WO2024067469A1 - 一种二烷基氨基硅烷的制备方法及其用途 - Google Patents
一种二烷基氨基硅烷的制备方法及其用途 Download PDFInfo
- Publication number
- WO2024067469A1 WO2024067469A1 PCT/CN2023/121047 CN2023121047W WO2024067469A1 WO 2024067469 A1 WO2024067469 A1 WO 2024067469A1 CN 2023121047 W CN2023121047 W CN 2023121047W WO 2024067469 A1 WO2024067469 A1 WO 2024067469A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- bis
- preparation
- monosilane
- reaction
- dialkylaminosilane
- Prior art date
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 17
- IUBQJLUDMLPAGT-UHFFFAOYSA-N potassium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([K])[Si](C)(C)C IUBQJLUDMLPAGT-UHFFFAOYSA-N 0.000 claims abstract description 11
- YBLVILVQEZRPFO-UHFFFAOYSA-N calcium;bis(trimethylsilyl)azanide Chemical compound [Ca+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C YBLVILVQEZRPFO-UHFFFAOYSA-N 0.000 claims abstract description 7
- MLAOBMVRIIOEPO-UHFFFAOYSA-N strontium;bis(trimethylsilyl)azanide Chemical compound [Sr+2].C[Si](C)(C)[N-][Si](C)(C)C.C[Si](C)(C)[N-][Si](C)(C)C MLAOBMVRIIOEPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 15
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 13
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 claims description 12
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 9
- QYCOIUXBCXXOCL-UHFFFAOYSA-N C(CC)N[SiH2]NCCC Chemical compound C(CC)N[SiH2]NCCC QYCOIUXBCXXOCL-UHFFFAOYSA-N 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- VYIRVGYSUZPNLF-UHFFFAOYSA-N n-(tert-butylamino)silyl-2-methylpropan-2-amine Chemical compound CC(C)(C)N[SiH2]NC(C)(C)C VYIRVGYSUZPNLF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 10
- XMIJDTGORVPYLW-UHFFFAOYSA-N [SiH2] Chemical compound [SiH2] XMIJDTGORVPYLW-UHFFFAOYSA-N 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000005046 Chlorosilane Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 125000005265 dialkylamine group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- -1 polysiloxane Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 2
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- C07F7/025—Silicon compounds without C-silicon linkages
Definitions
- the present invention relates to the technical field of organic synthesis, and in particular to a preparation method of dialkylaminosilane and application thereof.
- Polyaminosilane is usually used as a raw material (precursor) to manufacture silicon-based semiconductor thin film materials such as silicon oxide, silicon nitride and silicon carbide through traditional vapor deposition and more precisely controlled atomic layer deposition. These silicon-based semiconductor thin film materials have been used to manufacture high-end capacitors, solar cells, memory devices, lasers, light-emitting diodes, and gas sensors.
- dialkylaminosilane can be prepared by traditional chlorosilane amination reaction.
- JPWO2016152226A1 produces dialkylaminosilane by direct reaction of chlorosilane and dialkylamine, and in addition to the target product, a large amount of by-product hydrochloride is generated.
- Patent CN107365416A proposes a method for preparing side chain modified polysiloxane, by mixing dichlorosilane with an organic solvent, then adding acrylic acid, acryl alcohol or allylamine to the mixed solution, and removing the organic solvent by vacuum distillation after the reaction is completed to obtain a chlorosilane substitution product; the chlorosilane substitution product and a catalyst are added to a solvent for reaction, and the organic solvent is removed by vacuum distillation to obtain a hydrosilylation product; the hydrosilylation product is then co-hydro
- the raw materials are cheap and easy to obtain and the product yield is high, but there are too many operating steps and the product contains chlorine impurities.
- a large amount of solid byproduct hydrochloride is formed during the reaction process, and the reaction requires the use of a large amount of solvent, which will reduce the volume efficiency, and the product contains chlorine impurities.
- the main purpose of the present invention is to provide a preparation method of dialkylaminosilane and its use, so as to overcome the shortcomings of the prior art.
