CN114835126A - Preparation method and device of diiodosilane - Google Patents
Preparation method and device of diiodosilane Download PDFInfo
- Publication number
- CN114835126A CN114835126A CN202210638045.6A CN202210638045A CN114835126A CN 114835126 A CN114835126 A CN 114835126A CN 202210638045 A CN202210638045 A CN 202210638045A CN 114835126 A CN114835126 A CN 114835126A
- Authority
- CN
- China
- Prior art keywords
- microchannel
- temperature
- channel
- diiodosilane
- precooling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- AIHCVGFMFDEUMO-UHFFFAOYSA-N diiodosilane Chemical compound I[SiH2]I AIHCVGFMFDEUMO-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000011630 iodine Substances 0.000 claims abstract description 42
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 42
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 41
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims abstract description 33
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000011541 reaction mixture Substances 0.000 claims abstract description 10
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005086 pumping Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims abstract description 3
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000002572 peristaltic effect Effects 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 8
- -1 phenylsilane compound Chemical class 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910000856 hastalloy Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 abstract description 15
- 239000000463 material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 229960001701 chloroform Drugs 0.000 description 14
- 239000011259 mixed solution Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 238000004364 calculation method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000010606 normalization Methods 0.000 description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/10778—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention relates to a preparation method and a device of diiodosilane, relating to the field of a synthetic method of a semiconductor material, and comprising the following steps of 1, mixing and dissolving iodine and at least one of chloroform, dichloromethane and dichloroethane according to a volume ratio of 1 (2-5); the mass ratio of the phenylsilane to at least one of ethyl acetate, tert-butyl acetate and butyl acetate is 100: (1-5) mixing; pre-cooling the iodine solution and the phenylsilane solution at the temperature of-40-0 ℃; pumping into a microchannel reactor, mixing and reacting at a low temperature of-40-10 ℃ for 100-300 s in a microchannel, and then reacting at a room temperature of 20-30 ℃ for 100-400 s in a microchannel to obtain a reaction mixture; and 2, carrying out reduced pressure rectification on the reaction mixture obtained in the step 1, and collecting a product with the fraction temperature of 35-40 ℃ under 20 +/-3 mmHg to obtain the high-purity diiodosilane. The diiodosilane is synthesized by the microchannel reactor, the original synthesis period can be reduced to 700 seconds, the content of the obtained mixture product is high, and the content of impurity metal ions is low.
Description
Technical Field
The invention relates to the field of synthesis methods of semiconductor materials, in particular to a preparation method and a device of diiodosilane.
Background
High purity diiodosilane plays an increasingly important role in high-end semiconductor chips as a silicon source for chemical Vapor deposition, which can deposit silicide films on a wide variety of semiconductor substrates by Vapor phase chemical cvd (chemical Vapor deposition) and atomic layer deposition ald (atomic layer deposition) methods at lower temperatures and with more controlled pressure operation. The diiodosilane has unique advantages and wide market prospect. However, the existing synthesis method of high-purity diiodosilane is complex and dangerous, so that the industrialization of the product is severely limited, the application direction determines that the purity requirement is high, and the preparation of the product with 99.9999 +% effective purity is also a very great challenge.
At present, the synthetic method of diiodosilane mainly comprises the following steps:
firstly, the method comprises the following steps: synthesizing diiodosilane by using dichlorosilane and lithium iodide. WO2019/212808 discloses a process for preparing diiodosilane by reacting dichlorosilane through a jacketed stainless steel tube containing anhydrous lithium iodide at a temperature of 40 ℃ to obtain a mixture containing diiodosilane, and rectifying and purifying to obtain the product. Although the method is feasible, the content of chloride ions in the product is not well controlled; and because the equipment is complicated, hydrochloric acid gas is easy to escape, the equipment is harmful to the environment, and industrialization is not easy to realize.
