CN108084219B - Synthesis method of bis (diethylamino) silane - Google Patents
Synthesis method of bis (diethylamino) silane Download PDFInfo
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- CN108084219B CN108084219B CN201810137099.8A CN201810137099A CN108084219B CN 108084219 B CN108084219 B CN 108084219B CN 201810137099 A CN201810137099 A CN 201810137099A CN 108084219 B CN108084219 B CN 108084219B
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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 System
- C07F7/02—Silicon compounds
- C07F7/025—Silicon compounds without C-silicon linkages
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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Abstract
The invention provides a method for synthesizing bis (diethylamino) silane, which is characterized by comprising the following steps of: adding 100 parts by weight of dichlorosilane, 2000 parts by weight of hexane and 1000 parts by weight of clay catalyst, introducing nitrogen into a reactor, dropwise adding 600 parts by weight of diethylamine under the stirring condition for reaction, keeping the temperature of the reaction system at 40-60 ℃, preserving the heat for 5-10 hours after the dropwise addition is finished, and obtaining the bis (diethylamino) silane by the impurity removal and purification technology known in the industry.
Description
Technical Field
The invention relates to a preparation method of silane, in particular to a synthesis method of bis (diethylamino) silane.
Background
the organoaminosilane precursor can be used in a variety of deposition processes including, but not limited to, atomic layer deposition ("ALD"), chemical vapor deposition ("CVD"), plasma enhanced chemical vapor deposition ("PECVD"), low pressure chemical vapor deposition ("LPCVD"), and atmospheric pressure chemical vapor deposition. Several classes of compounds are useful as precursors for silicon-containing films, such as, but not limited to, silicon oxide or silicon nitride films. Examples of such compounds suitable as precursors include silanes, chlorosilanes, polysilazanes, aminosilanes and azidosilanes. Inert carrier gases or diluents (such as, but not limited to, helium, hydrogen, nitrogen, etc.) are also used to deliver the precursors to the reaction chamber.
JPWO2016152226A1 provides a method for producing a dialkylamine, in which a target dialkylamine is synthesized by a reaction of a chlorosilane and a dialkylamine, a hydrochloride of the dialkylamine is produced as a by-product in a large amount, and thus, when the target dialkylamine is obtained, it is necessary to prevent a decrease in volume efficiency due to a large amount of a solvent, thereby producing the target dialkylamine in a large amount 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.
US3467686 discloses a method of regenerating dialkylamine by reacting a hydrochloride of dialkylamine with a metal (magnesium or the like) while controlling the temperature of the hydrochloride to thereby convert the hydrochloride into dialkylamine, a metal chloride (magnesium chloride or the like) and hydrogen, thereby reducing the amount of the salt.
CN107365416A relates to a method for preparing side chain modified polysiloxane, comprising the steps of: (1) uniformly mixing dichlorosilane and an organic solvent, dripping acrylic acid or allyl alcohol or allylamine into the mixed solution in an ice bath, stirring for reaction, and removing the organic solvent by reduced pressure distillation after the reaction is finished to obtain a chlorosilane substitution product; (2) adding a chlorosilane substitution product and a catalyst into a solvent, reacting for 4-20 hours at 30-90 ℃, and removing the organic solvent by reduced pressure distillation to obtain a hydrosilylation product; (3) the hydrosilylation product and bifunctional alkoxy silane or chlorosilane are subjected to cohydrolysis, a proper amount of end capping agent is added, and the side chain modified polysiloxane is prepared through catalytic equilibrium reaction. The method provided by the invention has the advantages of cheap and easily-obtained raw materials, high product yield, simple and convenient operation steps, no need of complicated steps such as protection and deprotection and the like, and easy realization of industrialization.
