CN108147378B - A kind of refining methd of trimethylsilyl amine - Google Patents
A kind of refining methd of trimethylsilyl amine Download PDFInfo
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- CN108147378B CN108147378B CN201810121080.4A CN201810121080A CN108147378B CN 108147378 B CN108147378 B CN 108147378B CN 201810121080 A CN201810121080 A CN 201810121080A CN 108147378 B CN108147378 B CN 108147378B
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- trimethylsilyl amine
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- amine
- trimethylsilyl
- rectifying
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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
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
- C01B21/0687—After-treatment, e.g. grinding, purification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention relates to a kind of refining methds of trimethylsilyl amine, technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane, 10-30 DEG C of temperature, flow velocity 1-5BV/h, pressure 0.3-0.7MPa, the trimethylsilyl amine of primary purification is obtained, then is rectifying to obtain the trimethylsilyl amine of high-purity.
Description
Technical field
The present invention relates to a kind of purification process of silylation amine, especially a kind of refining methd of trimethylsilyl amine.
Background technique
Trimethylsilyl amine (chemical molecular formula is N (SiH3) 3, in the present invention referred to as " TSA ") is variable, colourless
, the spontaneously inflammable and liquid that can easily hydrolyze, the boiling point with -105.6 DEG C of fusing points and+52 DEG C.Nitrogenous silication
It closes object such as trimethylsilyl amine is substance important in semi-conductor industry.Silicon nitride layer is prepared using TSA.More particularly have found
TSA is in chip manufacturing as the application in the layer precursor of silicon nitride layer or silicon oxynitride layer.Since it is in chip manufacturing
Purposes, it is important to be able to it is safe and reliable, consistently with it is required be usually that the quality of high-purity prepares trimethylsilyl
Amine.
The method that CN103974958B prepares trimethylsilyl amine in the liquid phase, the method includes by monochlorosilane
(A or A') is previously charged into reactor (1) with the liquid form in the solution in solvent (H), wherein the solvent is for a chlorine
Monosilane, ammonia and TSA be inert and have boiling point than TSA high, and by ammonia (B) with the solution form in solvent (H)
The reactor is imported, is reacted in reactor (1), then the products therefrom mixture of autoreactor in future (1) imports
With pass through filter unit (2), and solid ammonium chloride (C) and inherent filtration in future device list are isolated from the product mixtures
The filtrate of first (2) imports destilling tower (3), distills out excessive monochlorosilane (A') by tower top in destilling tower (3), is cold
It coagulates and is mixed with the solvent and is delivered as a liquid to reactor (1), and gaseous matter (D) is passed through to the tower of destilling tower (3)
Top row goes out, and bottom product (E) is transported to destilling tower (4), by the product trimethylsilyl amine (G) in destilling tower (4)
It is distilled out and is condensed by tower top.Mainly by distilation.
CN106659999A, which is disclosed, is related to a kind of method for preparing trimethylsilyl amine in the liquid phase, wherein a chlorosilane with
Liquid form is present in the solvent of high temperature, and a chlorosilane is reacted with the NH3 of stoichiometric excess.The preparation of the TSA
It is carried out according to following reaction equation: (1) 3SIH3Cl+4NH3 → 3NH4Cl+ (SiH3) 3N.The purity of TSA through distillation purifying
Higher than 99.5 weight %.
