CN116375038A - Preparation method of diiodosilane - Google Patents
Preparation method of diiodosilane Download PDFInfo
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- CN116375038A CN116375038A CN202310157969.9A CN202310157969A CN116375038A CN 116375038 A CN116375038 A CN 116375038A CN 202310157969 A CN202310157969 A CN 202310157969A CN 116375038 A CN116375038 A CN 116375038A
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- diiodosilane
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- iodide
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- dichlorosilane
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- AIHCVGFMFDEUMO-UHFFFAOYSA-N diiodosilane Chemical compound I[SiH2]I AIHCVGFMFDEUMO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title abstract description 12
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 80
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 4
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000003222 pyridines Chemical class 0.000 claims description 3
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- CLZGJKHEVKJLLS-UHFFFAOYSA-N n,n-diheptylheptan-1-amine Chemical compound CCCCCCCN(CCCCCCC)CCCCCCC CLZGJKHEVKJLLS-UHFFFAOYSA-N 0.000 claims description 2
- DIAIBWNEUYXDNL-UHFFFAOYSA-N n,n-dihexylhexan-1-amine Chemical compound CCCCCCN(CCCCCC)CCCCCC DIAIBWNEUYXDNL-UHFFFAOYSA-N 0.000 claims description 2
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims 1
- 230000036632 reaction speed Effects 0.000 abstract description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- 239000000047 product Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000001978 electrochemical passivation Methods 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006073 displacement reaction Methods 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910014299 N-Si Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- UJPJVFMGMITNJK-UHFFFAOYSA-N iodo(phenyl)silane Chemical compound I[SiH2]c1ccccc1 UJPJVFMGMITNJK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- IDIOJRGTRFRIJL-UHFFFAOYSA-N iodosilane Chemical compound I[SiH3] IDIOJRGTRFRIJL-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 1
- XJWOWXZSFTXJEX-UHFFFAOYSA-N phenylsilicon Chemical compound [Si]C1=CC=CC=C1 XJWOWXZSFTXJEX-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention discloses a preparation method of diiodosilane, and relates to the technical field of inorganic compound preparation. The invention discloses a new technology for preparing diiodosilane by using halogen element exchange method, wherein halogenated alkane is used as solvent, nitrogenous organic matters are used as catalyst, alkali metal iodide and dichlorosilane are used as raw materials. The preparation method is suitable for large-scale production of diiodosilane, and has the advantages of high reaction speed and high product yield.
Description
Technical Field
The invention relates to the technical field of inorganic compound preparation, in particular to a preparation method of diiodosilane.
Background
Diiodosilane (H) 2 SiI 2 ) The boiling point of (2) is 56-60 ℃, has unique physical and chemical properties compared with other halogenated silanes, can form a uniform and compact silicon nitride (N-Si) film layer at a high speed in a lower temperature window area in an atomic layer deposition film forming process, the deposited N-Si film layer can meet the requirements of the integrated circuit chip manufacturing process, so diiodosilane is widely used in the advanced semiconductor chip manufacturing field, is an indispensable silicon-based precursor material, and has wide application prospect.
Chinese patent number CN110606491B discloses a preparation method of high-purity diiodosilane, and specifically discloses a method for preparing diiodosilane by reacting mono-phenylsilane with elemental iodine in a halogenated hydrocarbon solvent and under the condition that oxygen-containing organic matters are taken as catalysts. The reaction is carried out in two steps, wherein the first step is that the phenyl silane reacts with iodine simple substance to generate phenyl monoiodo silane and hydrogen iodide gas, the first step is very fast and releases high heat, and the reaction needs to be controlled at low temperature. The second step is that the generated intermediate mono phenyl monoiodo silane and hydrogen iodide gas are further reacted with each other to generate target product diiodo silane, and the second step is that the reaction is slow and needs to be carried out at relatively high temperature. The process has the following defects: (1) The first step has high reaction speed, needs to be controlled at a lower temperature (-100 ℃ to-20 ℃), has large reaction heat release and high temperature rise, and is easy to generate a runaway reaction; (2) The HI produced in the first step gathers in the reactor and generates pressure; (3) The second step has low reaction speed and needs to be carried out under the condition that the temperature is increased to more than 30 ℃; (4) The competing reaction exists in the reaction process, and the hydrogen iodide generated in the first step of reaction can be rapidly reacted with the raw material of the monosilane to produce the monoiodo Silane (SiH) 3 I) Benzene, and making the reaction yield low; (5) the monosilane product is not available to suppliers in China.
