CN115304632B - Preparation method and application of electronic-grade tetraalkoxysilane - Google Patents
Preparation method and application of electronic-grade tetraalkoxysilane Download PDFInfo
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- CN115304632B CN115304632B CN202210863067.2A CN202210863067A CN115304632B CN 115304632 B CN115304632 B CN 115304632B CN 202210863067 A CN202210863067 A CN 202210863067A CN 115304632 B CN115304632 B CN 115304632B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 21
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- -1 polytetrafluoroethylene Polymers 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 20
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052796 boron Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 238000000227 grinding Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 11
- 239000012043 crude product Substances 0.000 description 11
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 9
- 230000005611 electricity Effects 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/04—Esters of silicic acids
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30625—With simultaneous mechanical treatment, e.g. mechanico-chemical polishing
-
- 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
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
Abstract
The invention discloses a preparation method of electronic-grade tetraalkoxysilane, belonging to the field of synthesis of silane coupling agents. The invention adopts silicon powder, alcohol, solvent and titanium-copper composite catalyst as raw materials, directly reacts to prepare the tetraalkoxysilane, and then separates and purifies the tetraalkoxysilane through a specific rectification procedure to obtain the electronic grade tetraalkoxysilane. After the electronic grade tetraalkoxysilane preparation and the grinding particle preparation process are closed, the alcohol can be reused, so that the production cost is reduced. The product obtained by the invention meets the requirements of the semiconductor CVD process, the GC purity of the product is 4N, the purity of metal ions is 7-9N, and the impurity contents of chlorine (Cl), boron (B), copper (Cu) and the like are all less than 10ppb.
Description
Technical Field
The invention relates to the field of synthesis of silane coupling agents, in particular to a preparation method of electronic-grade tetraalkoxysilane.
Background
In recent years, with the vigorous development of the electronic and semiconductor industries, the attention of the precursors commonly used in the fields is getting higher and higher. However, the synthesis process of tetraalkoxysilane in the industry at present is mostly prepared by taking silicon tetrachloride which is byproduct of polysilicon and alcohols (methanol, ethanol, propanol or isopropanol) as raw materials through esterification reaction and subsequent rectification procedures. However, due to the factors of raw materials, equipment and the like, certain amount of metal and nonmetal impurities can be carried into the prepared product, so that the application of the tetraalkoxysilane in the high-end industry is limited. Meanwhile, some manufacturers directly synthesize tetraalkoxysilane by adopting silicon powder and alcohols under the action of copper catalysts, but because the adopted catalyst is cuprous chloride, chlorine is inevitably introduced into the system, so that the subsequent chlorine removal operation is not facilitated, and the production cost is further increased.
In order to prepare electronic-grade tetraalkoxysilane, the crude tetraalkoxysilane is usually used as a raw material to remove metal and nonmetal impurities introduced in the synthesis process of the tetraalkoxysilane through a series of subsequent complicated adsorption and rectification operations, so that the requirements of fields such as semiconductors, single-wafer abrasives, chip encapsulation, ultra-pure synthetic quartz sand and the like on a silicon source are met. For example, chinese patent CN201910119724.0 discloses a purification method of tetraethoxysilane, wherein at least six purification steps are required from crude tetraethoxysilane to electronic grade tetraethoxysilane, and the purification method has the disadvantages of long process route, large equipment investment, high energy consumption and the like. For example, chinese patent CN201310747619.4 discloses a method for preparing electronic grade tetraethoxysilane, wherein at least 4 purification steps are required to prepare electronic grade tetraethoxysilane, and the method has the disadvantages of long process route, poor process stability, low production efficiency, high energy consumption and the like.
Disclosure of Invention
In order to solve the defects existing in the prior art, the invention aims to provide the preparation method of the electronic-grade tetraalkoxysilane, which directly prepares the electronic-grade tetraalkoxysilane by selecting a halogen-free catalyst and optimizing a purification process, and has the advantages of simple synthesis and purification process and contribution to industrialization.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
(1) Adding a certain amount of solvent, silicon powder and catalyst into a reaction kettle, heating to 180-250 ℃, starting alcohol introduction, continuously heating to 210-240 ℃ and reacting for 20-28h to obtain a crude tetraalkoxysilane product;
(2) And rectifying the crude tetraalkoxysilane to obtain the electronic-grade tetraalkoxysilane.
Preferably: in the step (1), the solvent comprises one or more of diphenyl ether, dodecylbenzene, dimethyl benzene ether and triethanolamine.