TWI585037B discloses kind of the method for manufacturing three silicon alkanamines in liquid phase, it is characterised in that (a) is at least dissolved in
A chloromethane silicon alkane (monochlorosilane, MCS) in solvent (L) is fed in reacting furnace (1) in liquid, wherein the solvent
It is inertia relative to MCS, ammonia (NH3) and TSA, and having compared with TSA is high boiling point, stirs the solution, and by the solution
Temperature T is set as 10 DEG C or higher, and (b) reaction carries out in reacting furnace (1), wherein will be relative to MCS stoichiometry mistake
The NH3 of amount introduces the reacting furnace (1), wherein maintain temperature T, and then the reacting furnace is depressured by (c), pressure be set as from
0.5bar a to 0.8bar a heats the reacting furnace, defeated with gas types via distilling apparatus (2) from reacting furnace (1) tower top
The product mixtures (TSA, L, NH4Cl, DSA, NH3) are led, are separated the NH3 by vacuum plant (8), in heat exchanger (7)
It is middle the product mixtures (TSA, L, NH4Cl, DSA) are condensed and collect in the container (6) product mixtures (TSA, L,
NH4Cl, DSA), and the product mixtures (d) are filtered by filter device (3), and separate solid from the product mixtures
Ammonium chloride (NH4Cl), and from the filter device (3) by filtrate transporting to the rectifying tubing string (4), divide in the rectifying tubing string (4)
From the filtrate it is that DSA and mixture (TSA, L), the DSA are isolated from tower top, and by mixture (TSA, the L) transporting to rectifying
Tubing string (11), separation solvent (L) and TSA, the TSA are isolated from tower top in the rectifying tubing string (11), and the solvent is followed again
Ring, or from the filter device (3) by the filtrate transporting to batch rectifying tubing string (4), it will from batch rectifying tubing string (4) tower top
DSA is isolated and is then isolated TSA in tower top, and the solvent is recycled, and (e) from the reacting furnace (1) via
Filter device (5) transporting bottom product mixture (L, NH4Cl), and solid ammonium chloride is separated in the filter device (5)
(NH4Cl), and the solvent (L) is obtained, which is to be collected in container (9), and (f) follow 0 to 99% solvent again
Ring and the solvent that non-recirculated is replaced with solvent (L).Reach more than the TSA purity of 99.5 weight %.
Existing patent and the used trimethylsilyl amine of technical literature are after rectification process, trimethylsilyl amine purity
It is difficult to more than 99.99%.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide a kind of trimethylsilyl amine
Refining methd.
In order to solve the above technical problems, present invention employs the following technical solutions: a kind of trimethylsilyl amine
Refining methd, comprising the following steps:
(1) by weight, dry with 5-10 parts of methanol clean the surfaces by 100 parts of homogeneous-phase anion exchange films, dry film
Leaching is embedded in 1000-2000 parts of propenyl-1,3-sulfonic acid lactones, 0.0001-0.001 parts of dimethylsilyl (cyclopentadiene) (9-
Fluorenyl) zirconium dichloride, 0.01-0.1 parts of 9- octadecenic acid copper, in 0.1-1 parts of allyl Octyl Ether mixed solutions, N2 protection is used
60Co gamma-rays exposure dose is 10-50kGy or so, irradiation time 10-60 minutes, graft copolymer membrane is taken out, with 1000-2000 parts
Tetrahydrofuran cleans the surface of film, dry, obtains trimethylsilyl amine purification permeable membrane.
(2) technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane,
10-30 DEG C of temperature, flow velocity 1-5BV/h, the trimethylsilyl amine of primary purification is obtained, then be rectifying to obtain the three of high-purity
Methyl-monosilane base amine.
Further, membrane reactor pressure 0.3-0.7MPa.
The rectifying, including multistage rectification and single-stage rectifying.
The homogeneous-phase anion exchange film, propenyl-1,3-sulfonic acid lactone, dimethylsilyl (cyclopentadiene) (9-
Fluorenyl) zirconium dichloride, 9- octadecenic acid copper is commercial product.
Compared with prior art, the invention has the following advantages:
Pass through grafted propylene base -1,3- sultones, dimethyl-silicon through this patent trimethylsilyl amine purification permeable membrane
Alkyl (cyclopentadiene) (9- fluorenyl) zirconium dichloride, 9- octadecenic acid copper and its metal complex formed, can adsorb three
Impurity in methyl-monosilane base amine, technical grade trimethylsilyl amine can obtain volume point after film process, then through rectifying
The high-purity trimethylsilyl amine of number 99.999%.