Secondly, the method comprises the following steps: hydrogen iodide reacts with diphenylsilane. Ben Altabef, Aida, Oberhammer, Heinz describes the reaction of hydrogen iodide gas at-40 ℃ into a diphenylsilane system followed by rectification to give the product [ Journal of Molecular Structure,2002, vol.641, #2-3, p.259-261 ]. The method has the defects that hydrogen iodide gas is not easy to obtain, and no supplier exists in China.
Thirdly, the method comprises the following steps: iodine reacts with phenyl silane, chloroform is used as a solvent, ethyl acetate is used as a catalyst, the iodine and chloroform are firstly added into a reaction bottle, the phenyl silane and the ethyl acetate are mixed and dripped at a low temperature, and then the temperature is gradually raised in stages, but a severe temperature rise stage occurs in the reaction process, and the temperature is difficult to control, so that the industrialization is difficult to realize. The Shanzhong Hutke corporation in patent No. CN111072030A describes a method for increasing the reaction speed by increasing the temperature by continuously or intermittently taking out a small amount of the reaction mixture from the reaction tank during the gradual temperature increase, i.e., by performing the step of removing the reaction mixture while increasing the temperature. Since the reaction mixture is continuously or intermittently taken out from the reaction tank in a small amount, even if the reaction speed is increased by raising the temperature, the reaction temperature becomes easy to control, so that the risk of reaction runaway can be reduced. In this way, Shanzhong Hutecg, Inc. solved the problem of heat release during the industrial preparation. However, the device is too complex and has low reaction efficiency, and chloroform, which is a solvent adopted in the method, is easy to poison, thereby further limiting the industrial production of the method.
Therefore, the application provides a novel method for synthesizing high-purity diiodosilane, aiming at the problems of long synthesis period, complex reaction, more byproducts and difficulty in realizing product purification caused by the phenomena that raw materials are difficult to obtain, the device requirement is high or the reaction heat release is difficult to control in the method.
Disclosure of Invention
The invention aims to provide a method and a device for preparing diiodosilane. According to the invention, the micro-channel reactor is utilized to continuously synthesize diiodosilane, so that the reaction efficiency is obviously improved, and the reaction time is shortened; the large amount of heat release of the system can be stably controlled, compared with the traditional kettle type system, the reaction risk is reduced, and the method is particularly suitable for industrial production; and methylene dichloride or dichloroethane replaces toxic solvents such as chloroform, so that the purification cost is reduced.
In order to solve the above technical problems, a first object of the present invention is to provide a method for preparing diiodosilane, comprising the steps of:
step 1, mixing and dissolving iodine and at least one of chloroform, dichloromethane and dichloroethane according to a volume ratio of 1 (2-5) to obtain an iodine solution; mixing phenylsilane with at least one of ethyl acetate, tert-butyl acetate and butyl acetate in a mass ratio of 100: (1-5) mixing to obtain a phenylsilane solution; pre-cooling the obtained iodine solution and the obtained phenylsilane solution at the temperature of minus 40-0 ℃, then respectively pumping into a microchannel reactor, mixing and reacting for 100-300 s in a low-temperature microchannel at the temperature of minus 40-10 ℃, and then continuously reacting for 100-400 s in a room-temperature microchannel at the temperature of 20-30 ℃ to obtain a reaction mixture;
and 2, carrying out reduced pressure rectification on the reaction mixture obtained in the step 1, and collecting a product with the fraction temperature of 35-40 ℃ under 20 +/-3 mmHg to obtain the high-purity diiodosilane.
The reaction equation is as follows:
wherein, the structural formula of the diiodosilane is as follows:
the invention has the beneficial effects that: the invention synthesizes diiodosilane by using the microchannel reactor, the microchannel reactor has better heat exchange efficiency, surface area and special material, the original synthesis period can be reduced to be less than 700s, and the obtained mixture has high product content and low impurity metal ion content.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in step 1, in the microchannel reactor, firstly, the mixture reacts for 150-.
Further, in the step 1, the ratio of the iodine in the iodine solution pumped into the microchannel reactor to the amount of the phenylsilane material in the phenylsilane solution is (1:2) to (2: 1).