Preferably: in the step (1), the mass ratio of the solvent to the silicon powder to the catalyst is 500:100:0.2-0.4.
Preferably: in the step (1), the catalyst is titanium-copper alloy.
Preferably: the preparation method of the catalyst titanium-copper alloy comprises the following steps:
firstly ball milling nano Cu powder and nano Ti powder to obtain mixed powder, then placing the mixed powder into a high-temperature furnace, introducing high-purity nitrogen for pretreatment, and calcining at 700-1300 ℃ for 2-6h to obtain the titanium-copper alloy material.
Preferably: the mass percentage of Cu powder in the mixed powder is 70% -90%, the inlet flow rate of the high-purity nitrogen is 50mL/min, and the pretreatment time is 1h.
Preferably: in the step (1), the alcohol passing rate is 30g/h.
Preferably: in the step (2), the rectification temperature is 95-130 ℃, the pressure is-0.098 MPa, the reflux ratio is 1-10, the rectification equipment is made of fully-lined polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall ring.
The invention also claims electronic grade tetraalkoxysilane prepared by the preparation method: the structure of the compound is shown as formula I:
Si(OR) 4 a formula I;
wherein, in the formula I, R represents methyl, ethyl, propyl or isopropyl;
the GC purity of the electronic grade tetraalkoxysilane product is 4N, the purity of metal ions is 7-9N, and the impurity content of chlorine (Cl), boron (B) and copper (Cu) is less than 10ppb.
In addition, the invention also protects the application of the electronic grade tetraalkoxysilane as abrasive particles, wherein the abrasive particles are raw materials of polishing solution used for preparing high-end chips.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention uses titanium-copper alloy as catalyst for synthesizing tetraalkoxysilane by silica powder direct method for the first time, and the titanium-copper alloy has good synergistic catalytic reaction effect.
2. The whole reaction process of the invention does not introduce chloride ions, does not need a subsequent chlorine removal process, and has the advantages of easier purification of products and simpler process.
3. The process of purifying the crude tetraalkoxysilane into the electronic-grade tetraalkoxysilane is simple, the crude product obtained by the reaction is the high-purity tetraalkoxysilane, and the electronic-grade tetraalkoxysilane can be obtained only by strictly controlling the rectification process.
4. The GC purity of the electronic grade tetraalkoxysilane product is 4N, the purity of metal ions is 7-9N, and the impurity content of chlorine (Cl), boron (B) and copper (Cu) is less than 10ppb.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the following examples. Of course, the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Although the steps of the present invention are arranged by reference numerals, the order of the steps is not limited, and the relative order of the steps may be adjusted unless the order of the steps is explicitly stated or the execution of a step requires other steps as a basis. It is to be understood that the term "and/or" as used herein relates to and encompasses any and all possible combinations of one or more of the associated listed items.
Unless otherwise specified, both chemical reagents and materials in the present invention are purchased through a market route or synthesized from raw materials purchased through a market route.
Example 1
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of solvent diphenyl ether, 100 parts by mass of silicon powder and 0.2 part by mass of catalyst into a reaction kettle, heating to 200 ℃ and starting to introduce methanol (30 g/h), continuously heating to 220 ℃ and reacting for 25 hours to obtain a tetramethoxysilane crude product; and (3) carrying out subsequent rectification on the crude tetramethoxysilane, wherein the rectification temperature is 100 ℃, the pressure is-0.098 MPa, the reflux ratio is 2, the rectification equipment is made of full-lining polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic grade tetramethoxysilane is prepared.
The preparation method of the catalyst comprises the following steps: firstly, 70 parts by mass of nano Cu powder and 30 parts by mass of nano Ti powder are ball-milled for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 1300 ℃ for 5h to obtain the titanium-copper alloy material.
Example 2
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of solvent diphenyl ether, 100 parts by mass of silicon powder and 0.2 part by mass of catalyst into a reaction kettle, heating to 200 ℃ and starting to introduce ethanol (30 g/h), continuously heating to 225 ℃ and reacting for 26 hours to obtain a tetraethoxysilane crude product; and (3) carrying out subsequent rectification on the tetraethoxysilane crude product, wherein the rectification temperature is 105 ℃, the pressure is-0.098 MPa, the reflux ratio is 4, the rectification equipment is made of full-lining polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic grade tetraethoxysilane is obtained.
The preparation method of the catalyst comprises the following steps: firstly, 70 parts by mass of nano Cu powder and 30 parts by mass of nano Ti powder are ball-milled for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 1250 ℃ for 5h to obtain the titanium-copper alloy material.