The reactant is commercial product, preferably technical grade product.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is furture elucidated, but these the examples are only for explaining the invention, without
It is for limiting the scope of the invention.
Technical grade trimethylsilyl amine is commercial product, purity 95% in embodiment.
Embodiment 1
A kind of refining methd of trimethylsilyl amine, comprising the following steps:
(1) by weight, dry with 8 parts of methanol clean the surfaces by 100 parts of homogeneous-phase anion exchange films, dry film leaching is buried
In 1500 parts of propenyl-1,3-sulfonic acid lactones, 0.0003 part of dimethylsilyl (cyclopentadiene) (9- fluorenyl) zirconium dichloride,
0.04 part of 9- octadecenic acid copper, in 0.1 part of allyl Octyl Ether mixed solution, N2 protection is with 60Co gamma-rays exposure dose
34kGy or so irradiation time 30 minutes, graft copolymer membrane is taken out, and the surface of film is cleaned with 1800 parts of tetrahydrofurans, dry, is obtained
Trimethylsilyl amine purifies permeable membrane.
(2) technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane,
22 DEG C of temperature, flow velocity 2BV/h, membrane reactor pressure 0.4MPa.The trimethylsilyl amine of primary purification is obtained, then through rectifying
Obtain the trimethylsilyl amine of high-purity.Trimethylsilyl amine purity is shown in Table 1.
Embodiment 2
A kind of refining methd of trimethylsilyl amine, comprising the following steps:
(1) by weight, dry with 5 parts of methanol clean the surfaces by 100 parts of homogeneous-phase anion exchange films, dry film leaching is buried
In 1000 parts of propenyl-1,3-sulfonic acid lactones, 0.0001 part of dimethylsilyl (cyclopentadiene) (9- fluorenyl) zirconium dichloride,
0.01 part of 9- octadecenic acid copper, in 0.4 part of allyl Octyl Ether mixed solution, N2 protection is with 60Co gamma-rays exposure dose
10kGy or so irradiation time 60 minutes, graft copolymer membrane is taken out, and the surface of film is cleaned with 1000 parts of tetrahydrofurans, dry, is obtained
Trimethylsilyl amine purifies permeable membrane.
(2) technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane,
10 DEG C of temperature, flow velocity 1BV/h, membrane reactor pressure 0.3MPa obtain the trimethylsilyl amine of primary purification, then through rectifying
Obtain the trimethylsilyl amine of high-purity.Trimethylsilyl amine purity is shown in Table 1.
Embodiment 3
A kind of refining methd of trimethylsilyl amine, comprising the following steps:
(1) by weight, dry with 10 parts of methanol clean the surfaces by 100 parts of homogeneous-phase anion exchange films, dry film leaching
It is embedded in 2000 parts of propenyl-1,3-sulfonic acid lactones, 0.001 part of dimethylsilyl (cyclopentadiene) (9- fluorenyl) zirconium dichloride,
0.1 part of 9- octadecenic acid copper, in 1 part of allyl Octyl Ether mixed solution, N2 protection is with 60Co gamma-rays exposure dose
50kGy or so irradiation time 10 minutes, graft copolymer membrane is taken out, and the surface of film is cleaned with 2000 parts of tetrahydrofurans, dry, is obtained
Trimethylsilyl amine purifies permeable membrane.
(2) technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane,
30 DEG C of temperature, flow velocity 5BV/h, membrane reactor pressure 0.7MPa obtain the trimethylsilyl amine of primary purification, then through rectifying
Obtain the trimethylsilyl amine of high-purity.Trimethylsilyl amine purity is shown in Table 1.
Comparative example 1
Propenyl-1,3-sulfonic acid lactone is added without, the other the same as in Example 1, and trimethylsilyl amine purity is shown in Table 1.
Comparative example 2
Dimethylsilyl (cyclopentadiene) (9- fluorenyl) zirconium dichloride is added without, the other the same as in Example 1, trimethyl silane
Base amine purity is shown in Table 1.