A method for preparing diiodosilane by reacting dichlorosilane with solid lithium iodide is disclosed in patent publication No. WO 2019/212808A1, which is a halogen element exchange method, wherein specifically, the diiodosilane is prepared by reacting dichlorosilane with lithium iodide. The reaction method is that anhydrous lithium iodide solid is arranged in a stainless steel jacketed reaction tube with the diameter of 0.5 inch and the length of 29 inches, then excessive dichlorosilane gas is added into the reaction tube for reaction, the temperature of the jacketed tube is controlled within the range of minus 6 ℃ to 40 ℃, the pressure in the reaction tube is 0.05 MPa to 0.2MPa, and the high-purity diiodosilane product is obtained after the mixture is obtained by the reaction and the rectification and the purification of a rectifying still. The process has the following defects: (1) The reaction scale belongs to the laboratory scale, and the large-scale production is difficult; (2) The reaction is heterogeneous reaction of solid and compressed liquid, and the material is difficult to completely contact and react without stirring and mixing; (3) The lithium iodide has large crystalline particles and small surface area, and influences the reactionThe response speed; (4) Reaction of lithium iodide with excess dichlorosilane results in intermediate H 2 SiI (Cl) cannot be completely converted into diiodosilane, and the diiodosilane is treated as a byproduct according to hazardous waste, so that environmental pollution is caused; (5) the process has low product yield.
Disclosure of Invention
The invention aims to provide a preparation method of diiodosilane, which solves the following technical problems:
in the prior art, dichlorosilane and lithium iodide are utilized to react in a heterogeneous system, the reaction is difficult to completely proceed, excessive dichlorosilane is easy to generate hazardous waste byproducts, the hazardous waste byproducts are difficult to treat, the environment is polluted, and the yield of reaction products is low.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing diiodosilane, comprising the steps of:
(1) Adding alkali metal iodide, a solvent and a catalyst into a reaction kettle in an inert gas atmosphere, stirring, cooling, adding dichlorosilane, heating, preserving heat and stirring to obtain a reaction solution;
(2) Filtering and rectifying the reaction liquid, and collecting fractions between 55 and 60 ℃ to obtain diiodosilane.
The reaction formula is as follows:
H 2 SiCl 2 +LiI→H 2 Si(Cl)I+LiCl
H 2 Si(Cl)I+LiI→H 2 SiI 2 +LiCl。
as a further aspect of the invention: the alkali metal iodide is any one of lithium iodide, sodium iodide and potassium iodide.
As a further aspect of the invention: the alkali iodide is 200-400 mesh granule.
As a further aspect of the invention: the solvent is chloroform, dichloromethane, acetonitrile, methyl iodide, 1-ethyl iodide, 1-iodopropane, 1-iodobutane and C6-C12 iodoalkane.
As a further aspect of the invention: the structural general formula of the C6-C12 iodo alkane is as follows: r is R 1 -I, said R 1 C6-C12, straight-chain C6-C12, C6-C12 alkyl ring as branched chainAny one of alkyl and C6-C12 cycloalkylalkyl.
As a further aspect of the invention: the difference between the boiling point of the solvent and the boiling point of diiodosilane is more than 10 ℃.
As a further aspect of the invention: the catalyst is any one of triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, pyridine and alkyl substituted pyridine;
as a further aspect of the invention: the structural general formula of the alkyl substituted pyridine is as follows:
wherein Rn is substituent groups on the pyridine ring, rn is any one of branched C3-C5 and straight-chain C1-C5, n is the number of substituent groups on the pyridine ring, and n is any one of 1-3.
As a further aspect of the invention: the catalyst is a nitrogen-containing compound, and the difference between the boiling point of the catalyst and the boiling point of diiodosilane is more than 10 ℃.
As a further aspect of the invention: the molar ratio of dichlorosilane to alkali metal iodide is 1:2.0 to 2.2.
As a further aspect of the invention: the mol ratio of the catalyst to the dichlorosilane is 1:10-50.
As a further aspect of the invention: the temperature is reduced to-10 to-50 ℃ in the step (1).