- the technical solution adopted by the present invention includes:
- An embodiment of the present invention provides a method for preparing dialkylaminosilane, which comprises:
- the monosilane is introduced into a sealed reaction chamber containing a mixture of an amine source and a catalyst, and reacted at a temperature of -10 to 30° C. to obtain dialkylaminosilane;
- the molar ratio of monosilane to amine source is ⁇ 0.5; the catalyst includes any one of dibutyl magnesium, potassium bis(trimethylsilyl)amide, calcium bis(hexamethyldisilazide), and strontium bis(hexamethyldisilazide); and the input rate of monosilane is 1 to 5 L/min.
- the dialkylaminosilane includes any one of bis( diethylamino )silane ( SiH2 [N( CH2CH3 ) 2 ] 2 ), bis(tert-butylamino)silane ( SiH2 [ NH ( C4H9 )] 2 ), and bis(n-propylamino)silane ( SiH2 [ N (CH2CH2CH3 ) 2 ] 2 ).
- the embodiment of the present invention also provides the use of the dialkylaminosilane prepared by the above-mentioned preparation method in the preparation of silicon-based semiconductor thin film materials.
- the present invention has the following beneficial effects:
- the preparation method of dialkylaminosilane provided by the present invention is a one-step reaction, and the yield of dialkylaminosilane is as high as 95.9%.
- FIG1 is a nuclear magnetic spectrum of bis(diethylamino)silane prepared in Example 1 of the present invention.
- FIG. 2 is a mass spectrum of bis(diethylamino)silane prepared in Example 1 of the present invention.
- a method for preparing a dialkylaminosilane includes:
- the monosilane is introduced into a sealed reaction chamber containing a mixture of an amine source and a catalyst, and reacted at a temperature of -10 to 30° C. to obtain dialkylaminosilane;
- the molar ratio of monosilane to amine source is ⁇ 0.5; the catalyst includes any one of dibutyl magnesium, potassium bis(trimethylsilyl)amide, calcium bis(hexamethyldisilazide), and strontium bis(hexamethyldisilazide); and the input rate of monosilane is 1 to 5 L/min.
- the amine source includes any one of diethylamine, tert-butylamine, and di-n-propylamine, but is not limited thereto.
- the water content in the amine source is ⁇ 300 ppm.
- the silane used in the present invention is in excess relative to the amine source.
- the dialkylaminosilane includes any one of bis( diethylamino )silane ( SiH2 [N( CH2CH3 ) 2 ] 2 , also referred to as BDEAS), bis(tert - butylamino)silane ( SiH2 [NH( C4H9 )] 2 , also referred to as BTBAS), and bis(n -propylamino)silane (SiH2[N(CH2CH2CH3 ) 2 ] 2 ) , but is not limited thereto.
- the catalyst includes any one of potassium bis(trimethylsilyl)amide, calcium bis(hexamethyldisilazide), and strontium bis(hexamethyldisilazide).
- the raw materials used in the present invention and the generated products are all chlorine-free materials and there will be no chlorine pollution.
- the first pressure in the closed reaction device is controlled to be 1 to 15 bar.
- the mass ratio of the catalyst to the amine source is 0.01 to 0.05:1.
- the reaction temperature is 15-25°C.
- monosilane is introduced into the sealed reaction chamber by means of back pressure or pressure suppression.
- the preparation method specifically includes: introducing monosilane into the sealed reaction chamber at one time by means of holding pressure, and carrying out the reaction, and when the pressure no longer rises during the reaction, ending the reaction.
- the preparation method specifically comprises: continuously introducing monosilane into the sealed reaction chamber by back pressure, The reaction is carried out, and the pressure in the sealed reaction chamber is kept constant during the reaction. When the amount of monosilane introduced into the sealed reaction chamber reaches a specified value, the reaction is terminated.
- the pressure relief pressure of the back pressure valve at the gas outlet of the reactor is adjusted to a specified value, and then monosilane is continuously introduced into the reactor.
- the pressure of the reactor reaches the specified value of the back pressure valve, the reactor is depressurized through the back pressure valve. In this way, monosilane is continuously introduced into the reactor during the reaction process, and the pressure is always maintained at the specified value of the back pressure valve. This process is called a back pressure reaction method.