Example 3
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of solvent dodecylbenzene, 100 parts by mass of silicon powder and 0.3 part by mass of catalyst into a reaction kettle, heating to 200 ℃ to start ethanol (30 g/h), continuously heating to 232 ℃ and reacting for 24 hours to obtain tetraethoxysilane crude product; and (3) carrying out subsequent rectification on the tetraethoxysilane crude product, wherein the rectification temperature is 106 ℃, the pressure is-0.098 MPa, the reflux ratio is 4, the rectification equipment is made of full-lining polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic grade tetraethoxysilane is obtained.
The preparation method of the catalyst comprises the following steps: firstly, carrying out ball milling on 75 parts by mass of nano Cu powder and 25 parts by mass of nano Ti powder for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 1200 ℃ for 5h to obtain the titanium-copper alloy material.
Example 4
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of dodecylbenzene serving as a solvent, 100 parts by mass of silicon powder and 0.3 part by mass of catalyst into a reaction kettle, heating to 200 ℃ to start introducing propanol (30 g/h), continuously heating to 215 ℃ and reacting for 24 hours to obtain a tetrapropoxy silane crude product; and (3) carrying out subsequent rectification on the crude tetrapropoxy silane product, wherein the rectification temperature is 115 ℃, the pressure is-0.098 MPa, the reflux ratio is 5, the rectification equipment is made of fully-lined polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic-grade tetrapropoxy silane is obtained.
The preparation method of the catalyst comprises the following steps: firstly, carrying out ball milling on 75 parts by mass of nano Cu powder and 25 parts by mass of nano Ti powder for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 1200 ℃ for 5h to obtain the titanium-copper alloy material.
Example 5
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of dimethyl phenyl ether serving as a solvent, 100 parts by mass of silicon powder and 0.4 part by mass of catalyst into a reaction kettle, heating to 200 ℃ to start introducing propanol (30 g/h), continuously heating to 218 ℃ and reacting for 22 hours to obtain a tetrapropoxy silane crude product; and (3) carrying out subsequent rectification on the crude tetrapropoxysilane, wherein the rectification temperature is 117 ℃, the pressure is-0.098 MPa, the reflux ratio is 7, the rectification equipment is made of fully-lined polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic-grade tetrapropoxysilane is obtained.
The preparation method of the catalyst comprises the following steps: firstly, 80 parts by mass of nano Cu powder and 20 parts by mass of nano Ti powder are ball-milled for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 1100 ℃ for 5h to obtain the titanium-copper alloy material.
Example 6
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of dimethyl phenyl ether serving as a solvent, 100 parts by mass of silicon powder and 0.4 part by mass of catalyst into a reaction kettle, heating to 200 ℃, starting to introduce methanol (30 g/h), continuously heating to 222 ℃ and reacting for 23 hours to obtain a tetramethoxysilane crude product; and (3) carrying out subsequent rectification on the crude tetramethoxysilane, wherein the rectification temperature is 100 ℃, the pressure is-0.098 MPa, the reflux ratio is 6, the rectification equipment is made of full-lining polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic grade tetramethoxysilane is obtained.
The preparation method of the catalyst comprises the following steps: firstly, 80 parts by mass of nano Cu powder and 20 parts by mass of nano Ti powder are ball-milled for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 1000 ℃ for 5h to obtain the titanium-copper alloy material.
Example 7
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of triethanolamine, 100 parts by mass of silicon powder and 0.4 part by mass of catalyst into a reaction kettle, heating to 200 ℃ and starting to introduce methanol (30 g/h), continuously heating to 230 ℃ and reacting for 24 hours to obtain a tetramethoxysilane crude product; and (3) carrying out subsequent rectification on the crude tetramethoxysilane, wherein the rectification temperature is 102 ℃, the pressure is-0.098 MPa, the reflux ratio is 4, the rectification equipment is made of fully-lined polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic grade tetramethoxysilane is obtained.
The preparation method of the catalyst comprises the following steps: firstly, carrying out ball milling on 90 parts by mass of nano Cu powder and 10 parts by mass of nano Ti powder for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 900 ℃ for 5h to obtain the titanium-copper alloy material.