As a further aspect of the invention: in the step (1), the temperature is raised, the reaction is carried out at 40-100 ℃, and the temperature is kept and stirred for 5-6 h.
As a further aspect of the invention: the inert gas atmosphere in the step (1) is specifically that the inert gas is replaced for 4-5 times by vacuum/inert gas, and the oxygen content in the inert gas in the reaction kettle is less than 3ppm.
As a further aspect of the invention: the inert gas is any one of nitrogen and argon.
As a further aspect of the invention: in the step (1), the stirring speed is 500-1200 rpm.
The invention has the beneficial effects that:
the invention uses excessive anhydrous alkali metal iodide and dichlorosilane to react in a solvent, adds catalytic amount of organic amine in the reaction to accelerate the reaction speed and improve the product yield, and the prepared crude solution of diiodosilane is rectified and purified in a rectifying kettle to obtain high-purity diiodosilane. First, the present application uses a suitable excess of anhydrous alkali iodide to provide intermediate H 2 Si (Cl) I is converted into diiodosilane as much as possible, and the product yield is high. The alkali metal iodide particles are selected to be 200-400 meshes, so that the specific surface area of the solid raw material is increased, the mutual collision of molecules between solid and liquid reactants is facilitated in the high-speed stirring process, the reaction speed is improved, and meanwhile, the solubility of the alkali metal iodide in the solution is also facilitated.
The reaction is carried out in a halogen-containing solvent, especially an alkyl iodide, so that the solubility of lithium iodide is improved and the reaction speed is increased. The nitrogen-containing organic matter is used as a catalyst, so that the overall reaction rate and the yield of diiodosilane are improved. The preparation method disclosed by the invention is suitable for large-scale preparation of diiodosilane,
drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a gas chromatogram of diiodosilane prepared in example 1 of the present application.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Referring to fig. 1, a preparation method of diiodosilane includes the following steps:
(1) A5L jacketed stainless steel reaction kettle is selected, a nitrogen port valve, a vacuum port valve, a solid feed port valve, a liquid feed port valve and a pressure gauge and a thermometer in the kettle are arranged on the top of the kettle, and the inside of the kettle is subjected to electrochemical passivation treatment and is cleaned. Before use, the air tightness of the reaction kettle is detected. The inlet and outlet of the jacket are connected with a heating and refrigerating cycle with the temperature working range of 150 ℃ to-40 ℃. Reducing the oxygen content in the nitrogen of the reaction kettle to below 3ppm by vacuum/nitrogen replacement for 4-5 times;
(2) Adding 400g LiI with 200 meshes, 1000mL acetonitrile and 9.52g triethylamine, adding 190g dichlorosilane at 800rpm and minus 30 ℃, keeping the pressure in a kettle at not more than 0.3MPa in the process of adding the dichlorosilane, heating to 40 ℃ after the dichlorosilane is added, preserving heat and stirring for 5 hours, and detecting the ratio of diiodosilane to dichlorosilane by extracting reaction liquid in the reaction process, wherein the reaction is stopped when the reaction detection shows that the conversion rate exceeds 90%, so as to obtain a reaction liquid;
(3) The reaction solution is filtered, rectified at normal pressure and the fraction with the temperature of 55-60 ℃ is collected to obtain diiodosilane, the product yield is 70.5%, and the purity of the obtained diiodosilane is 98.5%.
Example 2
A method for preparing diiodosilane, comprising the steps of:
(1) A5L jacketed stainless steel reaction kettle is selected, a nitrogen port valve, a vacuum port valve, a solid feed port valve, a liquid feed port valve and a pressure gauge and a thermometer in the kettle are arranged on the top of the kettle, and the inside of the kettle is subjected to electrochemical passivation treatment and is cleaned. Before use, the air tightness of the reaction kettle is detected. The inlet and outlet of the jacket are connected with a heating and refrigerating cycle with the temperature working range of 150 ℃ to-40 ℃. Reducing the oxygen content in the nitrogen of the reaction kettle to below 3ppm by vacuum/nitrogen displacement for 4 to 5 times;
(2) Adding 400g LiI with 200 meshes, 1000mL acetonitrile and 13.48g tripropylamine, adding 190g dichlorosilane at 800rpm and minus 30 ℃, keeping the pressure in a kettle at not more than 0.3MPa in the process of adding the dichlorosilane, heating to 40 ℃ after the dichlorosilane is added, preserving heat and stirring for 5 hours, and detecting the ratio of diiodosilane to dichlorosilane by extracting reaction liquid in the reaction process, wherein the reaction is stopped when the reaction detection shows that the conversion exceeds 90%, so as to obtain a reaction liquid;
(3) The reaction solution is filtered, rectified at normal pressure and the fraction with the temperature of 55-60 ℃ is collected to obtain diiodosilane, the product yield is 72.3%, and the purity of the obtained diiodosilane is 97.8%.