- the preparation method of the dialkylaminosilane includes (taking the preparation of BDEAS, BTBAS, and bis(n-propylamino)silane as an example):
- the catalyst includes dibutyl magnesium (Mg(C 4 H 9 ) 2 ), bis(trimethylsilyl) potassium amide (KN((CH 3 ) 3 Si) 2 ), bis(hexamethyldisilazide) calcium (Ca(N((CH 3 ) 3 Si) 2 ) 2 ) or bis(hexamethyldisilazide) strontium (Sr(N((CH 3 ) 3 Si) 2 ) 2 );
- Another aspect of the technical solution of the present invention also provides the use of the dialkylaminosilane prepared by the aforementioned preparation method in the preparation of silicon-based semiconductor thin film materials.
- the silicon-based semiconductor thin film material includes any one of silicon oxide, silicon nitride, and silicon carbide, but is not limited thereto.
- experimental materials used in the following examples can be purchased from conventional biochemical reagent companies.
- Embodiment 1 is a diagrammatic representation of Embodiment 1:
- a method for synthesizing bis(diethylamino)silane under pressure holding conditions comprises the following steps:
- the NMR spectrum of the bis(diethylamino)silane prepared in this example is shown in FIG1 , and the mass spectrum is shown in FIG2 .
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- a method for synthesizing bis(tert-butylamino)silane under back pressure conditions comprises the following steps:
- Embodiment 3 is a diagrammatic representation of Embodiment 3
- a method for synthesizing bis(n-propylamino)silane under pressure holding conditions comprises the following steps:
- Embodiment 4 is a diagrammatic representation of Embodiment 4:
- a method for synthesizing bis(diethylamino)silane under pressure holding conditions comprises the following steps:
- Embodiment 5 is a diagrammatic representation of Embodiment 5:
- a method for synthesizing bis(diethylamino)silane under pressure holding conditions comprises the following steps:
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
