction flask and mixed thoroughly with stirring at 750 rpm. Then, 71.0 g of HMePhSiOSiMePhH was added dropwise over 3.0 h. After the addition was complete, the reaction was allowed to continue at room temperature for 2.5 h. Infrared spectroscopy revealed a result at 2160 cm⁻¹. -1 The disappearance of the Si-H absorption peak indicates that the HMePhSiOSiMePhH reaction is complete. 340 g of toluene and 3.1 g of AIBN were added to the reaction flask, stirred at 900 r / min until homogeneous, heated to 80 °C, and reacted for 9 h. The mixture was then filtered and dried under vacuum to obtain 140.0 g of Si-O-Si bonded polyvinylbenzene.

[0081] The 140.0 g of Si-O-Si bonded polyvinylbenzene and 4.9 g of MgBr2 prepared above were mixed evenly and then loaded into a reaction tower equipped with a vacuum system. A water content of 1.0 × 10⁻⁶ g was introduced from the bottom of the reaction tower. -9 Dry HBr gas was introduced at a flow rate of 2.5 L / min to 5.0 L / min to contact the HBr gas with divinylbenzene containing Si-O-Si bonds. The reaction temperature was maintained at 85 °C, and the reaction pressure was controlled at 30 kPa. After 5.0 h of reaction, the volume content of moisture in the gas discharged from the reaction tower was 9.1 × 10⁻⁶ m³ / h, as measured by a trace moisture gas analyzer. -9 This indicates that the Si-O-Si bonded polyvinylbenzene has been converted to the Si-Br bonded polyvinylbenzene, and the introduction of dry HBr gas should be stopped. The volume content of water introduced from the bottom of the reaction tower is 6.2 × 10⁻⁶. -6 HBr gas at a flow rate of 1.5 L / min was introduced into contact with Si-Br bonded divinylbenzene, and the reaction temperature was maintained at -5℃. After 2.5 h of reaction, the volume content of moisture in the HBr gas discharged from the reaction tower was 6.7 × 10⁻⁶ m³ / h, as measured by a trace moisture gas analyzer. -8 .

[0082] Infrared absorption peaks of a mixture of bis(vinylphenethyl)dimethyldiphenyldisiloxane and divinylbenzene: 2957.82, 1603.42, 1495.47, 1448.31, 1257.60, 1033.15, 905.93, 784.25 cm⁻¹ -1 .

[0083] Infrared absorption peaks of poly(divinylbenzene) containing Si-O-Si bonds: 2965.12, 1600.57, 1492.14, 1445.25, 1256.67, 1034.28, 865.19, 785.54 cm⁻¹ -1 .

[0084] Table 7 shows the change in the volume content of moisture in the HBr gas discharged from the reaction tower with reaction time during the reaction of Si-O-Si bonded polyvinylbenzene with dry HBr.

[0085] Table 7. Changes in moisture content with reaction time Reaction time (h) Dry HBr gas flow rate (L / min) Reaction pressure (kPa) Moisture volume content 1.0 2.5 30 1.5 x 10 -6 ]]> 2.0 3.0 30 2.5 x 10 -6 ]]> 3.0 3.5 30 6.4 x 10 -7 ]]> 4.0 4.0 30 9.0 x 10 -8 <!-- 10 -->]]> 5.0 5.0 30 9.1 x 10 -9 ]]> Table 8 shows the change in water volume content in the HBr gas discharged from the reaction tower with reaction time during the hydrolysis reaction of polydivinylbenzene containing Si-Br bonds.

[0086] Table 8. Changes in moisture content with hydrolysis reaction time. Reaction time (h) Moisture volume content 0.5 4.8 x 10 -6 ]]> 1.0 2.2 x 10 -6 ]]> 1.5 9.8 x 10 -7 ]]> 2.0 2.1 x 10 -7 ]]> 2.5 6.7 x 10 -8 ]]> The specific embodiments described herein are merely illustrative of the spirit of the invention. Those skilled in the art to which this invention pertains may make various modifications or additions to the described specific embodiments or use similar methods to substitute them, without departing from the spirit of the invention or exceeding the scope defined by the appended claims.

