CN108147378A - A kind of process for purification of trimethylsilyl amine - Google Patents
A kind of process for purification of trimethylsilyl amine Download PDFInfo
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- CN108147378A CN108147378A CN201810121080.4A CN201810121080A CN108147378A CN 108147378 A CN108147378 A CN 108147378A CN 201810121080 A CN201810121080 A CN 201810121080A CN 108147378 A CN108147378 A CN 108147378A
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- purification
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- trimethylsilyl
- trimethylsilyl amine
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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
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Abstract
The present invention relates to a kind of process for purification 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, 1 5BV/h of flow velocity, 0.3 0.7MPa of pressure, 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, particularly a kind of process for purification of trimethylsilyl amine.
Background technology
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 point and+52 DEG C.Nitrogenous silication
It is substance important in semi-conductor industry to close object such as trimethylsilyl amine.Silicon nitride layer is prepared using TSA.More particularly it is found that
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 the liquid form of the solution in solvent (H) in reactor (1), wherein the solvent is for a chlorine
Monosilane, ammonia and TSA are inert and with the 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 across 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), and excessive monochlorosilane (A') is distilled out by tower top in destilling tower (3), is cold
It coagulates and the tower for being delivered as a liquid to reactor (1) and gaseous matter (D) being passed through into destilling tower (3) is mixed with the solvent
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 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 liquid in reacting furnace (1), wherein the solvent
It is inertia relative to MCS, ammonia (NH3) and TSA, and with being high boiling point compared with TSA, stirs the solution, and by the solution
Temperature T is set as 10 DEG C or the progress in reacting furnace (1) of higher and (b) reaction, wherein will be relative to MCS stoichiometry mistakes
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 heat 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 detached 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 (d) filter the product mixtures by filter device (3), and solid is detached from the product mixtures
Ammonium chloride (NH4Cl), and from the filter device (3) by filtrate transporting to the rectifying tubing string (4), in the rectifying tubing string (4) point
It is isolated from the filtrate for DSA and mixture (TSA, L), the DSA from tower top, and by mixture (TSA, the L) transporting to rectifying
Tubing string (11), separation solvent (L) and TSA, the TSA are isolated, and the solvent is followed again from tower top in the rectifying tubing string (11)
Ring or from the filter device (3) by the filtrate transporting to batch rectifying tubing string (4), will from batch rectifying tubing string (4) tower top
DSA is isolated and is then isolated TSA in tower top, and by the solvent recycle and (e) from the reacting furnace (1) via
Filter device (5) transporting bottom product mixture (L, NH4Cl), and the separation solid ammonium chloride in the filter device (5)
(NH4Cl), and the solvent (L) is obtained, which is to be collected in container (9) and (f) follows 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 technical literature use trimethylsilyl amine after rectification process, trimethylsilyl amine purity
It is difficult to more than 99.99%.
Invention content
The technical problems to be solved by the invention overcome the deficiencies of the prior art and provide a kind of trimethylsilyl amine
Process for purification.
In order to solve the above technical problems, present invention employs following technical solutions：A kind of trimethylsilyl amine
Process for purification includes the following steps：
(1) by weight, by 100 parts of homogeneous-phase anion exchange films, surface is cleaned with 5-10 parts of methanol, dry, dry film leaching is buried
In 1000-2000 parts of propenyl-1,3-sulfonic acid lactones, 0.0001-0.001 parts of dimethylsilyls (cyclopentadiene) (9- fluorenyls)
Zirconium dichloride, 0.01-0.1 parts of 9- octadecenic acid copper, in 0.1-1 parts of pi-allyl Octyl Ether mixed solutions, N2 protections, with 60Co γ
Radiation exposure dose is 10-50kGy or so, and exposure time 10-60 minutes takes out graft copolymer membrane, with 1000-2000 parts of tetrahydrochysene furans
It mutters and cleans the surface of film, it is dry, obtain 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 obtain the trimethylsilyl amine of primary purification, then are 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 advantages that：
Pass through grafted propylene base -1,3- sultones, dimethylsilyl through this patent trimethylsilyl amine purification permeable membrane
(cyclopentadiene) (9- fluorenyls) zirconium dichloride, 9- octadecenic acids copper and its metal complex formed, can adsorb trimethyl
Impurity in silylation amine, technical grade trimethylsilyl amine can obtain volume fraction after film process, then through rectifying
99.999% high-purity trimethylsilyl amine.
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 embodiments are only used for explaining the present invention, without
It is for limiting the scope of the invention.
In embodiment technical grade trimethylsilyl amine be commercial product, purity 95%.