本发明是关于一种二烷基氨基硅烷的制备方法及其用途。所述制备方法包括:将甲硅烷输入容置有胺源和催化剂的混合物的密封反应室内,并在-10~30℃的温度条件下进行反应,制得二烷基氨基硅烷;其中,所述甲硅烷与胺源的摩尔比值≥0.5;所述催化剂包括二丁基镁、双(三甲基硅烷基)氨基钾、双(六甲基二硅叠氮)钙、双(六甲基二硅叠氮)锶中的任意一种;所述甲硅烷输入的速率为1~5L/min。本发明提供的二烷基氨基硅烷的制备方法为一步反应,且反应过程中不会形成大量固体,空间利用率高。
Description
本发明要求2022年09月26日向中国专利局提交的、申请号为202211172427.0、发明名称为“一种二烷基氨基硅烷的制备方法及其用途”的中国专利申请的优先权,该申请的全部内容通过引用结合在本文中。
本发明关于有机合成技术领域,具体涉及一种二烷基氨基硅烷的制备方法及其用途。
多氨基硅烷通常作为原材料(前驱体)可以通过传统的气相沉积法和更精密可控的原子层沉积法被用来制造硅基半导体薄膜材料,例如氧化硅、氮化硅和碳化硅等。这些硅基半导体薄膜材料已被用于制造高端电容器、太阳能电池、存储器件、激光器、发光二极管、以及气敏元件等领域。
目前,二烷基氨基硅烷可以通过传统的氯硅烷胺化反应制备。例如:JPWO2016152226A1通过氯硅烷与二烷基胺的直接反应,制造二烷基氨基硅烷,除了目标产物之外,会有大量的副产物盐酸盐生成。该方法需要额外的过滤步骤去得到目标产物,同时会有少量的盐酸盐溶解在产物中需要后期分离,导致产物中含有氯杂质;US3467686提供了一种处理该盐酸盐副产物的方法,使其与金属(镁、钙和锌)反应,生成二烷基胺、金属氯化物和氢,达到了再生二烷基胺并且减少盐酸盐的形成;专利CN107365416A中提出了一种制备侧链改性聚硅氧烷的方法,通过二氯氢硅烷与有机溶剂混合均匀,然后将丙烯酸、丙烯醇或烯丙胺加入到该混合溶液中,反应完成后减压蒸馏除去有机溶剂,得到氯硅烷取代产物;将氯硅烷取代产物和催化剂加入到溶剂中进行反应,减压蒸馏脱除有机溶剂,得到硅氢加成产物;再将硅氢加成产物与双官能度的烷氧基硅烷或氯硅烷共水解,加入适量的封端剂后制得侧链改性聚硅氧烷。该发明中,原料便宜易得并且产品收率高,但操作步骤过多且产物中含有氯杂质。现有专利及文献涉及的方法中,反应过程中会有大量固体副产物盐酸盐的形成,并且反应需要使用大量的溶剂,会造成体积效率降低,同时产物含有氯杂质。为解决以上这些技术问题,提供一种简单、高效制备二烷基氨基硅烷的方法是亟待解决的问题。
发明内容
本发明的主要目的在于提供一种二烷基氨基硅烷的制备方法及其用途,以克服现有技术的不足。
为实现前述发明目的,本发明采用的技术方案包括:
本发明实施例提供了一种二烷基氨基硅烷的制备方法,其包括:
将甲硅烷输入容置有胺源和催化剂的混合物的密封反应室内,并在-10~30℃的温度条件下进行反应,制得二烷基氨基硅烷;
其中,所述甲硅烷与胺源的摩尔比值≥0.5;所述催化剂包括二丁基镁、双(三甲基硅烷基)氨基钾、双(六甲基二硅叠氮)钙、双(六甲基二硅叠氮)锶中的任意一种;所述甲硅烷输入的速率为1~5L/min。
在一些较为具体的实施方案中,所述二烷基氨基硅烷包括双(二乙基氨基)硅烷(SiH2[N(CH2CH3)2]2)、双(叔丁基氨基)硅烷(SiH2[NH(C4H9)]2)、双(正丙基氨基)硅烷(SiH2[N(CH2CH2CH3)2]2)中的任意一种。
本发明实施例还提供了前述的制备方法制得的二烷基氨基硅烷在制备硅基半导体薄膜材料中的用途。
与现有技术相比,本发明的有益效果在于:
(1)现有技术中二烷基氨基硅烷的反应过程中,会有大量的固体盐类形成,反应体积利用率低且需要额外的分离步骤;而本发明的反应过程中不会形成大量固体,空间利用率高且产物可直接得到;
(2)本发明提供的二烷基氨基硅烷的制备方法为一步反应,二烷基氨基硅烷的收率高达95.9%。
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明中记载的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明实施例1制备的双(二乙基氨基)硅烷的核磁图谱;
图2是本发明实施例1制备的双(二乙基氨基)硅烷的质谱图谱。
鉴于现有技术的缺陷,本案发明人经长期研究和大量实践,得以提出本发明的技术方案,下面将对本发明的技术方案进行清楚、完整地描述,显然,所描述的实施例是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
具体的,作为本发明技术方案的一个方面,其所涉及的一种二烷基氨基硅烷的制备方法包括:
将甲硅烷输入容置有胺源和催化剂的混合物的密封反应室内,并在-10~30℃的温度条件下进行反应,制得二烷基氨基硅烷;
其中,所述甲硅烷与胺源的摩尔比值≥0.5;所述催化剂包括二丁基镁、双(三甲基硅烷基)氨基钾、双(六甲基二硅叠氮)钙、双(六甲基二硅叠氮)锶中的任意一种;所述甲硅烷输入的速率为1~5L/min。
