CN108250232B - Refining method of bis (diethyl) aminosilane - Google Patents
Refining method of bis (diethyl) aminosilane Download PDFInfo
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- CN108250232B CN108250232B CN201810130861.XA CN201810130861A CN108250232B CN 108250232 B CN108250232 B CN 108250232B CN 201810130861 A CN201810130861 A CN 201810130861A CN 108250232 B CN108250232 B CN 108250232B
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- aminosilane
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- RWSLHLQWGULCLI-UHFFFAOYSA-N [amino(ethyl)silyl]ethane Chemical compound CC[SiH](N)CC RWSLHLQWGULCLI-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000007670 refining Methods 0.000 title claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 239000003463 adsorbent Substances 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- FNXZGQRYAJYZLP-UHFFFAOYSA-N 6-bromoquinolin-4-amine Chemical compound C1=C(Br)C=C2C(N)=CC=NC2=C1 FNXZGQRYAJYZLP-UHFFFAOYSA-N 0.000 claims description 9
- YNJXNPTWSQAFPQ-UHFFFAOYSA-M iodozinc(1+);3h-thiophen-3-ide Chemical compound I[Zn+].C1=CSC=[C-]1 YNJXNPTWSQAFPQ-UHFFFAOYSA-M 0.000 claims description 9
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 8
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- IDXLUNCVVBZUEN-UHFFFAOYSA-N (3-formyl-5-methylphenyl)boronic acid Chemical compound CC1=CC(C=O)=CC(B(O)O)=C1 IDXLUNCVVBZUEN-UHFFFAOYSA-N 0.000 claims description 7
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 6
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
- 125000005265 dialkylamine group Chemical group 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- DJFNDGIKNBLDGV-UHFFFAOYSA-N (3-formyl-5-methylphenoxy)boronic acid Chemical compound C(=O)C=1C=C(C=C(C=1)C)OB(O)O DJFNDGIKNBLDGV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- 125000006552 (C3-C8) cycloalkyl group Chemical group 0.000 description 1
- QCQCHGYLTSGIGX-GHXANHINSA-N 4-[[(3ar,5ar,5br,7ar,9s,11ar,11br,13as)-5a,5b,8,8,11a-pentamethyl-3a-[(5-methylpyridine-3-carbonyl)amino]-2-oxo-1-propan-2-yl-4,5,6,7,7a,9,10,11,11b,12,13,13a-dodecahydro-3h-cyclopenta[a]chrysen-9-yl]oxy]-2,2-dimethyl-4-oxobutanoic acid Chemical compound N([C@@]12CC[C@@]3(C)[C@]4(C)CC[C@H]5C(C)(C)[C@@H](OC(=O)CC(C)(C)C(O)=O)CC[C@]5(C)[C@H]4CC[C@@H]3C1=C(C(C2)=O)C(C)C)C(=O)C1=CN=CC(C)=C1 QCQCHGYLTSGIGX-GHXANHINSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- FGPZBVIFLOFHFM-UHFFFAOYSA-N dodecyl benzenesulfonate;iron Chemical compound [Fe].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 FGPZBVIFLOFHFM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material Substances 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
- 150000003377 silicon compounds Chemical class 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
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
-
- 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/20—Purification, separation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a refining method of bis (diethyl) aminosilane, wherein industrial bis (diethyl) aminosilane enters a reactor filled with a novel impurity decomposer, the temperature is 30-80 ℃, and the flow rate is 1-5BV/h, so as to obtain primarily refined bis (diethyl) aminosilane gas; then the mixture enters an adsorption tower filled with an adsorbent, the temperature is 20-40 ℃, and the flow rate is 1-5 BV/h; the bis (diethyl) aminosilane is obtained in high purity after adsorption.
Description
Technical Field
The invention relates to a method for purifying silane, in particular to a method for refining bis (diethyl) aminosilane.