Further, in the step 1, when the iodine solution is pumped into a microchannel reactor, the flow ratio of the iodine solution to the phenylsilane solution is (6-10): 1.
the beneficial effect of adopting the further scheme is that: under the conditions of the above reaction, the yield of diiodosilane obtained is higher.
Further, in step 1, the microchannel reactor uses an inert gas to displace the internal gas before pumping in the iodine solution and the phenylsilane solution. The inert gas can be nitrogen or argon; wherein the nitrogen used is high-purity nitrogen.
The beneficial effect of adopting the further scheme is that: the air of the microchannel reactor is replaced by inert gas, so that the reaction risk is effectively reduced, and the reaction efficiency is improved.
The second purpose of the invention is to provide a device for preparing diiodosilane, which comprises two groups of raw material tanks, a first metering peristaltic pump, a second metering peristaltic pump, a precooling microchannel I, a precooling microchannel II and a microchannel reactor; the group of raw material tanks are communicated with the first metering peristaltic pump, the first metering peristaltic pump is communicated with the precooling microchannel I, and the precooling microchannel I is communicated with the microchannel reactor; and the other group of the raw material tanks is communicated with the second metering peristaltic pump, the second metering peristaltic pump is communicated with the precooling microchannel II, and the precooling microchannel II is communicated with the microchannel reactor.
The beneficial effect who adopts above-mentioned scheme is: by adopting the precooling microchannels I and II and the microchannel reactor, the mass transfer and heat transfer performance can be enhanced, the rapid and complete reaction can be realized, the sudden and violent temperature rise can be avoided, and the occurrence of side reactions can be reduced.
Further, the microchannel reactor is a continuous flow microchannel reactor; the microchannel reactor consists of a low-temperature microchannel and a room-temperature microchannel, and the low-temperature microchannel is communicated with the room-temperature microchannel.
The beneficial effect of adopting the further scheme is that: the micro-channel reactor can be used for realizing the continuous synthesis of diiodosilane; the iodine solution and the phenylsilane solution are precooled and enter the microchannel reactor after passing through the precooled microchannel I and the precooled microchannel II respectively, and then react in the low-temperature microchannel, and then react in the microchannel at room temperature, so that the reaction is quickly and fully completed.
Furthermore, the channel of the precooling microchannel I is a snake-shaped, rhombus-shaped or heart-shaped channel, and the channel of the precooling microchannel II is a snake-shaped, rhombus-shaped or heart-shaped channel; the channel of the low-temperature micro-channel is a snake-shaped, rhombus-shaped or heart-shaped channel; the channel of the room temperature micro-channel is a snake-shaped, rhombus-shaped or heart-shaped channel.
Further, the length of the precooling microchannel I is 6-12m, and the radial width is 1-3 mm; the length of the precooling micro-channel II is 6-12m, and the radial width is 1-3 mm; the length of the low-temperature micro-channel is 6-12m, and the radial width is 1-3 mm; the length of the room temperature micro-channel is 6-12m, and the radial width is 1-3 mm.
The beneficial effect of adopting the further scheme is that: by controlling the shapes and the lengths of the micro-channels pumped into the pre-cooling micro-channel I, the pre-cooling micro-channel II, the low-temperature micro-channel and the room-temperature micro-channel, the proportion and the reaction time of materials can be accurately controlled. Precooling micro-channels I and II are connected with a micro-channel reactor, so that the reaction temperature is easier to control.
Further, the microchannel reactor is made of hastelloy or silicon carbide; the first metering peristaltic pump for pumping the iodine solution is made of polytetrafluoroethylene; the first metering peristaltic pump which pumps the phenylsilane solution is made of polytetrafluoroethylene.
The beneficial effect of adopting the further scheme is that: the content of impurity metal ions in the reaction can be effectively controlled by changing the materials of the micro-channel reactor, the first metering peristaltic pump and the second metering peristaltic pump.