在一些优选实施方案中,所述胺源包括二乙胺、叔丁胺、二正丙基胺中的任意一种,且不限于此。
在一些优选实施方案中,所述胺源中的含水量≤300ppm。
在一些优选实施方案中,本发明中使用的甲硅烷相对于胺源是过量的。
在一些优选实施方案中,所述二烷基氨基硅烷包括双(二乙基氨基)硅烷(SiH2[N(CH2CH3)2]2,同时记为BDEAS)、双(叔丁基氨基)硅烷(SiH2[NH(C4H9)]2,同时记为BTBAS)、双(正丙基氨基)硅烷(SiH2[N(CH2CH2CH3)2]2)中的任意一种,且不限于此。
在一些优选实施方案中,所述催化剂包括双(三甲基硅烷基)氨基钾、双(六甲基二硅叠氮)钙、双(六甲基二硅叠氮)锶中的任意一种,采用上述这些催化剂时,本发明中使用的原料及生成的产物均是无氯材料,不会有氯污染。
在一些优选实施方案中,控制所述密闭反应装置内的第一压力为1~15bar。
在一些优选实施方案中,所述催化剂与胺源的质量比为0.01~0.05:1。
在一些优选实施方案中,所述反应的温度为15~25℃。
在一些优选实施方案中,采用背压或憋压的方式将甲硅烷输入所述密封反应室。
进一步地,所述制备方法具体包括:采用憋压方式将甲硅烷一次性通入所述密封反应室内,并进行所述的反应,在反应过程中,当压力不再上升,结束所述的反应。
进一步地,所述制备方法具体包括:采用背压方式将甲硅烷连续通入所述密封反应室,
并进行所述的反应,且在反应过程中使所述密封反应室内的压力保持不变,当所述密封反应室内的甲硅烷通入量达到指定值后,结束所述的反应。
具体地,本发明实施过程中,在加入胺和催化剂后,甲硅烷一次性通入到指定压力,反应在密闭条件下进行直至结束,该过程称之为憋压反应方式。
本发明实施过程中,在加入胺和催化剂后,调节反应釜气体排出口背压阀泄压压力到指定值,然后开始连续通入甲硅烷于反应釜中,当反应釜压力达到背压阀调节指定值后,反应釜通过背压阀泄压。通过该方式,反应过程中甲硅烷连续通入反应釜中,压力一直保持在背压阀泄压指定值,该过程称之为背压反应方式。
在一些较为具体的实施方案中,所述二烷基氨基硅烷的制备方法包括(以制备BDEAS、BTBAS、双(正丙基氨基)硅烷为例):
(1)采用不高于300ppm水含量的二乙胺、叔丁胺或二正丙基胺为原料;
(2)在密闭不锈钢反应釜中加入二乙胺、叔丁胺或二正丙基胺、催化剂,然后向反应釜中通入甲硅烷;
(3)甲硅烷以背压或/和憋压的方式通入反应釜,压力控制在1bar至15bar之间;反应过程中会有氢气释放。所述催化剂包括二丁基镁(Mg(C4H9)2)、双(三甲基硅烷基)氨基钾(KN((CH3)3Si)2)、双(六甲基二硅叠氮)钙(Ca(N((CH3)3Si)2)2)或双(六甲基二硅叠氮)锶(Sr(N((CH3)3Si)2)2);
(4)从反应釜釜底出料,得到BDEAS、BTBAS或双(正丙基氨基)硅烷。
本发明技术方案的另一个方面还提供了前述的制备方法制得的二烷基氨基硅烷在制备硅基半导体薄膜材料中的用途。
进一步地,所述硅基半导体薄膜材料包括氧化硅、氮化硅、碳化硅中的任一者,且不限于此。
下面结合若干优选实施例对本发明的技术方案做进一步详细说明,本实施例在以发明技术方案为前提下进行实施,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。
下面所用的实施例中所采用的实验材料,如无特殊说明,均可由常规的生化试剂公司购买得到。
实施例1:
一种双(二乙基氨基)硅烷在憋压条件下的合成方法,包括以下步骤:
1)加入20毫升二乙胺于250毫升不锈钢反应釜中,反应温度控制在15℃;
2)加入催化剂双(三甲基硅烷基)氨基钾于二乙胺中,催化剂加入量为二乙胺加入质量的2%;
3)将甲硅烷通入反应釜中,通入速度为5L/min,反应釜压力升至8bar后停止通入;
4)在该条件下进行反应,当反应釜内压力不再上升,随即反应结束;
5)从反应釜釜底出料,计算得到双(二乙基氨基)硅烷产品收率为95.9%。
本实施例制备的双(二乙基氨基)硅烷的核磁图谱如图1所示,质谱图谱如图2所示。
实施例2:
一种双(叔丁基氨基)硅烷在背压条件下的合成方法,包括以下步骤:
1)加入3升叔丁胺于5升不锈钢反应釜中,反应温度控制在-10℃;
2)加入催化剂二丁基镁于叔丁胺中,催化剂加入量为叔丁胺加入质量的2%;
3)将反应釜顶部气相出口的背压调节阀压力设置在7bar;
4)将甲硅烷通入反应釜中,反应釜压力升至并保持在7bar;
5)在该条件下,当甲硅烷通入摩尔量和加入的叔丁胺摩尔量一样时,随即反应结束;
6)从反应釜釜底出料,计算得到双(叔丁基氨基)硅烷产品收率为64.6%。
实施例3:
一种双(正丙基氨基)硅烷在憋压条件下合成方法,包括以下步骤:
1)加入20毫升二正丙基胺于250毫升不锈钢反应釜中,反应温度控制在25℃;
2)加入催化剂双(三甲基硅烷基)氨基钾于二正丙基胺中,催化剂加入量为二正丙基胺加入质量的2%;