Background
Electronic circuits, such as integrated circuits, display circuits, memory circuits, and power circuits, have been made smaller and smaller today to increase portability and computing power. Silicon dioxide layers are used in a variety of applications for fabricating active or passive features of electronic circuits. In one application, where a silicon dioxide layer is used to fabricate a multi-layer etch-resistant stack, a specific film formation method of ALD method is as follows: the unreacted precursor is evacuated in a state where only one layer of the precursor is adsorbed, utilizing a so-called self-limiting effect: when the substrate surface is covered with adsorbed precursor, no further adsorption of this gas will occur. Next, a reactive gas is introduced, and the precursor is oxidized or reduced to obtain only one thin film having a desired composition, and then the reactive gas is exhausted. Such a process is set as one cycle, and the cycle is repeated, thereby growing the thin film. Therefore, in the ALD method, a thin film grows two-dimensionally. Si-containing films are widely used in the semiconductor, photovoltaic, LCD-TFT, flat panel, refractory, or aerospace industries. The Si-containing film can be used, for example, as an insulating dielectric material having electrical properties (SiO2, SiN, SiCN, SiCOH, MSiOx, where M is Hf, Zr, Ti, Nb, Ta, or Ge and x is greater than zero), and the Si-containing film can be used as a conductive film, such as a metal silicide or a metal silicon nitride. Due to the stringent requirements imposed by the downscaling of electrical device architectures towards the nanometer scale (especially below 28nm nodes), increasingly fine-tuned molecular precursors are required which, in addition to having high deposition rates, conformality and robustness of the resulting films, also fulfill the requirements of volatility (for ALD processes), lower process temperatures, reactivity with various oxidizing agents and low film contamination. As a precursor material of the ALD film, for example, Trimethylaluminum (TMA), titanium tetrachloride (TiCl4), tris (dimethylamino) silane (3DMAS), bis (diethylamino) silane (BDEAS) can be used. The demand for electronic grade bis (diethylamino) silane (BDEAS) has also increased accordingly.
CN107406466A discloses a method for producing a dialkylaminosilane, in which a large amount of a hydrochloride salt of dialkylamine is produced as a by-product in addition to a target dialkylamine in a method for synthesizing the dialkylamine by reaction of a chlorosilane and the dialkylamine, and therefore, when the target dialkylamine is obtained, it is necessary to prevent a decrease in volume efficiency due to a large amount of a solvent, and to produce the dialkylamine in large quantities at low cost. As the solvent for reacting a dialkylamine with a chlorosilane, an aprotic polar solvent having high solubility for a hydrochloride of the dialkylamine and a metal chloride which are by-produced in the reaction and a linear hydrocarbon or a branched hydrocarbon having high solubility and hardly dissolving a halogen compound are used, whereby a dialkylaminosilane having a small halogen content can be produced with high volume efficiency. Rectification is carried out, which makes it possible to obtain high-quality dialkylaminosilanes having a low halogen content (chlorine).
CN104080944B discloses Si-containing thin film forming precursors, methods of synthesizing the same, and methods of using the same to deposit silicon-containing thin films using vapor deposition methods for manufacturing semiconductors, photovoltaic devices, LCD-TFTs, flat panel devices, refractory materials, or aerospace materials.
Si-containing precursors are disclosed in US2010/0164057, including silicon compounds having the formula R4-xSiLx, wherein x is an integer having a value of 1-3; r can be selected from H, branched and unbranched C1-C6 alkyl, C3-C8 cycloalkyl and C6-C13 aryl; and L may be selected from isocyanate, methyl ethyl ketoxime, trifluoroacetate, trifluoromethanesulfonate, acyloxy, β -diketoimine (β -diketotinate), β -di-imine (β -di-imidate), amidine, guanidine, alkylamino, hydride, alkoxide or formate ligands.
In the purification of bis (diethylamino) silane (BDEAS) used in the prior art and the prior art, a rectification method is often used, and the purity of bis (diethylamino) silane is difficult to exceed 99.99%.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a refining method of bis (diethyl) aminosilane.