TW201233680A is intended to provide a high-purity aminosilane having reduced halogen impurities suitable for use in electronic materials. The solution is to provide a method for producing a purified aminosilane, which comprises at least a step of treating an aminosilane containing 1ppm (w/w) or more of a halogen as an impurity with an alkyl metal reagent and a step of distilling the treated aminosilane, wherein the aminosilane is an aminosilane having a Si-N bond and not having a Si-halogen bond.
since the hydrochloride of dialkylamine is a by-product in a large amount in the reaction of the prior art and the prior art, the metal alkyl reagent is easily lost and wasted, and the reaction yield is low, it is necessary to reduce the volume efficiency by a large amount of solvent or to perform a solid-liquid separation operation such as filtration or decantation in order to obtain the dialkylaminosilane.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the following technical scheme: a method for synthesizing bis (diethylamino) silane comprises the following steps:
1) with Cu (NO)3)2Dissolving in water to obtain Cu (NO) with mass percent concentration of 20-40%3)2The solution is used as a pillared solution for standby;
2) adding clay into water to make the weight ratio of clay to water be 1:1-3, stirring until the clay is dispersed in the water, adding 4-fluorobenzamide oxime accounting for 0.01-0.05% of the mass of the clay, lithium tris (1, 2-dimethoxyethane) tetraphenylborate adduct accounting for 0.001-0.005% of the mass of the clay, ethylenebis (tetrahydroindenyl) titanium dichloride accounting for 0.001-0.005% of the mass of the clay and zinc 2-ethylhexanoate accounting for 1-5% of the mass of the clay, and continuously stirring to obtain a clay solution;
3) mixing the pillared liquid obtained in the step 1) with the clay solution obtained in the step 2) to ensure that Cu (NO) is added3)2Heating to 90-120 deg.C, stirring for 50-80h, granulating, and oven drying to obtain clay catalyst.
4) Adding 100 parts by weight of dichlorosilane, 2000 parts by weight of hexane and 1000 parts by weight of clay catalyst, introducing nitrogen into a reactor, dropwise adding 600 parts by weight of diethylamine under the stirring condition for reaction, keeping the temperature of the reaction system at 40-60 ℃, preserving the heat for 5-10 hours after the dropwise addition is finished, and obtaining the bis (diethylamino) silane by the impurity removal and purification technology known in the industry.
The impurity removal and purification techniques known in the art include distillation separation techniques, including multi-stage distillation and single-stage distillation.
The impurity removal and refining technology known in the industry comprises the processes of water washing, acid washing and alkali washing.
The impurity removal and purification techniques known in the art include adsorption, the adsorbent includes X-type molecular sieve, A-type molecular sieve, and activated carbon, and the adsorbent may be subjected to pretreatment such as acid treatment, heat treatment, and steam treatment before use.
Compared with the prior art, the invention has the following beneficial effects:
the clay catalyst is added in the method, so that the catalyst cannot enter a solvent to be lost, is easy to separate, and can improve the yield.
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.
Example 1
A method for synthesizing bis (diethylamino) silane, comprising the following steps:
1) with Cu (NO)3)2Dissolving in water to obtain Cu (NO) with a mass percent concentration of 28%3)2The solution is used as a pillared solution for standby;
2) adding argil into water to enable the weight ratio of the argil to the water to be 1:2, stirring until the argil is dispersed in the water, adding 4-fluorobenzamide oxime accounting for 0.03 percent of the mass of the argil, lithium tris (1, 2-dimethoxyethane) tetraphenylborate adduct accounting for 0.003 percent of the mass of the argil, ethylene bis (tetrahydroindenyl) titanium dichloride accounting for 0.002 percent of the mass of the argil and zinc 2-ethylhexanoate accounting for 3 percent of the mass of the argil, and continuously stirring to obtain an argil solution;
3) mixing the pillared liquid obtained in the step 1) with the clay solution obtained in the step 2) to ensure that Cu (NO) is added3)2The clay accounts for 5 percent of the mass of the clay, the temperature is raised to 98 ℃, the mixture is stirred for 60 hours, and then the clay catalyst is obtained after granulation and drying.
4) Adding 100 parts by weight of dichlorosilane, 1300 parts by weight of hexane and 11 parts by weight of clay catalyst into a reactor, introducing nitrogen, dropwise adding 500 parts by weight of diethylamine under the condition of stirring for reaction, keeping the temperature of a reaction system at 47 ℃, preserving heat for 6 hours after dropwise adding, and obtaining the bis (diethylamino) silane by an impurity removal refining technology known in the industry.