3)将甲硅烷通入反应釜中,通入速度为5L/min,反应釜压力升至8bar后停止通入;
4)在该条件下进行反应,当反应釜内压力不再上升,随即反应结束;
5)从反应釜釜底出料,计算得到双(正丙基氨基)硅烷产品收率为86.2%。
实施例4:
一种双(二乙基氨基)硅烷在憋压条件下合成方法,包括以下步骤:
1)加入150毫升二乙胺于250毫升不锈钢反应釜中,反应温度控制在30℃;
2)加入催化剂双(三甲基硅烷基)氨基钾于二乙胺中,催化剂加入量为二乙胺加入质量的5%;
3)将反应釜顶部气相出口的背压调节阀压力设置在1bar;
4)将甲硅烷通入反应釜中,反应釜压力升至并保持在1bar;
5)在该条件下,当甲硅烷通入摩尔量和加入的叔丁胺摩尔量一样时,随即反应结束;
6)从反应釜釜底出料,计算得到双(二乙基氨基)硅烷产品收率为83.1%。
实施例5:
一种双(二乙基氨基)硅烷在憋压条件下合成方法,包括以下步骤:
1)加入20毫升二乙胺于250毫升不锈钢反应釜中,反应温度控制在15℃;
2)加入催化剂双(三甲基硅烷基)氨基钾于二乙胺中,催化剂加入量为二乙胺加入质量的1%;
3)将甲硅烷通入反应釜中,通入速度为5L/min,反应釜压力升至15bar后停止通入;
4)在该条件下,保持1h,随即反应结束;
5)从反应釜釜底出料,计算得到双(二乙基氨基)硅烷产品收率为88.7%。
此外,本案发明人还参照前述实施例,以本说明书述及的其它原料、工艺操作、工艺条件进行了试验,并均获得了较为理想的结果。
应当理解,本发明的技术方案不限于上述具体实施案例的限制,凡是在不脱离本发明宗旨和权利要求所保护的范围情况下,根据本发明的技术方案做出的技术变形,均落于本发明的保护范围之内。
Claims (10)
- 一种二烷基氨基硅烷的制备方法,其特征在于包括:将甲硅烷输入容置有胺源和催化剂的混合物的密封反应室内,并在-10~30℃的温度条件下进行反应,制得二烷基氨基硅烷;其中,所述甲硅烷与胺源的摩尔比值≥0.5;所述催化剂包括二丁基镁、双(三甲基硅烷基)氨基钾、双(六甲基二硅叠氮)钙、双(六甲基二硅叠氮)锶中的任意一种;所述甲硅烷输入的速率为1~5L/min。
- 根据权利要求1所述的制备方法,其特征在于:所述胺源包括二乙胺、叔丁胺、二正丙基胺中的任意一种;和/或,所述胺源中的含水量≤300ppm。
- 根据权利要求1所述的制备方法,其特征在于:所述二烷基氨基硅烷包括双(二乙基氨基)硅烷、双(叔丁基氨基)硅烷、双(正丙基氨基)硅烷中的任意一种。
- 根据权利要求1所述的制备方法,其特征在于:所述催化剂选自双(三甲基硅烷基)氨基钾、双(六甲基二硅叠氮)钙、双(六甲基二硅叠氮)锶中的任意一种;和/或,所述催化剂与胺源的质量比为0.01~0.05:1。
- 根据权利要求1所述的制备方法,其特征在于:所述反应的温度为15~25℃。
- 根据权利要求1所述的制备方法,其特征在于:采用背压或憋压的方式将甲硅烷输入所述密封反应室。
- 根据权利要求6所述的制备方法,其特征在于具体包括:采用憋压方式将甲硅烷一次性通入所述密封反应室内,并进行所述的反应,且在反应过程中,当压力不再上升,结束所述的反应。
- 根据权利要求6所述的制备方法,其特征在于包括:采用背压方式将甲硅烷连续通入所述密封反应室,并进行所述的反应,且在反应过程中使所述密封反应室内的压力保持不变,当所述密封反应室内的甲硅烷通入量达到指定值后,结束所述的反应。
- 权利要求1-8中任一项所述的制备方法制得的二烷基氨基硅烷在制备硅基半导体薄膜材料中的用途。
- 根据权利要求9所述的用途,其特征在于:所述硅基半导体薄膜材料包括氧化硅、氮化硅、碳化硅中的任一者。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202211172427.0A CN115260222B (zh) | 2022-09-26 | 2022-09-26 | 一种二烷基氨基硅烷的制备方法及其用途 |
CN202211172427.0 | 2022-09-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2024067469A1 true WO2024067469A1 (zh) | 2024-04-04 |
Family
ID=83756522
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2023/121047 WO2024067469A1 (zh) | 2022-09-26 | 2023-09-25 | 一种二烷基氨基硅烷的制备方法及其用途 |
Country Status (2)
Country | Link |
---|---|
CN (1) | CN115260222B (zh) |