In order to solve the technical problems, the invention adopts the following technical scheme: a refining method of bis (diethyl) aminosilane comprises the following steps:
(1) according to the weight portion, 100 portions of silica gel are washed and dried, 5 to 15 portions of mercaptopropyltriethoxysilane, 0.001 to 0.01 portion of 3-formyl-5-methylphenylboronic acid, 1 to 5 portions of triethylamine, 1000 portions of acetone containing 300 organic silicon, the reaction is carried out for 10 to 24 hours at the temperature of 50 to 80 ℃, the filtration, the washing and the drying are carried out to obtain the mercaptosilanized silica gel, 1000 portions of acetone containing 300 organic silicon is added, 0.1 to 1 portion of ferric dodecyl benzene sulfonate, 0.005 to 0.02 portion of 3-thienyl zinc iodide and 0.01 to 0.1 portion of 4-amino-6-bromoquinoline are added, and the reflux is carried out for 20 to 40 hours under the mechanical stirring; after the reaction is stopped, filtering, washing and drying to prepare a novel impurity decomposer;
(2) putting industrial-grade bis (diethyl) aminosilane into a reactor filled with a novel impurity decomposer, wherein the temperature is 30-80 ℃, and the flow rate is 1-5BV/h to obtain primarily refined bis (diethyl) aminosilane gas;
(3) the primarily refined bis (diethyl) aminosilane gas enters an adsorption tower filled with an adsorbent, the temperature is 20-40 ℃, and the flow rate is 1-5 BV/h; the bis (diethyl) aminosilane is obtained in high purity after adsorption.
The silica gel, the mercaptopropyltriethoxysilane, the 3-formyl-5-methyl phenyl boric acid, the triethylamine, the acetone, the ferric dodecyl benzene sulfonate, the 3-thienyl zinc iodide and the 4-amino-6-bromoquinoline are all commercially available products.
The adsorbent is a known desiccant, and examples of the desiccant preferably used include a type X molecular sieve, a type A molecular sieve, activated carbon, which is subjected to a pretreatment such as an acid treatment, a heat treatment or a steam treatment before use.
Compared with the prior art, the invention has the following beneficial effects:
the novel impurity decomposer adopts sulfydryl silanized silica gel loaded ferric dodecyl benzene sulfonate, 3-thienyl zinc iodide, 4-amino-6-bromoquinoline and 3-formyl-5-methyl phenyl boric acid, can adsorb nitrogen-containing and phosphorus-containing impurities in silane, has a microporous structure, is large in surface of adsorbed gas, is easy to fill in a reactor in a spherical structure, and can obtain high-purity bis (diethyl) aminosilane with the volume fraction of 99.999%.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, which are provided only for the purpose of illustration and are not intended to limit the scope of the present invention.
In the examples, the technical bis (diethyl) aminosilane was a commercially available product, such as that developed by Borre electronics technologies, Inc., at 97% level.
Example 1
A refining method of bis (diethyl) aminosilane comprises the following steps:
(1) according to the weight portion, 100 portions of silica gel are washed and dried, 11 portions of mercaptopropyltriethoxysilane, 0.003 portion of 3-formyl-5-methylphenylboronic acid, 2 portions of triethylamine and 800 portions of acetone are added, reaction is carried out for 15 hours at 70 ℃, filtration, washing and drying are carried out, thus obtaining the mercaptosilanized silica gel, 700 portions of acetone are added, 0.3 portion of ferric dodecyl benzene sulfonate, 0.01 portion of 3-thienyl zinc iodide and 0.03 portion of 4-amino-6-bromoquinoline are added, and the mixture is refluxed for 24 hours under mechanical stirring; after the reaction is stopped, filtering, washing and drying to prepare a novel impurity decomposer;
(2) putting industrial-grade bis (diethyl) aminosilane into a reactor filled with a novel impurity decomposer, and obtaining primarily refined bis (diethyl) aminosilane gas at the temperature of 60 ℃ and the flow rate of 2 BV/h;
(3) the primarily refined bis (diethyl) aminosilane gas enters an adsorption tower filled with an adsorbent, the temperature is 26 ℃, and the flow rate is 3 BV/h; the bis (diethyl) aminosilane is obtained in high purity after adsorption. The bis (diethyl) aminosilane purity is shown in table 1.
Example 2
A refining method of bis (diethyl) aminosilane comprises the following steps:
(1) according to the weight portion, 100 portions of silica gel are washed and dried, 5 portions of mercaptopropyltriethoxysilane, 0.001 portion of 3-formyl-5-methylphenylboronic acid, 1 portion of triethylamine and 300 portions of acetone are added, the mixture is reacted for 10 hours at 50 ℃, filtered, washed and dried to obtain the mercaptosilanized silica gel, 300 portions of acetone are added, 0.1 portion of ferric dodecyl benzene sulfonate, 0.005 portion of 3-thienyl zinc iodide and 0.01 portion of 4-amino-6-bromoquinoline are added, and the mixture is refluxed for 20 hours under mechanical stirring; after the reaction is stopped, filtering, washing and drying to prepare a novel impurity decomposer;
(2) putting industrial-grade bis (diethyl) aminosilane into a reactor filled with a novel impurity decomposer, wherein the temperature is 30 ℃, and the flow rate is 1BV/h to obtain primarily refined bis (diethyl) aminosilane gas;
(3) the primarily refined bis (diethyl) aminosilane gas enters an adsorption tower filled with an adsorbent, the temperature is 20 ℃, and the flow rate is 1 BV/h; the bis (diethyl) aminosilane is obtained in high purity after adsorption. The bis (diethyl) aminosilane purity is shown in table 1.