Example 2
A method for synthesizing bis (diethylamino) silane comprises the following steps:
1) with Cu (NO)3)2Dissolving in water to obtain Cu (NO) with a mass percent concentration of 20%3)2The solution is used as a pillared solution for standby;
2) adding argil into water to enable the weight ratio of the argil to the water to be 1:1, stirring until the argil is dispersed in the water, adding 4-fluorobenzamide oxime accounting for 0.01% of the mass of the argil, lithium tris (1, 2-dimethoxyethane) tetraphenylborate adduct accounting for 0.001% of the mass of the argil, ethylene bis (tetrahydroindenyl) titanium dichloride accounting for 0.001% of the mass of the argil and zinc 2-ethylhexanoate accounting for 1% of the mass of the argil, and continuously stirring to obtain an argil solution;
3) mixing the pillared liquid obtained in the step 1) with the clay solution obtained in the step 2) to ensure that Cu (NO) is added3)2The clay accounts for 3 percent of the mass of the clay, the temperature is raised to 90 ℃, the mixture is stirred for 80 hours, and then the clay catalyst is obtained after granulation and drying.
4) Adding 100 parts by weight of dichlorosilane, 1000 parts by weight of hexane and 5-20 parts by weight of clay catalyst into a reactor, introducing nitrogen, dropwise adding 300 parts by weight of diethylamine under the condition of stirring for reaction, keeping the temperature of a reaction system at 40 ℃, preserving heat for 10 hours after dropwise adding, and obtaining the bis (diethylamino) silane by an impurity removal refining technology known in the industry.
Example 3
A method for synthesizing bis (diethylamino) silane comprises the following steps:
1) dissolving Cu (NO3)2 in water to obtain a Cu (NO3)2 solution with the mass percentage concentration of 40% as a pillared solution for later use;
2) adding argil into water to enable the weight ratio of the argil to the water to be 1:3, stirring until the argil is dispersed in the water, adding 4-fluorobenzamide oxime accounting for 0.05% of the mass of the argil, lithium tris (1, 2-dimethoxyethane) tetraphenylborate adduct accounting for 0.005% of the mass of the argil, ethylene bis (tetrahydroindenyl) titanium dichloride accounting for 0.005% of the mass of the argil and zinc 2-ethylhexanoate accounting for 5% of the mass of the argil, and continuously stirring to obtain an argil solution;
3) mixing the pillared solution obtained in the step 1) with the clay solution obtained in the step 2) to enable Cu (NO3)2 to account for 10% of the mass of the clay, heating to 120 ℃, stirring for 50h, granulating, and drying to obtain the clay catalyst.
4) Adding 100 parts by weight of dichlorosilane, 2000 parts by weight of hexane and 20 parts by weight of clay catalyst into a reactor, introducing nitrogen, dropwise adding 600 parts by weight of diethylamine under the condition of stirring for reaction, keeping the temperature of a reaction system at 60 ℃, preserving heat for 5 hours after dropwise adding, and obtaining the bis (diethylamino) silane by an impurity removal refining technology known in the industry.
Comparative example 1
The same procedure as in example 1 was repeated except that 4-fluorobenzamide oxime was not added.
Comparative example 2
The tris (1, 2-dimethoxyethane) lithium tetraphenylborate adduct was not added, as in example 1.
Comparative example 3
The procedure of example 1 was otherwise the same as that of example 1 except that ethylene bis (tetrahydroindenyl) titanium dichloride was not added.
Comparative example 4
Zinc 2-ethylhexanoate was prepared in the same manner as in example 1, except that it was not added.
Comparative example 5
The procedure of example 1 was repeated except that no clay catalyst was used.
Table 1: comparison of the percent yields of bis (diethylamino) silane for the test samples made by the different processes.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any changes or modifications within the technical field of the present invention by those skilled in the art are covered by the claims of the present invention.