Example 3
A method for preparing diiodosilane, comprising the steps of:
(1) A5L jacketed stainless steel reaction kettle is selected, a nitrogen port valve, a vacuum port valve, a solid feed port valve, a liquid feed port valve and a pressure gauge and a thermometer in the kettle are arranged on the top of the kettle, and the inside of the kettle is subjected to electrochemical passivation treatment and is cleaned. Before use, the air tightness of the reaction kettle is detected. The inlet and outlet of the jacket are connected with a heating and refrigerating cycle with the temperature working range of 150 ℃ to-40 ℃. Reducing the oxygen content in the nitrogen of the reaction kettle to below 3ppm by vacuum/nitrogen displacement for 4 to 5 times;
(2) Sequentially adding 400g LiI with 200 meshes, 1000mL ethyl iodide and 9.52g triethylamine, adding 190g dichlorosilane at 800rpm and minus 30 ℃, keeping the pressure in a kettle at not more than 0.3MPa in the process of adding the dichlorosilane, heating to 40 ℃ after the dichlorosilane is added, preserving heat and stirring for 4 hours, and detecting the ratio of diiodosilane to dichlorosilane by extracting reaction liquid in the reaction process, wherein the reaction is stopped when the reaction detection shows that the conversion rate exceeds 90%, so as to obtain the reaction liquid;
(3) The reaction solution is filtered, rectified at normal pressure and the fraction with the temperature of 55-60 ℃ is collected to obtain diiodosilane, the product yield is 73.3%, and the purity of the obtained diiodosilane is 98.1%.
Example 4
A method for preparing diiodosilane, comprising the steps of:
(1) A5L jacketed stainless steel reaction kettle is selected, a nitrogen port valve, a vacuum port valve, a solid feed port valve, a liquid feed port valve and a pressure gauge and a thermometer in the kettle are arranged on the top of the kettle, and the inside of the kettle is subjected to electrochemical passivation treatment and is cleaned. Before use, the air tightness of the reaction kettle is detected. The inlet and outlet of the jacket are connected with a heating and refrigerating cycle with the temperature working range of 150 ℃ to-40 ℃. Reducing the oxygen content in the nitrogen of the reaction kettle to below 3ppm by vacuum/nitrogen displacement for 4 to 5 times;
(2) Adding 400g LiI with 200 meshes, 1000mL of ethyl iodide and 13.48g tripropylamine, adding 190g of dichlorosilane at 800rpm and minus 30 ℃, keeping the pressure in a kettle at not more than 0.3MPa in the process of adding the dichlorosilane, heating to 40 ℃ after the dichlorosilane is added, preserving heat and stirring for 6 hours, and detecting the ratio of the diiodosilane to the dichlorosilane by extracting a reaction liquid in the reaction process, wherein the reaction is stopped when the reaction detection shows that the conversion exceeds 90%, so as to obtain a reaction liquid;
(3) The reaction solution is filtered, rectified at normal pressure and the fraction with the temperature of 55-60 ℃ is collected to obtain diiodosilane, the product yield is 75.4%, and the purity of the obtained diiodosilane is 98.5%.