Example 3
A refining method of bis (diethyl) aminosilane comprises the following steps:
(1) according to the weight portion, 100 portions of silica gel are washed and dried, 15 portions of mercaptopropyltriethoxysilane, 0.01 portion of 3-formyl-5-methylphenylboronic acid, 5 portions of triethylamine and 1000 portions of acetone are added, the mixture is reacted for 24 hours at 80 ℃, filtered, washed and dried to obtain the mercaptosilanized silica gel, 1000 portions of acetone are added, 1 portion of ferric dodecyl benzene sulfonate, 0.02 portion of 3-thienyl zinc iodide and 0.1 portion of 4-amino-6-bromoquinoline are added, and the mixture is refluxed for 40 hours under mechanical stirring; after the reaction is stopped, filtering, washing and drying to prepare a novel impurity decomposer;
(2) putting industrial bis (diethyl) aminosilane into a reactor filled with a novel impurity decomposer, wherein the temperature is 80 ℃, and the flow rate is 5BV/h, so as to obtain primarily refined bis (diethyl) aminosilane gas;
(3) the primarily refined bis (diethyl) aminosilane gas enters an adsorption tower filled with an adsorbent, the temperature is 40 ℃, and the flow rate is 5 BV/h; the bis (diethyl) aminosilane is obtained in high purity after adsorption. The bis (diethyl) aminosilane purity is shown in table 1.
Comparative example 1
3-formyl-5-methylphenylboronic acid was not added as in example 1 except that the bis (diethyl) aminosilane purity was as shown in Table 1.
Comparative example 2
Iron dodecylbenzenesulfonate was not added, and otherwise the same as in example 1, the purity of bis (diethyl) aminosilane is shown in Table 1.
Comparative example 3
3-Thienylzinc iodide was not added and otherwise as in example 1, the bis (diethyl) aminosilane had a purity as shown in Table 1.
Comparative example 4
4-amino-6-bromoquinoline was not added, otherwise as in example 1, and the bis (diethyl) aminosilane purity is shown in Table 1.
Comparative example 5
Step one was omitted, otherwise the same as in example 1. The bis (diethyl) aminosilane purity is shown in table 1.
Table 1: comparison of the% purity of bis (diethyl) aminosilane after adsorption of test samples made by different processes.
Claims (5)
1. A refining method of bis (diethyl) aminosilane is characterized by comprising the following steps:
putting industrial-grade bis (diethyl) aminosilane into a reactor filled with an impurity decomposing agent, wherein the temperature is 30-80 ℃, and the flow rate is 1-5BV/h to obtain primarily refined bis (diethyl) aminosilane gas; the primarily refined bis (diethyl) aminosilane gas enters an adsorption tower filled with an adsorbent, the temperature is 20-40 ℃, and the flow rate is 1-5 BV/h; obtaining high-purity bis (diethyl) aminosilane after adsorption;
the preparation method of the impurity decomposing agent comprises the following steps:
according to the weight portion, 100 portions of silica gel are washed and dried, 5 to 15 portions of mercaptopropyltriethoxysilane, 0.001 to 0.01 portion of 3-formyl-5-methylphenylboronic acid, 1 to 5 portions of triethylamine, 1000 portions of acetone containing 300 organic silicon, the reaction is carried out for 10 to 24 hours at the temperature of 50 to 80 ℃, the filtration, the washing and the drying are carried out to obtain the mercaptosilanized silica gel, 1000 portions of acetone containing 300 organic silicon is added, 0.1 to 1 portion of ferric dodecyl benzene sulfonate, 0.005 to 0.02 portion of 3-thienyl zinc iodide and 0.01 to 0.1 portion of 4-amino-6-bromoquinoline are added, and the reflux is carried out for 20 to 40 hours under the mechanical stirring; after the reaction is stopped, filtering, washing and drying to prepare a novel impurity decomposer;
the adsorbent is selected from X type molecular sieve, A type molecular sieve and active carbon.