Drawings
FIG. 1 is a flow diagram of a microchannel reaction according to the present invention;
FIG. 2 is a GC chromatogram of diiodosilane prepared in example 1;
FIG. 3 is a GC chromatogram of diiodosilane prepared in example 2;
FIG. 4 is a GC chromatogram of diiodosilane prepared in example 3;
FIG. 5 is a GC chromatogram of the crude, secondary purified diiodosilane of examples 1-3;
FIG. 6 is a chart of the hydrogen spectrum of the crude, twice purified diiodosilane of examples 1-3;
FIG. 7 is a GC chromatogram of diiodosilane prepared in example 4;
FIG. 8 is a GC chromatogram of diiodosilane prepared in example 5;
FIG. 9 is a diagram of an apparatus for the production process of the present invention.
In the drawings, the components represented by the respective reference numerals are listed below:
the system comprises a 1-iodine solution tank, a 2-phenylsilane solution tank, a 3-first metering peristaltic pump, a 4-second metering peristaltic pump, a 5-precooling microchannel I, a 6-precooling microchannel II, a 7-low-temperature microchannel, an 8-room-temperature microchannel and a 9-crude product receiving tank.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
The GC detection condition is that n-hexane is used for diluting gas phase, the initial temperature of GC is controlled to be 50 ℃, the gas phase is kept for 2min, and after the temperature is raised to 220 ℃ within 10 ℃/min, the gas phase is kept for 2 min; the dosage is 1 mu L.
Example 1: chloroform as iodine solvent
Under the protection of nitrogen, 3518.1g of iodine and 10L of chloroform are prepared into a uniform mixed solution, simultaneously, 1500g of mixed solution of phenylsilane and 58.8ml of ethyl acetate are respectively pumped into a microchannel reactor, and the volume flow ratio of the iodine mixed solution to the phenylsilane solution is 8: 1, precooling at-40 ℃, and then sequentially passing through a low-temperature microchannel at-35 ℃ and a room-temperature microchannel at +25 ℃ for 200s and 300s respectively to obtain a mixture. The mixture was rectified to give 3625g, 92.11% product as a colorless liquid. The calculation method is as follows: 3625/(1500 × 283.91/108.21) × 100% ═ 92.11%.
The diiodosilane was 99.9 +%, as shown in table 1 and fig. 2, using GC chromatographic area normalization.
TABLE 1 purity calculation for diiodosilane from example 1
Example 2: chloroform as iodine solvent
Under the protection of nitrogen, 3518.1g of iodine and 10L of chloroform are prepared into a uniform mixed solution, simultaneously, 1500g of mixed solution of phenylsilane and 58.8ml of ethyl acetate are respectively pumped into a microchannel reactor, and the volume flow ratio of the iodine solution to the phenylsilane solution is 8: 1, precooling at-20 ℃, and then sequentially passing through a low-temperature micro-channel at-15 ℃ and a room-temperature micro-channel at +25 ℃ for 200s and 300s respectively to obtain a mixture. The mixture was rectified to give 3683g, 93.58% product as a colorless liquid. The purity of diiodosilane was greater than 99.9 +%, as shown in table 2 and figure 3, using GC chromatographic area normalization.
Table 2 purity calculation of diiodosilane from example 2
Example 3: chloroform as iodine solvent
Under the protection of nitrogen, 3518.1g of iodine and 10L of chloroform are prepared into a uniform mixed solution, simultaneously, 1500g of mixed solution of phenylsilane and 58.8ml of ethyl acetate are respectively pumped into a microchannel reactor, and the volume flow ratio of the iodine solution to the phenylsilane solution is 10: 1, precooling at 0 ℃, and then sequentially passing through a low-temperature micro-channel at 10 ℃ and a room-temperature micro-channel at +25 ℃ for 100s and 300s respectively to obtain a mixture. The mixture was rectified to give 3541g, 89.97% product as a colorless liquid. The purity of diiodosilane was greater than 99.9 +%, as shown in table 3 and figure 4, using GC chromatographic area normalization.