Example 8
A method for preparing electronic grade tetraalkoxysilane, comprising the following steps:
a thermometer and a mechanical stirring device are arranged on a specially-made long-neck three-port reactor, and the outside of the reactor is heated by electricity. Adding 500 parts by mass of triethanolamine, 100 parts by mass of silicon powder and 0.4 part by mass of catalyst into a reaction kettle, heating to 200 ℃ to start introducing isopropanol (30 g/h), continuously heating to 230 ℃ and reacting for 23h to obtain a tetraisopropoxysilane crude product; and (3) carrying out subsequent rectification on the crude tetraisopropoxysilane, wherein the rectification temperature is 120 ℃, the pressure is-0.098 MPa, the reflux ratio is 8, the rectification equipment is made of fully-lined polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall rings, so that the electronic-grade tetraisopropoxysilane is obtained.
The preparation method of the catalyst comprises the following steps: firstly, carrying out ball milling on 90 parts by mass of nano Cu powder and 10 parts by mass of nano Ti powder for 30min to obtain a mixture; and then placing the mixture into a high-temperature furnace, introducing high-purity nitrogen (99.99%) with the flow rate of 50mL/min for 1h for pretreatment, and calcining at the high temperature of 800 ℃ for 5h to obtain the titanium-copper alloy material.
The electronic-grade tetraalkoxysilanes in examples 1 to 8 were each subjected to performance measurement, and the results are shown in table 1.
The results of analysis and measurement of electronic-grade tetraalkoxysilane in table 1 and examples 1 to 8.
As shown in Table 1, the electronic grade tetraalkoxysilane products in examples 1 to 8 have GC purity of 4N, metal ion purity of 7-9N, and impurity contents of chlorine (Cl), boron (B) and copper (Cu) of less than 10ppb, which satisfies the preparation requirement of the key raw material grinding particles of the polishing solution for the high-end chip manufacturing CMP technology in the semiconductor industry.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (6)
1. The preparation method of the electronic grade tetraalkoxysilane is characterized by comprising the following steps:
(1) Adding a certain amount of solvent, silicon powder and catalyst into a reaction kettle, heating to 180-250 ℃, starting alcohol introduction, continuously heating to 210-240 ℃ and reacting for 20-28h to obtain a crude tetraalkoxysilane product;
(2) Rectifying the crude tetraalkoxysilane to obtain electronic-grade tetraalkoxysilane;
in the step (1), the catalyst is titanium-copper alloy;
the preparation method of the catalyst titanium-copper alloy comprises the following steps:
firstly ball milling nano Cu powder and nano Ti powder to obtain mixed powder, then placing the mixed powder into a high-temperature furnace, introducing high-purity nitrogen for pretreatment, and calcining at 700-1300 ℃ for 2-6h to obtain the titanium-copper alloy material.
2. The method for preparing electronic grade tetraalkoxysilane according to claim 1, wherein: in the step (1), the solvent comprises one or more of diphenyl ether, dodecylbenzene, dimethyl benzene ether and triethanolamine.
3. The method for preparing electronic grade tetraalkoxysilane according to claim 1, wherein: in the step (1), the mass ratio of the solvent to the silicon powder to the catalyst is 500:100:0.2-0.4.
4. The method for preparing electronic grade tetraalkoxysilane according to claim 1, wherein: the mass percentage of Cu powder in the mixed powder is 70-90%, the inlet flow rate of the high-purity nitrogen is 30-50mL/min, and the pretreatment time is 0.5-2h.
5. The method for preparing electronic grade tetraalkoxysilane according to claim 1, wherein: in the step (1), the alcohol is one or more of methanol, ethanol, propanol or isopropanol, and the alcohol passing rate is 18-60g/h.
6. The method for preparing electronic grade tetraalkoxysilane according to claim 1, wherein: in the step (2), the rectification temperature is 95-130 ℃, the pressure is-0.098 MPa, the reflux ratio is 1-10, the rectification equipment is made of fully-lined polytetrafluoroethylene, and the filler is polytetrafluoroethylene pall ring.
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| CN103772424A (en) * | 2013-12-31 | 2014-05-07 | 贵州威顿晶磷电子材料有限公司 | Preparation method of electronic grade tetraethoxysilane |
| CN109748931A (en) * | 2019-02-18 | 2019-05-14 | 苏州金宏气体股份有限公司 | A kind of preparation method and production system of high-purity ethyl orthosilicate |
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| CN103772424A (en) * | 2013-12-31 | 2014-05-07 | 贵州威顿晶磷电子材料有限公司 | Preparation method of electronic grade tetraethoxysilane |
| CN109748931A (en) * | 2019-02-18 | 2019-05-14 | 苏州金宏气体股份有限公司 | A kind of preparation method and production system of high-purity ethyl orthosilicate |
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