2. The method of refining a bis (diethyl) aminosilane according to claim 1, characterized in that
The adsorbent is subjected to acid treatment, heat treatment or steam treatment before use.
3. The method of refining a bis (diethyl) aminosilane according to claim 1, characterized in that
The impurity decomposer adopts ferric dodecyl benzene sulfonate loaded on sulfydryl silanized silica gel and 3-thienyl zinc iodide,
4-amino-6-bromoquinoline and 3-formyl-5-methylphenylboronic acid adsorb nitrogen-containing and phosphorus-containing impurities in silane.
4. The method of refining a bis (diethyl) aminosilane according to claim 1, characterized in that
The novel impurity decomposing agent has a microporous structure and is in a spherical structure.
5. The method of purifying bis (diethyl) aminosilane according to claim 1, characterized in that the high purity bis (diethyl) aminosilane has a purity of 99.999%.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0770619A2 (en) * | 1995-10-23 | 1997-05-02 | Dow Corning Corporation | Process for purifying halosilanes |
| CN1455764A (en) * | 2001-01-15 | 2003-11-12 | 昭和电工株式会社 | Process for purifying octafluoropropane, process for preparing same and use thereof |
| CN101407526A (en) * | 2007-10-12 | 2009-04-15 | 赢创德固赛有限责任公司 | Removal of polar organic compounds and extraneous metals from organosilanes |
| CN101597301A (en) * | 2008-06-03 | 2009-12-09 | 赢创德固赛有限责任公司 | Be used for the method for aftertreatment from the saliferous residue of preparation amino-functional organosilane |
| CN104789785A (en) * | 2015-05-19 | 2015-07-22 | 河北工程大学 | Method for extracting germanium from germanium-containing smoke dust |
| CN104817579A (en) * | 2015-05-12 | 2015-08-05 | 苏州普耀光电材料有限公司 | Efficient purifying method of triethyl gallium |
| CN106345264A (en) * | 2016-07-19 | 2017-01-25 | 浙江博瑞电子科技有限公司 | Method for purifying organic fluorine gas by using novel impurity decomposing agent |
| CN107501124A (en) * | 2017-08-26 | 2017-12-22 | 宁波德欣科技有限公司 | A kind of preparation method of the formonitrile HCN of 1 amino 4 (ethylamino) anthraquinone 2 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012136472A (en) * | 2010-12-27 | 2012-07-19 | Shin-Etsu Chemical Co Ltd | Process for producing refined aminosilane |
-
2018
- 2018-02-09 CN CN201810130861.XA patent/CN108250232B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0770619A2 (en) * | 1995-10-23 | 1997-05-02 | Dow Corning Corporation | Process for purifying halosilanes |
| CN1455764A (en) * | 2001-01-15 | 2003-11-12 | 昭和电工株式会社 | Process for purifying octafluoropropane, process for preparing same and use thereof |
| CN101407526A (en) * | 2007-10-12 | 2009-04-15 | 赢创德固赛有限责任公司 | Removal of polar organic compounds and extraneous metals from organosilanes |
| CN101597301A (en) * | 2008-06-03 | 2009-12-09 | 赢创德固赛有限责任公司 | Be used for the method for aftertreatment from the saliferous residue of preparation amino-functional organosilane |
| CN104817579A (en) * | 2015-05-12 | 2015-08-05 | 苏州普耀光电材料有限公司 | Efficient purifying method of triethyl gallium |
| CN104789785A (en) * | 2015-05-19 | 2015-07-22 | 河北工程大学 | Method for extracting germanium from germanium-containing smoke dust |
| CN106345264A (en) * | 2016-07-19 | 2017-01-25 | 浙江博瑞电子科技有限公司 | Method for purifying organic fluorine gas by using novel impurity decomposing agent |
| CN107501124A (en) * | 2017-08-26 | 2017-12-22 | 宁波德欣科技有限公司 | A kind of preparation method of the formonitrile HCN of 1 amino 4 (ethylamino) anthraquinone 2 |
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