Table 3 calculation of purity of diiodosilane from example 3
As can be seen from examples 1, 2 and 3, the synthesis time was greatly shortened in the process of synthesizing diiodosilane in the microchannel reactor, and the obtained product content was high. And the problem of a large amount of heat release in the traditional kettle type synthesis is solved, and the synthesis risk is reduced.
The crude products of the batches of the example 1, the example 2 and the example 3 are combined and transferred into a 5L four-neck flask, and the product is distilled under reduced pressure for the second time, so that the gas phase purity of the final product is 99.9 +%, as shown in Table 4 and figure 5; h 1 NMR hydrogen spectrum showed diiodosilane, H 1 NMR (400MHz, C6D6):3.25-3.96(m, 2H), shown in FIG. 6. The total impurity content was detected to be less than 10ppm by inductively coupled plasma mass spectrometry (ICP-MS) in the inorganic material analysis test center of Shanghai silicate research institute, Chinese academy of sciences, as shown in Table 5.
Table 4 calculation of purity of crude product of examples 1-3 Secondary purification of diiodosilane
TABLE 5ICP-MS method for detecting total impurity content
Example 4: solvent using dichloromethane as iodine
Under the protection of nitrogen, 3518.1g of iodine and 10L of dichloromethane are prepared into a uniform mixed solution, simultaneously, 1500g of mixed solution of phenylsilane and 58.8ml of ethyl acetate are respectively pumped into a microchannel reactor, and the volume flow ratio of the iodine solution to the phenylsilane solution is 8: 1, precooling at-20 ℃, and then sequentially passing through a low-temperature micro-channel at-15 ℃ and a room-temperature micro-channel at +25 ℃ for 200s and 300s respectively to obtain a mixture. The mixture was rectified to give 3659g, 92.97% product as a colorless liquid. The purity of diiodosilane greater than 99.9 +% using GC chromatographic area normalization is shown in table 6 and figure 7.
Table 6 purity calculation of diiodosilane from example 4
Example 5: using dichloroethane as iodine solvent
Under the protection of nitrogen, 3518.1g of iodine and 10L of dichloroethane are prepared into a uniform mixed solution, simultaneously, 1500g of mixed solution of phenylsilane and 58.8ml of ethyl acetate are respectively pumped into a microchannel reactor, and the volume flow ratio of the iodine solution to the phenylsilane solution is 8: 1, precooling at-20 ℃, and then sequentially passing through a low-temperature microchannel at-15 ℃ and a room-temperature microchannel at +25 ℃ for 200s and 300s respectively to obtain a mixture. The mixture was rectified to give 3492g of product colorless liquid, 88.73%. The purity of diiodosilane greater than 99.9 +% using GC chromatographic area normalization is shown in table 7 and figure 8.
TABLE 7 purity calculation for diiodosilane from example 5
By substituting the solvent chloroform for dichloromethane or dichloroethane in examples 4 and 5, the reaction can proceed with yield and purity comparable to those of examples 1-3 using chloroform as the iodine solvent. Since trichloromethane is easy to be toxic, methylene dichloride or dichloroethane can effectively avoid environmental pollution, so that the solvent after replacement reduces the difficulty in obtaining raw materials and further reduces the production cost.
In order to improve the purity of the product, the crude product can be combined and rectified twice or for many times to obtain the pure colorless transparent liquid with the purity of 99.9999+ Si percent, thereby achieving the purpose of purification.
Example 6: device for preparing diiodosilane
The device for the preparation method of diiodosilane comprises two groups of raw material tanks, a first metering peristaltic pump, a second metering peristaltic pump, a precooling microchannel I, a precooling microchannel II and a microchannel reactor, wherein the two groups of raw material tanks are shown in figure 9; the group of stock tanks are communicated with the first metering peristaltic pump, the first metering peristaltic pump is communicated with the precooling microchannel I, and the precooling microchannel I is communicated with the microchannel reactor; and the other group of the raw material tanks is communicated with the second metering peristaltic pump, the second metering peristaltic pump is communicated with the precooling microchannel II, and the precooling microchannel II is communicated with the microchannel reactor.