Embodiment 1
A kind of process for purification of trimethylsilyl amine, includes the following steps：
(1) by weight, by 100 parts of homogeneous-phase anion exchange films, surface is cleaned with 8 parts of methanol, dry, dry film leaching is embedded in
1500 parts of propenyl-1,3-sulfonic acid lactones, 0.0003 part of dimethylsilyl (cyclopentadiene) (9- fluorenyls) zirconium dichloride, 0.04
Part 9- octadecenic acid copper, in 0.1 part of pi-allyl Octyl Ether mixed solution, N2 protections, are 34kGy with 60Co gamma-rays exposure doses
Left and right, exposure time 30 minutes take out graft copolymer membrane, and the surface of film is cleaned with 1800 parts of tetrahydrofurans, dry, obtain trimethyl
Silylation amine purifies permeable membrane.
(2) technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane,
22 DEG C, flow velocity 2BV/h of temperature, 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 process for purification of trimethylsilyl amine, includes the following steps：
(1) by weight, by 100 parts of homogeneous-phase anion exchange films, surface is cleaned with 5 parts of methanol, dry, dry film leaching is embedded in
1000 parts of propenyl-1,3-sulfonic acid lactones, 0.0001 part of dimethylsilyl (cyclopentadiene) (9- fluorenyls) zirconium dichloride, 0.01
Part 9- octadecenic acid copper, in 0.4 part of pi-allyl Octyl Ether mixed solution, N2 protections, are 10kGy with 60Co gamma-rays exposure doses
Left and right, exposure time 60 minutes take out graft copolymer membrane, and the surface of film is cleaned with 1000 parts of tetrahydrofurans, dry, obtain trimethyl
Silylation amine purifies permeable membrane.
(2) technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane,
10 DEG C, flow velocity 1BV/h of temperature, membrane reactor pressure 0.3MPa obtains 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 process for purification of trimethylsilyl amine, includes the following steps：
(1) by weight, by 100 parts of homogeneous-phase anion exchange films, surface is cleaned with 10 parts of methanol, dry, dry film leaching is embedded in
2000 parts of propenyl-1,3-sulfonic acid lactones, 0.001 part of dimethylsilyl (cyclopentadiene) (9- fluorenyls) zirconium dichloride, 0.1
Part 9- octadecenic acid copper, in 1 part of pi-allyl Octyl Ether mixed solution, N2 protections are a 50kGy left sides with 60Co gamma-rays exposure doses
The right side, exposure time 10 minutes, graft copolymer membrane is taken out, and the surface of film is cleaned with 2000 parts of tetrahydrofurans, dry, obtains trimethyl silicane
Alkylamine purifies permeable membrane.
(2) technical grade trimethylsilyl amine enters in the membrane reactor equipped with trimethylsilyl amine purification permeable membrane,
30 DEG C, flow velocity 5BV/h of temperature, membrane reactor pressure 0.7MPa obtains 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- fluorenyls) zirconium dichloride is added without, the other the same as in Example 1, trimethylsilyl 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
Pi-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 (4)
1. a kind of process for purification of trimethylsilyl amine, it is characterised in that include the following steps：
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.
A kind of 2. process for purification of trimethylsilyl amine according to claim 1, it is characterised in that trimethylsilyl
The preparation method of amine purification permeable membrane includes：By weight, it is clear with 5-10 parts of methanol by 100 parts of homogeneous-phase anion exchange films
Surface is washed, dry, dry film leaching is embedded in 1000-2000 parts of propenyl-1,3-sulfonic acid lactones, 0.0001-0.001 parts of dimethylsilanes
Base (cyclopentadiene) (9- fluorenyls) zirconium dichloride, in 0.01-0.1 parts of 9- octadecenic acid copper mixed solutions, N2 protections, with 60Co γ
Radiation exposure dose is 10-50kGy or so, and exposure time 10-60 minutes takes out graft copolymer membrane, with 1000-2000 parts of tetrahydrochysene furans
It mutters and cleans the surface of film, it is dry, obtain trimethylsilyl amine purification permeable membrane.
A kind of 3. process for purification of trimethylsilyl amine according to claim 1, it is characterised in that membrane reactor pressure
0.3-0.7MPa。
4. a kind of process for purification 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 CN108147378B (en) | 2019-08-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912029A (en) * | 2021-10-18 | 2022-01-11 | 浙江博瑞电子科技有限公司 | Method for preparing trisilylamine at ultralow temperature |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113912029A (en) * | 2021-10-18 | 2022-01-11 | 浙江博瑞电子科技有限公司 | Method for preparing trisilylamine at ultralow temperature |
| 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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