Comparative example 3
9- octadecenic acid copper is added without, the other the same as in Example 1, and trimethylsilyl amine purity is shown in Table 1.
Comparative example 4
Allyl Octyl Ether is added without, the other the same as in Example 1, and trimethylsilyl amine purity is shown in Table 1.
Comparative example 5
Without the purification permeable membrane absorption of trimethylsilyl amine, rectifying is only carried out.Trimethylsilyl amine purity is shown in Table 1.
Comparative example 6
Without rectifying, the other the same as in Example 1, trimethylsilyl amine purity is shown in Table 1.
Table 1: the comparison of trimethylsilyl amine purity % after the test specimen absorption that different process is made.
Claims (3)
1. a kind of refining methd of trimethylsilyl amine, it is characterised in that the following steps are included:
Technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane, temperature 10-
30 DEG C, flow velocity 1-5BV/h, the trimethylsilyl amine of primary purification is obtained, then be rectifying to obtain the trimethyl silane of high-purity
Base amine；
The preparation method of trimethylsilyl amine purification permeable membrane includes: that by weight, 100 parts of homogeneous-phase anions are exchanged
Film, dry with 5-10 parts of methanol clean the surfaces, dry film leaching is embedded in 1000-2000 parts of propenyl-1,3-sulfonic acid lactones, 0.0001-
0.001 part of dimethylsilyl (cyclopentadiene) (9- fluorenyl) zirconium dichloride, 0.01-0.1 parts of 9- octadecenic acid copper, 0.1-1 parts
In allyl Octyl Ether mixed solution, N2 protection is 10-50kGy with 60Co gamma-rays exposure dose, and irradiation time 10-60 divides
Clock takes out graft copolymer membrane, and the surface of film is cleaned with 1000-2000 parts of tetrahydrofurans, dry, obtains the purification of trimethylsilyl amine
Permeable membrane.
2. a kind of refining methd of trimethylsilyl amine according to claim 1, it is characterised in that membrane reactor pressure
0.3-0.7MPa。
3. a kind of refining methd of trimethylsilyl amine according to claim 1, it is characterised in that: the rectifying,
Including multistage rectification and single-stage rectifying.
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| CN201810121080.4A CN108147378B (en) | 2018-02-07 | 2018-02-07 | A kind of refining methd of trimethylsilyl amine |
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| CN201810121080.4A CN108147378B (en) | 2018-02-07 | 2018-02-07 | A kind of refining methd of trimethylsilyl amine |
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| CN108147378B true CN108147378B (en) | 2019-08-20 |
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| CN113912029B (en) * | 2021-10-18 | 2023-02-21 | 浙江博瑞电子科技有限公司 | Method for preparing trisilylamine at ultralow temperature |
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| CN101735471A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Method for preparing homogeneous phase strong alkali anion exchange membrane by radiation grafting method |
| DE102011075974A1 (en) * | 2011-05-17 | 2012-11-22 | Evonik Degussa Gmbh | Process for the preparation of trisilylamine in the gas phase |
| DE102011078749A1 (en) * | 2011-07-06 | 2013-01-10 | Evonik Degussa Gmbh | Process for the preparation of trisilylamine from monochlorosilane and ammonia |
| WO2013052673A2 (en) * | 2011-10-07 | 2013-04-11 | Voltaix, Inc. | Apparatus and method for the condensed phase production of trisilylamine |
| US20130209343A1 (en) * | 2012-02-10 | 2013-08-15 | American Air Liquide, Inc. | Liquid phase synthesis of trisilylamine |
| DE102012214290A1 (en) * | 2012-08-10 | 2014-02-13 | Evonik Industries Ag | Process for the coupled preparation of polysilazanes and trisilylamine |
| US9284198B2 (en) * | 2013-06-28 | 2016-03-15 | Air Products And Chemicals, Inc. | Process for making trisilylamine |
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