Wherein the microchannel reactor is a continuous flow microchannel reactor; the microchannel reactor consists of a low-temperature microchannel and a room-temperature microchannel, and the low-temperature microchannel is communicated with the room-temperature microchannel. The two groups of raw material tanks are respectively an iodine solution tank and a phenylsilane solution tank.
The precooling micro-channels I and II and the micro-channel reactor are adopted, so that the mass transfer performance and the heat transfer performance can be enhanced, the complete reaction can be rapidly and sufficiently realized, the sudden and violent temperature rise can be avoided, and the occurrence of side reactions can be reduced. The micro-channel reactor can be used for continuously synthesizing diiodosilane; the iodine solution and the phenylsilane solution are precooled and enter the microchannel reactor after passing through the precooled microchannel I and the precooled microchannel II respectively, and then react in the low-temperature microchannel, and then react in the microchannel at room temperature, so that the reaction is quickly and fully completed.
Preferably, the channel of the precooling microchannel I is a snake-shaped, rhombus-shaped or heart-shaped channel, and the channel of the precooling microchannel II is a snake-shaped, rhombus-shaped or heart-shaped channel; the channel of the low-temperature micro-channel is a snake-shaped, rhombus-shaped or heart-shaped channel; the channel of the room temperature micro-channel is a snake-shaped, rhombus-shaped or heart-shaped channel.
Preferably, the length of the precooling microchannel I is 6-12m, and the radial width is 1-3 mm; the length of the precooling micro-channel II is 6-12m, and the radial width is 1-3 mm; the length of the low-temperature micro-channel is 6-12m, and the radial width is 1-3 mm; the length of the room temperature micro-channel is 6-12m, and the radial width is 1-3 mm.
According to the invention, the shape and length of the micro-channel pumped into the pre-cooling micro-channel I, the pre-cooling micro-channel II, the low-temperature micro-channel and the room-temperature micro-channel are controlled, so that the proportion and the reaction time of materials can be accurately controlled. Wherein precooling microchannels I and precooling microchannels II are connected with a microchannel reactor, so that the reaction temperature is easier to control.
Preferably, the microchannel reactor is made of hastelloy or silicon carbide; the first metering peristaltic pump for pumping the iodine solution is made of polytetrafluoroethylene; the first metering peristaltic pump which pumps the phenylsilane solution is made of polytetrafluoroethylene.
The invention can effectively control the content of impurity metal ions in the reaction by changing the materials of the micro-channel reactor and the first and second metering peristaltic pumps.
In addition, the device also comprises a crude product collecting tank and a rectifying device for purifying the mixture, such as a rectifying tower and the like.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The preparation method of diiodosilane is characterized by comprising the following steps:
step 1, mixing and dissolving iodine and at least one of chloroform, dichloromethane and dichloroethane according to a volume ratio of 1 (2-5) to obtain an iodine solution; mixing phenylsilane with at least one of ethyl acetate, tert-butyl acetate and butyl acetate in a mass ratio of 100: (1-5) mixing to obtain a phenylsilane solution; pre-cooling the obtained iodine solution and the obtained phenylsilane solution at the temperature of minus 40-0 ℃, then respectively pumping into a microchannel reactor, mixing and reacting for 100-300 s in a low-temperature microchannel at the temperature of minus 40-10 ℃, and then continuously reacting for 100-400 s in a room-temperature microchannel at the temperature of 20-30 ℃ to obtain a reaction mixture;
and 2, carrying out reduced pressure rectification on the reaction mixture obtained in the step 1, and collecting a product with the fraction temperature of 35-40 ℃ under 20 +/-3 mmHg to obtain the high-purity diiodosilane.
