KR20160144550A - Method for removing compounds having Si-O bond from aminosilanes - Google Patents
Method for removing compounds having Si-O bond from aminosilanes Download PDFInfo
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- KR20160144550A KR20160144550A KR1020150080671A KR20150080671A KR20160144550A KR 20160144550 A KR20160144550 A KR 20160144550A KR 1020150080671 A KR1020150080671 A KR 1020150080671A KR 20150080671 A KR20150080671 A KR 20150080671A KR 20160144550 A KR20160144550 A KR 20160144550A
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- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 150000001875 compounds Chemical class 0.000 title claims abstract description 30
- 229910018557 Si O Inorganic materials 0.000 title claims abstract description 25
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000004791 alkyl magnesium halides Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 abstract description 12
- 238000009835 boiling Methods 0.000 abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000004817 gas chromatography Methods 0.000 description 8
- -1 silicon halide Chemical class 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 239000002305 electric material Substances 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- OCLVCXBBVUEYHC-UHFFFAOYSA-N 1-N,1-N,1-N',1-N'-tetramethyl-2-silyloxyethane-1,1-diamine Chemical compound CN(C)C(CO[SiH3])N(C)C OCLVCXBBVUEYHC-UHFFFAOYSA-N 0.000 description 1
- KXEAZJHCOWBLLF-UHFFFAOYSA-N 3-methyl-3-(3-methylpentan-3-yloxy)pentane Chemical compound CCC(C)(CC)OC(C)(CC)CC KXEAZJHCOWBLLF-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DFWJSTNRZNMYAE-UHFFFAOYSA-N n,n,n',n'-tetramethyl-1-silylmethanediamine Chemical compound CN(C)C([SiH3])N(C)C DFWJSTNRZNMYAE-UHFFFAOYSA-N 0.000 description 1
- OWKFQWAGPHVFRF-UHFFFAOYSA-N n-(diethylaminosilyl)-n-ethylethanamine Chemical compound CCN(CC)[SiH2]N(CC)CC OWKFQWAGPHVFRF-UHFFFAOYSA-N 0.000 description 1
- TWVSWDVJBJKDAA-UHFFFAOYSA-N n-[bis(dimethylamino)silyl]-n-methylmethanamine Chemical compound CN(C)[SiH](N(C)C)N(C)C TWVSWDVJBJKDAA-UHFFFAOYSA-N 0.000 description 1
- QULMGWCCKILBTO-UHFFFAOYSA-N n-[dimethylamino(dimethyl)silyl]-n-methylmethanamine Chemical compound CN(C)[Si](C)(C)N(C)C QULMGWCCKILBTO-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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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 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
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
-
- 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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Abstract
Description
본 발명은 아미노실란으로부터 Si-O 결합을 갖는 화합물을 제거하는 방법 에 관한 것이다.The present invention relates to a method for removing a compound having an Si-O bond from an aminosilane.
전형적인 아미노실란 제조 방법은 실리콘 할라이드(Silicon Halide)와 아민(Amine) 화합물을 반응시키는 것이다. 그러나 아민과 염산과의 반응 부산물로 염(Salt)이 생성되고 이들 염은 할로겐 농도를 증가시키는 문제가 있다. 이를 해결하기 위한 기술로서 아미노실란 제조 공정의 부산물인 염을 메탈 아마이드(Metal Amide)로 감소시키는 방법이 일본 공개특허공보 제1981-068686호에 기재되어 있고, 또한 미국 공개특허공보 제2012/0165564호 A1에서는 이러한 할로겐을 알킬메탈로 감소시키는 방법이 제시되어 있다. 이와 같이 전기전자 소재의 물질 내 할로겐 함량은 중요하여, 여러 문헌 및 특허에서 할로겐 함량을 줄이기 위한 방법을 제시하고 있으며, 실제 제품에서 항상 사양으로서 관리되고 있다. A typical method for preparing aminosilane is to react a silicon halide with an amine compound. However, a salt is formed as a reaction by-product of amine and hydrochloric acid, and these salts have a problem of increasing the halogen concentration. As a technique for solving this problem, a method of reducing a salt, which is a byproduct of the amino silane manufacturing process, to a metal amide is disclosed in Japanese Patent Laid-Open Publication No. 1981-068686 and US Patent Application Publication No. 2012/0165564 In A1, a method of reducing such a halogen to an alkyl metal is proposed. As described above, the halogen content in the material of the electric and electronic materials is important, and various literatures and patents suggest a method for reducing the halogen content.