Example 5
A method for preparing diiodosilane, comprising the steps of:
(1) A5L jacketed stainless steel reaction kettle is selected, a nitrogen port valve, a vacuum port valve, a solid feed port valve, a liquid feed port valve and a pressure gauge and a thermometer in the kettle are arranged on the top of the kettle, and the inside of the kettle is subjected to electrochemical passivation treatment and is cleaned. Before use, the air tightness of the reaction kettle is detected. The inlet and outlet of the jacket are connected with a heating and refrigerating cycle with the temperature working range of 150 ℃ to-40 ℃. Reducing the oxygen content in the nitrogen of the reaction kettle to below 3ppm by vacuum/nitrogen displacement for 4 to 5 times;
(2) Adding 400g LiI with 200 meshes, 1000mL iodopropane and 9.52g triethylamine, adding 190g dichlorosilane at 800rpm and minus 30 ℃, keeping the pressure in a kettle at not more than 0.3MPa in the process of adding the dichlorosilane, heating to 40 ℃ after the dichlorosilane is added, preserving heat and stirring for 5 hours, and detecting the ratio of the diiodosilane to the dichlorosilane by extracting reaction liquid in the reaction process, wherein the reaction is stopped when the reaction detection shows that the conversion rate exceeds 90%, so as to obtain a reaction liquid;
(3) The reaction solution is filtered, rectified at normal pressure and the fraction with the temperature of 55-60 ℃ is collected to obtain diiodosilane, the product yield is 74.5%, and the purity of the obtained diiodosilane is 97.5%.
Example 6
A method for preparing diiodosilane, comprising the steps of:
(1) A5L jacketed stainless steel reaction kettle is selected, a nitrogen port valve, a vacuum port valve, a solid feed port valve, a liquid feed port valve and a pressure gauge and a thermometer in the kettle are arranged on the top of the kettle, and the inside of the kettle is subjected to electrochemical passivation treatment and is cleaned. Before use, the air tightness of the reaction kettle is detected. The inlet and outlet of the jacket are connected with a heating and refrigerating cycle with the temperature working range of 150 ℃ to-40 ℃. Reducing the oxygen content in the nitrogen of the reaction kettle to below 3ppm by vacuum/nitrogen displacement for 4 to 5 times;
(2) Adding 400g LiI with 200 meshes, 1000mL iodopropane and 13.48g tripropylamine, adding 190g dichlorosilane at 800rpm and minus 30 ℃, keeping the pressure in a kettle at not more than 0.3MPa in the process of adding the dichlorosilane, heating to 40 ℃ after the dichlorosilane is added, preserving heat and stirring for 5 hours, and detecting the ratio of the diiodosilane to the dichlorosilane by extracting a reaction liquid in the reaction process, wherein the reaction is stopped when the reaction detection shows that the conversion rate exceeds 90%, so as to obtain a reaction liquid;
(3) The reaction solution is filtered, rectified at normal pressure and the fraction with the temperature of 55-60 ℃ is collected to obtain diiodosilane, the product yield is 68.9%, and the purity of the obtained diiodosilane is 97.9%.
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.
Claims (10)
1. A method for preparing diiodosilane, which is characterized by comprising the following steps:
(1) Adding alkali metal iodide, a solvent and a catalyst into a reaction kettle in an inert gas atmosphere, stirring, cooling, adding dichlorosilane, heating, preserving heat and stirring to obtain a reaction solution;
(2) Filtering and rectifying the reaction liquid, and collecting fractions between 55 and 60 ℃ to obtain diiodosilane.
2. The method for producing diiodosilane according to claim 1, wherein the alkali metal iodide is any one of lithium iodide, sodium iodide and potassium iodide.
3. The method for preparing diiodosilane according to claim 1, wherein the alkali metal iodide is 200-400 mesh particles.
4. The method for preparing diiodosilane according to claim 1, wherein the solvent is any one of chloroform, dichloromethane, acetonitrile, methyl iodide, 1-ethyl iodide, 1-propyl iodide, 1-butyl iodide, and C6-C12 iodo alkane.
5. The method for preparing diiodosilane according to claim 1, wherein the catalyst is any one of triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, pyridine and alkyl-substituted pyridine.
6. The method for preparing diiodosilane according to claim 1, wherein the molar ratio of dichlorosilane to alkali metal iodide is 1:2 to 2.2.
7. The method for preparing diiodosilane according to claim 1, wherein the molar ratio of catalyst to dichlorosilane is 1:10-50.
8. The method for preparing diiodosilane according to claim 1, wherein the temperature in step (1) is specifically reduced to-10 to-50 ℃.
9. The method for preparing diiodosilane according to claim 1, wherein the heating and heat preservation reaction in the step (1) is specifically heating to 40-100 ℃, and stirring for 5-6 h.
10. The method for preparing diiodosilane according to claim 1, wherein the inert gas atmosphere in step (1) is replaced by vacuum/inert gas for 4-5 times, and the oxygen content in the inert gas in the reaction vessel is less than 3ppm.
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