Claims (4)
1. A method for synthesizing bis (diethylamino) silane is characterized by comprising the following steps: adding 100 parts by weight of dichlorosilane, 2000 parts by weight of hexane and 1000 parts by weight of clay catalyst and 5-20 parts by weight of nitrogen into a reactor, dropwise adding 600 parts by weight of diethylamine under the stirring condition for reaction, keeping the temperature of a reaction system at 40-60 ℃, preserving heat for 5-10 hours after dropwise adding, and obtaining bis (diethylamino) silane by an impurity removal refining technology;
the preparation method of the clay catalyst comprises the following steps: mixing the pillared liquid with a clay solution to make Cu (NO)3)2Heating to 90-120 deg.C, stirring for 50-80h, granulating, and oven drying to obtain clay catalyst;
the preparation method of the pillared liquid comprises the following steps: with Cu (NO)3)2Dissolving in water to obtain Cu (NO) with mass percent concentration of 20-40%3)2The solution is used as a pillared solution;
the preparation method of the carclazyte solution comprises the following steps: adding clay into water to make the weight ratio of clay to water be 1:1-3, stirring until the clay is dispersed in the water, adding 4-fluorobenzamide oxime accounting for 0.01-0.05% of the mass of the clay, lithium tris (1, 2-dimethoxyethane) tetraphenylborate adduct accounting for 0.001-0.005% of the mass of the clay, ethylenebis (tetrahydroindenyl) titanium dichloride accounting for 0.001-0.005% of the mass of the clay and zinc 2-ethylhexanoate accounting for 1-5% of the mass of the clay, and continuously stirring to obtain a clay solution.
2. A process for the synthesis of bis (diethylamino) silane as defined in claim 1, wherein said purification technique for removing impurities comprises rectification separation technique including multi-stage rectification and single-stage rectification.
3. A process for the synthesis of bis (diethylamino) silane as defined in claim 1, wherein said refining technique for removing impurities comprises water washing, acid washing, and alkali washing.
4. The method for synthesizing bis (diethylamino) silane as claimed in claim 1, wherein the purification technique for removing impurities comprises adsorption, the adsorbent for adsorption comprises X-type molecular sieve, A-type molecular sieve and activated carbon, and the adsorbent is pretreated before use.
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| KR102293698B1 (en) * | 2018-02-06 | 2021-08-27 | 와커 헤미 아게 | Method for preparing aminopropylalkoxysilane |
| CN115260222B (en) * | 2022-09-26 | 2023-01-31 | 江苏南大光电材料股份有限公司 | Preparation method and application of dialkyl aminosilane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3467686A (en) * | 1967-10-03 | 1969-09-16 | Union Carbide Corp | Preparation of organosilicon-nitrogen compounds |
| CN104876957A (en) * | 2014-02-28 | 2015-09-02 | 气体产品与化学公司 | Organoaminosilanes And Methods For Making Same |
| CN105837611A (en) * | 2015-01-13 | 2016-08-10 | 苏州复纳电子科技有限公司 | Preparation method of di(diethylamino)silane |
| CN107406466A (en) * | 2015-03-24 | 2017-11-28 | 捷恩智株式会社 | The manufacture method of dialkyl amino base silane |
-
2018
- 2018-02-10 CN CN201810137099.8A patent/CN108084219B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3467686A (en) * | 1967-10-03 | 1969-09-16 | Union Carbide Corp | Preparation of organosilicon-nitrogen compounds |
| CN104876957A (en) * | 2014-02-28 | 2015-09-02 | 气体产品与化学公司 | Organoaminosilanes And Methods For Making Same |
| CN105837611A (en) * | 2015-01-13 | 2016-08-10 | 苏州复纳电子科技有限公司 | Preparation method of di(diethylamino)silane |
| CN107406466A (en) * | 2015-03-24 | 2017-11-28 | 捷恩智株式会社 | The manufacture method of dialkyl amino base silane |
Non-Patent Citations (1)
| Title |
|---|
| 含硅二胺单体合成及应用研究;刘达;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20100315;B014-31 * |
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