또한, 할로겐 함량과 함께 아미노실란의 순도, 즉 아미노실란 제품 외에 부반응물의 함량이 얼마나 적은지가 제품의 사양에서 중요한 관리 대상이다. 순도를 높이기 위해 일반적으로 컬럼 증류를 통해 부반응물을 제거하게 된다. 일반적으로 전기전자 소재로 사용되기 위한 아미노실란의 순도는 99.8% 에서 99.9 %이며, 컬럼 증류과정에서 99.8% 이하의 제품은 다음 증류에서 혼합하여 재활용되기도 하지만, 일반적으로는 폐기되는 경우가 많다. In addition, the purity of the aminosilane, in other words, the content of the minor reactants in addition to the aminosilane product, is important in the specification of the product in addition to the halogen content. In order to increase the purity, the column reactant is generally removed by column distillation. Generally, the purity of aminosilane for use in electric and electronic materials is 99.8% to 99.9%. In the column distillation process, 99.8% or less of the product is mixed and recycled in the next distillation, but is generally discarded in general.
따라서, 폐기되는 양을 최소화하여 아미노실란의 수율을 향상시키고자 하는 노력이 계속되고 있다.Therefore, efforts are being made to improve the yield of aminosilane by minimizing the amount of waste.
본 발명은 Si-O 결합을 갖는 화합물을 불순물로 포함하는 아미노실란을 알킬메탈로 처리하여 상기 불순물을 아미노실란과 끓는점의 차이가 큰 화합물로 변형시키고 증류를 통해 불순물을 제거함으로써, 증류 공정을 단순화시키고 아미노실란을 수율을 향상시킬 수 있는, 아미노실란으로부터 Si-O 결합을 갖는 화합물을 제거하는 방법을 제공하는 것을 기술적 과제로 한다.The present invention simplifies the distillation process by treating an aminosilane containing an Si-O bond-containing compound as an impurity with an alkyl metal to transform the impurity into a compound having a large difference in boiling point from the aminosilane and removing impurities through distillation And a method for removing a compound having an Si-O bond from an aminosilane which can improve the yield of aminosilane.
상기한 기술적 과제를 해결하고자 본 발명은, Si-O 결합을 갖는 화합물을 포함하는 아미노실란을 알킬메탈로 처리하는 단계; 및 처리된 아미노실란을 증류하여 불순물을 제거하는 단계를 포함하는, 아미노실란으로부터 Si-O 결합을 갖는 화합물을 제거하는 방법을 제공한다.According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: treating an aminosilane containing a compound having a Si-O bond with an alkyl metal; And distilling the treated aminosilane to remove the impurities. The present invention also provides a method for removing a compound having an Si-O bond from an aminosilane.
본 발명의 방법을 이용하여 Si-O 결합을 갖는 화합물을 불순물로 포함하는 아미노실란을 알킬메탈로 처리하여 상기 불순물을 아미노실란과 끓는점의 차이가 큰 화합물로 변형시키고, 처리된 아미노실란 증류함으로써 Si-O 결합을 갖는 화합물을 용이하게 제거하고 아미노실란의 수율을 높일 수 있다.By using the method of the present invention, an aminosilane containing an Si-O bond-containing compound as an impurity is treated with an alkyl metal to transform the impurity into a compound having a large difference in boiling point from the aminosilane, and the treated aminosilane is distilled to obtain Si -O bond can be easily removed and the yield of aminosilane can be increased.
도 1은 본 발명의 일 구체예에 따른 제조예 1, 실시예 1, 비교예 1 및 2의 기체크로마토 그래프를 나타낸 것이다.
도 2는 Si-O 결합을 갖는 화합물을 알킬메틸로 처리하여 얻어진 생성물을 나타낸 것이다.
도 3은 본 발명의 일 구체예에 따른 제조예 2 및 실시예 2 내지 4의 기체크로마토 그래프를 나타낸 것이다.1 shows a gas chromatograph of Production Example 1, Example 1, and Comparative Examples 1 and 2 according to one embodiment of the present invention.
Figure 2 shows a product obtained by treating a compound having Si-O bonds with alkylmethyl.
3 shows gas chromatographs of Production Example 2 and Examples 2 to 4 according to one embodiment of the present invention.
이하, 도면을 참조하여 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail with reference to the drawings.
본 발명의 아미노실란으로부터 Si-O 결합을 갖는 화합물을 제거하는 방법은 Si-O 결합을 갖는 화합물을 포함하는 아미노실란을 알킬메탈로 처리하는 단계; 및 처리된 아미노실란을 증류하여 불순물을 제거하는 단계를 포함하는 것을 특징으로 한다.A method for removing a compound having an Si-O bond from the aminosilane of the present invention comprises: treating an aminosilane containing a compound having a Si-O bond with an alkyl metal; And distilling the treated aminosilane to remove impurities.
일반적으로 아미노실란의 불순물 중 하나인 Si-O 결합을 갖는 화합물은 아미노실란 제조에 사용되는 용매와 아민에서 유래되는 경우가 대부분이다. 제조과정에서 고순도화가 된 용매와 아민을 사용하는 경우 이러한 불순물을 획기적으로 줄일 수 있으나, 고가의 원재료비가 들어 경제성이 없다.In general, a compound having an Si-O bond, which is one of the impurities of the aminosilane, is most often derived from a solvent and an amine used in the production of an aminosilane. When using solvents and amines that are highly pure in the manufacturing process, these impurities can be drastically reduced, but they are not economical due to expensive raw material costs.