Claims

1. A polyvinylbenzene containing silicon-oxygen-silicon bonds, characterized in that, Includes a polyvinylbenzene backbone; The polydivinylbenzene backbone contains silicon-oxygen-silicon bonds; The silicon-oxygen-silicon bond structure is as follows: ， In the formula, R1 is methyl, and R2 is methyl or phenyl.

2. A method for preparing the silicon-oxygen-silicon bonded polyvinylbenzene as described in claim 1, characterized in that, Includes the following steps: (1) In the presence of a platinum catalyst, excess divinylbenzene undergoes a hydrosilylation reaction with hydrogen-containing disiloxane to obtain a mixture of bis(vinylphenylethyl)disiloxane and divinylbenzene; (2) Add an organic solvent and an initiator to the mixture of bis(vinylphenylethyl)disiloxane and divinylbenzene obtained in step (1), and then perform precipitation polymerization to obtain the silicon-oxygen-silicon bonded polyvinylbenzene.

3. The preparation method according to claim 2, characterized in that, The hydrogen-containing disiloxane is 1,3-dihydro-1,1,3,3-tetramethyldisiloxane or 1,3-dihydro-1,3-dimethyl-1,3-diphenyldisiloxane.

4. The preparation method according to claim 2 or 3, characterized in that, The molar ratio of the divinylbenzene to the hydrogen-containing disiloxane is 2.2 to 3.0:

1.

5. The preparation method according to claim 2, characterized in that, The platinum catalyst is a cassiterite catalyst, and its amount, based on the mass of platinum, is 0.001% to 0.005% of the total mass of divinylbenzene and hydrogen-containing disiloxane.

6. The preparation method according to claim 2, characterized in that, The precipitation polymerization reaction temperature is 65℃~80℃ and the reaction time is 8h~12h; the organic solvent is any one or more combinations of ethanol, acetonitrile, petroleum ether, and toluene; the initiator is azobisisobutyronitrile or diisopropylbenzene peroxide.

7. The application of the silicon-oxygen-silicon bonded polyvinylbenzene as described in claim 1 in reducing the moisture content of hydrogen bromide in electronic gases, characterized in that... Includes the following steps: (3) After the silicon-oxygen-silicon bonded polyvinylbenzene and Lewis acid catalyst are mixed evenly, they are filled into the reaction tower. Dry hydrogen bromide gas is introduced into the reaction tower under reduced pressure so that the hydrogen bromide gas comes into contact with the silicon-oxygen-silicon bonded polyvinylbenzene and is heated to react, so that the Si-O-Si bond is converted into the Si-Br bond, and the Si-Br bonded polyvinylbenzene is obtained. (4) After the reaction in step (3) is completed, water-containing hydrogen bromide gas is introduced into the reaction tower so that the hydrogen bromide gas comes into contact with the polyvinylbenzene containing Si-Br bonds. Through the hydrolysis reaction of Si-Br bonds, the moisture content in the hydrogen bromide gas is reduced.

8. The application according to claim 7, characterized in that, The Lewis acid catalyst is zinc bromide or magnesium bromide, and the mass ratio of the Lewis acid catalyst to the silicon-oxygen-silicon bonded polyvinylbenzene is 3-5:100; the pressure under the reduced pressure condition is 10 kPa-80 kPa; and the heating reaction temperature is 80℃-105℃.

9. The application according to claim 7, characterized in that, The hydrolysis reaction temperature is -10℃ to 10℃.

10. The application according to claim 7, characterized in that, The water content in the aqueous hydrogen bromide gas is 1×10⁻⁶ by volume. -6 ~1×10 -5 .

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