WO (1) | WO2024067469A1 (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115260222B (zh) * | 2022-09-26 | 2023-01-31 | 江苏南大光电材料股份有限公司 | 一种二烷基氨基硅烷的制备方法及其用途 |
CN117143141B (zh) * | 2023-10-30 | 2024-01-12 | 江苏南大光电材料股份有限公司 | 一种三(二甲胺基)硅烷的制备方法及制备*** |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103898601A (zh) * | 2012-12-27 | 2014-07-02 | 东京毅力科创株式会社 | 晶种层的形成方法、硅膜的成膜方法以及成膜装置 |
JP2019081711A (ja) * | 2017-10-27 | 2019-05-30 | 住友精化株式会社 | アミノシラン類の製造方法 |
CN112041323A (zh) * | 2018-05-23 | 2020-12-04 | 美国陶氏有机硅公司 | 制备有机氨基硅烷的方法 |
CN115073507A (zh) * | 2022-07-04 | 2022-09-20 | 浙江博瑞电子科技有限公司 | 一种无溶剂参与制备二(二乙基氨基)硅烷的方法 |
CN115260222A (zh) * | 2022-09-26 | 2022-11-01 | 江苏南大光电材料股份有限公司 | 一种二烷基氨基硅烷的制备方法及其用途 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102558219B (zh) * | 2011-12-16 | 2015-04-01 | 齐鲁工业大学 | 一种叔胺基硅烷的生产工艺 |
JP6812855B2 (ja) * | 2017-03-10 | 2021-01-13 | Jnc株式会社 | ジアルキルアミノシランの製造方法 |
CN108084219B (zh) * | 2017-12-26 | 2020-09-15 | 浙江博瑞电子科技有限公司 | 一种二(二乙基氨基)硅烷合成方法 |
-
2022
- 2022-09-26 CN CN202211172427.0A patent/CN115260222B/zh active Active
-
2023
- 2023-09-25 WO PCT/CN2023/121047 patent/WO2024067469A1/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103898601A (zh) * | 2012-12-27 | 2014-07-02 | 东京毅力科创株式会社 | 晶种层的形成方法、硅膜的成膜方法以及成膜装置 |
JP2019081711A (ja) * | 2017-10-27 | 2019-05-30 | 住友精化株式会社 | アミノシラン類の製造方法 |
CN112041323A (zh) * | 2018-05-23 | 2020-12-04 | 美国陶氏有机硅公司 | 制备有机氨基硅烷的方法 |
CN115073507A (zh) * | 2022-07-04 | 2022-09-20 | 浙江博瑞电子科技有限公司 | 一种无溶剂参与制备二(二乙基氨基)硅烷的方法 |
CN115260222A (zh) * | 2022-09-26 | 2022-11-01 | 江苏南大光电材料股份有限公司 | 一种二烷基氨基硅烷的制备方法及其用途 |
Non-Patent Citations (3)
Title |
---|
MICHAEL S. HILL ET AL: "Hetero-dehydrocoupling of silanes and amines by heavier alkaline earth catalyis", JOURNAL OF THE CHEMICAL SOCIETY , PERKIN TRANSACTIONS 2, CHEMICAL SOCIETY , LETCHWORTH, GB, vol. 4, 1 January 2013 (2013-01-01), GB , pages 4212 - 4222, XP002790840, ISSN: 1472-779X * |