2. The method as claimed in claim 1, wherein in step 1, the reaction mixture is obtained by mixing and reacting 150-350 s in a microchannel at-30 to-20 ℃ and then reacting 250-350s in a microchannel at 25 ℃.
3. The method of claim 1, wherein in step 1, the ratio of iodine in the iodine solution pumped into the microchannel reactor to the amount of the phenylsilane compound in the phenylsilane solution is (1:2) to (2: 1).
4. The method of claim 1, wherein in step 1, the microchannel reactor uses an inert gas to displace the internal gas prior to pumping the iodine solution and the phenylsilane solution.
5. The method for preparing diiodosilane according to claim 1, wherein in step 1, the flow ratio of the iodine solution to the phenylsilane solution is (6-10): 1.
6. the device for preparing diiodosilane according to any one of claims 1 to 5, comprising two sets of raw material tanks, and further comprising a first metering peristaltic pump, a second metering peristaltic pump, a precooling microchannel I, a precooling microchannel II and a microchannel reactor; the group of raw material tanks are communicated with the first metering peristaltic pump, the first metering peristaltic pump is communicated with the precooling microchannel I, and the precooling microchannel I is communicated with the microchannel reactor; and the other group of the raw material tanks is communicated with the second metering peristaltic pump, the second metering peristaltic pump is communicated with the precooling microchannel II, and the precooling microchannel II is communicated with the microchannel reactor.
7. The apparatus of claim 6, wherein the microchannel reactor is a continuous flow microchannel reactor; the microchannel reactor consists of a low-temperature microchannel and a room-temperature microchannel, and the low-temperature microchannel is communicated with the room-temperature microchannel.
8. The device for preparing diiodosilane according to claim 7, wherein the channel of said precooling microchannel I is a serpentine, rhomboid or heart-shaped channel, and the channel of said precooling microchannel II is a serpentine, rhomboid or heart-shaped channel; the channel of the low-temperature micro-channel is a snake-shaped, rhombus-shaped or heart-shaped channel; the channel of the room temperature micro-channel is a snake-shaped, rhombus-shaped or heart-shaped channel.
9. The device for preparing diiodosilane according to claim 7, wherein the length of said precooling microchannel I is 6-12m, and the radial width is 1-3 mm; the length of the precooling micro-channel II is 6-12m, and the radial width is 1-3 mm; the length of the low-temperature micro-channel is 6-12m, and the radial width is 1-3 mm; the length of the room temperature micro-channel is 6-12m, and the radial width is 1-3 mm.
10. The apparatus of claim 6, wherein the microchannel reactor is made of Hastelloy or silicon carbide; the first metering peristaltic pump for pumping the iodine solution is made of polytetrafluoroethylene; the first metering peristaltic pump which pumps the phenylsilane solution is made of polytetrafluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210638045.6A CN114835126A (en) | 2022-06-07 | 2022-06-07 | Preparation method and device of diiodosilane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210638045.6A CN114835126A (en) | 2022-06-07 | 2022-06-07 | Preparation method and device of diiodosilane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114835126A true CN114835126A (en) | 2022-08-02 |
Family
ID=82574140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210638045.6A Pending CN114835126A (en) | 2022-06-07 | 2022-06-07 | Preparation method and device of diiodosilane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114835126A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116081626A (en) * | 2023-03-30 | 2023-05-09 | 研峰科技(北京)有限公司 | Preparation method of diiodosilane |
| CN116375038A (en) * | 2023-02-23 | 2023-07-04 | 安徽博泰电子材料有限公司 | Preparation method of diiodosilane |
| CN116789140A (en) * | 2023-06-29 | 2023-09-22 | 铜陵安德科铭电子材料科技有限公司 | Diiodosilane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204952873U (en) * | 2015-09-08 | 2016-01-13 | 中国科学院广州能源研究所 | Millimeter passageway formula serialization preparation system |
| CN208320668U (en) * | 2018-05-02 | 2019-01-04 | 深圳太太药业有限公司 | Miniature mixed reactor |
| CN111072030A (en) * | 2018-10-18 | 2020-04-28 | 山中胡特克株式会社 | Process for producing diiodosilane |
| CN113548669A (en) * | 2021-09-01 | 2021-10-26 | 福建福豆新材料有限公司 | Preparation device and preparation method of high-purity electronic-grade diiodosilane |
-
2022
- 2022-06-07 CN CN202210638045.6A patent/CN114835126A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204952873U (en) * | 2015-09-08 | 2016-01-13 | 中国科学院广州能源研究所 | Millimeter passageway formula serialization preparation system |
| CN208320668U (en) * | 2018-05-02 | 2019-01-04 | 深圳太太药业有限公司 | Miniature mixed reactor |
| CN111072030A (en) * | 2018-10-18 | 2020-04-28 | 山中胡特克株式会社 | Process for producing diiodosilane |
| CN113548669A (en) * | 2021-09-01 | 2021-10-26 | 福建福豆新材料有限公司 | Preparation device and preparation method of high-purity electronic-grade diiodosilane |
Non-Patent Citations (1)
| Title |
|---|
| 杨启明等: "《石油化工过程设备设计》", 石油工业出版社, pages: 508 - 511 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375038A (en) * | 2023-02-23 | 2023-07-04 | 安徽博泰电子材料有限公司 | Preparation method of diiodosilane |
| CN116081626A (en) * | 2023-03-30 | 2023-05-09 | 研峰科技(北京)有限公司 | Preparation method of diiodosilane |
| CN116789140A (en) * | 2023-06-29 | 2023-09-22 | 铜陵安德科铭电子材料科技有限公司 | Diiodosilane and preparation method thereof |
| CN116789140B (en) * | 2023-06-29 | 2023-12-22 | 铜陵安德科铭电子材料科技有限公司 | Diiodosilane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114835126A (en) | Preparation method and device of diiodosilane | |
| CN110642897B (en) | Preparation method of beta-nicotinamide riboside chloride | |
| CN111269080B (en) | Perfluoro 1, 3-butadiene microreactor preparation system and preparation method thereof | |
| TW201139268A (en) | Preparation process of trisilylamine | |
| KR20110053834A (en) | Process for purification of monosilane | |
| CN211871826U (en) | Preparation system of perfluorobutadiene | |
| CN114835670A (en) | Method for preparing high-purity vinylene carbonate | |
| WO2015122386A1 (en) | Method for producing fluorinated hydrocarbon | |
| CN108084219B (en) | Synthesis method of bis (diethylamino) silane | |
| CN112456500A (en) | Preparation method of trichlorosilane | |
| CN111925388B (en) | Preparation method of titanium tetraisopropoxide | |
| CN116081626B (en) | Preparation method of diiodosilane | |
| CN109232633B (en) | Combined preparation method of trimethyl monomethoxysilane-hexamethyldisilazane | |
| CN113461538A (en) | Preparation method of 2-chloro-3-bromoaniline | |
| CN112110948A (en) | Preparation method of liquid diamino-substituted disilane and application of liquid diamino-substituted disilane product | |
| CN114736233B (en) | Synthesis method of tetramethylsilane | |
| CN118406074B (en) | Purification method of crude trimethylaluminum product | |
| CN108017060B (en) | A kind of purification process of disilicone hexachloride | |
| CN117228643A (en) | Preparation method of electronic grade phosphorus trifluoride | |
| WO2012100555A1 (en) | A method for the preparation of lower aluminum alkoxide by gas-solid phase reaction | |
| CN116239467A (en) | Preparation method of high-purity difluoroethyl acetate | |
| CN118206590A (en) | Preparation method of tris (dimethylamino) cyclopentadienyl zirconium | |
| CN118904237A (en) | Production system and production method of hexachlorodisiloxane | |
| CN117285028A (en) | Process method for co-production of tungsten halide and carbon tetrafluoride | |
| CN117718003A (en) | Adsorbent for removing metal impurities in organic amino tin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220802 |