NGUYEN THAO T., MUKHOPADHYAY TUFAN K., MACMILLAN SAMANTHA N., JANICKE MICHAEL T., TROVITCH RYAN J.: "Synthesis of Aminosilane Chemical Vapor Deposition Precursors and Polycarbosilazanes through Manganese-Catalyzed Si–N Dehydrocoupling", ACS SUSTAINABLE CHEMISTRY & ENGINEERING, AMERICAN CHEMICAL SOCIETY, US, vol. 10, no. 13, 4 April 2022 (2022-04-04), US , pages 4218 - 4226, XP093153626, ISSN: 2168-0485, DOI: 10.1021/acssuschemeng.2c00008 * |
SRINIVAS ANGA; YANN SARAZIN; JEAN‐FRANÇOIS CARPENTIER; TARUN K. PANDA: "Alkali‐Metal‐Catalyzed Cross‐Dehydrogenative Couplings of Hydrosilanes with Amines", CHEMCATCHEM, JOHN WILEY & SONS, INC., HOBOKEN, USA, vol. 8, no. 7, 22 February 2016 (2016-02-22), Hoboken, USA, pages 1373 - 1378, XP072432418, ISSN: 1867-3880, DOI: 10.1002/cctc.201501356 * |
Also Published As
Publication number | Publication date |
---|---|
CN115260222A (zh) | 2022-11-01 |
CN115260222B (zh) | 2023-01-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2024067469A1 (zh) | 一种二烷基氨基硅烷的制备方法及其用途 | |
WO2024066073A1 (zh) | 无氯催化剂于制备二异丙胺硅烷中的用途 | |
USRE45839E1 (en) | Pentakis(dimethylamino) disilane precursor comprising compound and method for the preparation thereof | |
CN1596324A (zh) | 用化学蒸气沉积技术沉积氮化硅膜和氧氮化硅膜的方法 | |
KR20110035935A (ko) | 반도체 장치의 제조 방법 및 기판 처리 장치 | |
JP2004217659A (ja) | アミノシラン製造方法 | |
CN101857270A (zh) | 一种合成高纯砷烷的方法 | |
JP2006096675A (ja) | 新規なアミノジシランおよび炭窒化珪素膜の形成方法 | |
JP5260148B2 (ja) | ストロンチウム含有薄膜の形成方法 | |
CN102850388B (zh) | 一种硅烷偶联剂的制备方法 | |
CN115536687B (zh) | 三烷基氨基硅烷的制备方法及其用途 | |
CN108409779B (zh) | 一种γ-氨丙基三硅氧烷的制备方法 | |
CN117185299B (zh) | 有机金属催化剂在制备乙硅烷中的用途及乙硅烷的制法 | |
KR102435330B1 (ko) | 트리실릴아민의 제조 장치 및 제조 방법 | |
JP2535525B2 (ja) | シランの製造方法 | |
JP4542209B2 (ja) | 多結晶シリコンの製造方法および高純度シリカの製造方法 | |
CN112661781A (zh) | 一种双(叔丁基氨基)硅烷的制备方法 | |
KR20170005305A (ko) | 트리스(알킬아미노)실란의 제조 방법 | |
JP2001019418A (ja) | モノシラン及びテトラアルコキシシランの製造方法 | |
JPH0829927B2 (ja) | シランガスの製造法 | |
CN117208914A (zh) | 一种高纯二碘硅烷的制备、纯化方法及设备 | |
JP2001019419A (ja) | モノシラン及びテトラアルコキシシランの製造方法 | |
CN118183755A (zh) | 一种电子级二氯氢硅的合成及纯化方法 | |
CN117756838A (zh) | 一种Ca(HMDS)2的连续合成方法及合成*** | |
CN114715900A (zh) | 一种电子级乙硅烷的连续生产制备***及其生产工艺 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 23870700 Country of ref document: EP Kind code of ref document: A1 |