아미노실란 제조에 일반적으로 사용되는 용매는 에테르(Ether)로서, 에테르 내의 수분 또는 에테르의 원료인 알코올 류가 불순물로 소량 함유되어 있다. 이러한 수분이나 알코올 류는 실리콘 할라이드와 먼저 반응을 하여 결과물질로 Si-O 결합을 갖는 (Si-OH 또는 Si-O-R) 화합물(아미노실란)이 형성되며, 이들의 끓는점은 중요한 제품인 Si-N 결합을 갖는 아미노실란과 차이가 크지 않아 컬럼 증류로 제거하기 어렵다. The solvent commonly used in the production of aminosilane is ether, and alcohol or water in the ether or alcohol as a raw material is contained in a small amount as an impurity. These moisture and alcohols first react with the silicon halide to form a compound (Si-OH or Si-OR) (Si-OR) having Si-O bonds as a resultant substance. Their boiling point is Si- And it is difficult to remove by column distillation.
또한 아미노실란 제조 시 사용되는 알킬아민은 암모니아와 알코올의 반응에 의해 제조되므로 수분과 알코올 불순물이 소량 함유되어 있으므로, 에테르와 마찬가지로 알킬아민에 포함된 수분이나 알코올류가 실리콘 할라이드와 먼저 반응하여 Si-O 결합을 갖는 아미노실란이 형성된다. Since alkylamines used in the preparation of aminosilanes are prepared by the reaction of ammonia with alcohols, they contain a small amount of water and alcohol impurities. Therefore, water and alcohols contained in alkylamines react with silicon halide first, like ether, O bonds are formed.
수분은 실리콘 할라이드와 반응하여 일반적으로 분자량이 아주 큰 고분자 또는 겔을 유도하는데, 이는 아미노실란과의 끓는점 차이가 크다. 그러나, 알코올은 실리콘 할라이드와 먼저 반응하고 나머지가 아민과 반응하기 때문에, 아민과 알코올의 아주 작은 분자량 차이에 의해 생성된 불순물의 분자량 및 끓는점은 아미노실란 제품과 유사한 값을 가질 때가 많다.Moisture reacts with silicon halides to induce polymers or gels with very high molecular weights, which have a large boiling point difference with aminosilanes. However, since the alcohol first reacts with the silicon halide and the remainder react with the amine, the molecular weight and the boiling point of the impurities produced by the very small molecular weight difference between the amine and the alcohol often have values similar to those of the aminosilane product.
이에 아미노실란 합성 후 Si-O 결합을 갖는 화합물을 불순물로 포함하는 아미노실란을 알킬메탈로 처리하여, 불순물을 아미노실란과 끓는점의 차이가 큰 화합물로 변형시킨 후, 증류 처리하여 분리시킬 수 있다.After the aminosilane synthesis, the aminosilane containing a compound having Si-O bond as an impurity is treated with an alkyl metal to transform the impurity into a compound having a large difference in boiling point from the aminosilane, followed by distillation treatment.
본 발명의 아미노실란은 특별히 한정하지 않으며, 예를 들어 탄소수가 1 내지 8인 테트라키스디알킬아미노실란, 트리스디알킬아미노실란, 비스디알킬아미노실란, 모노디알킬아미노실란 및 이들의 혼합물로부터 선택된 것일 수 있다. The aminosilane of the present invention is not particularly limited and is, for example, selected from tetrakis dialkylaminosilane having 1 to 8 carbon atoms, trisdialkylaminosilane, bisdialkylaminosilane, monodialkylaminosilane, and mixtures thereof .
본 발명의 방법에서 사용되는 알킬메탈은, 아미노실란 총 100 중량%에 대해 0.05 내지 10 중량%, 예컨대 0.1 내지 5 중량%, 예컨대 0.5 내지 3 중량%를 사용하여 처리할 수 있다. 알킬메탈의 양이 너무 작은 경우 Si-O 결합을 가진 불순물을 충분히 제거 할 수 없고, 반대로 너무 많은 경우 수소결합과 같은 다른 작용기까지 변형시켜 제2의 불순물이 생성되므로, 아미노실란의 수율이 저감되고 원재료비의 상승으로 인해 경제성이 떨어질 수 있다.The alkylmetal used in the process of the present invention can be treated with from 0.05 to 10% by weight, such as from 0.1 to 5% by weight, for example from 0.5 to 3% by weight, based on 100% by weight of the total of the amino silanes. If the amount of the alkyl metal is too small, the impurities having Si-O bonds can not be removed sufficiently. On the contrary, if too much, other functional groups such as hydrogen bonds are modified to produce second impurities, The economic cost can be lowered due to the rise in raw material costs.
특별히 한정하지 않으나, 알킬메탈로는 탄소수가 1 내지 8인 알킬리튬, 알킬소듐 또는 알킬마그네슘할라이드를 사용할 수 있다. As the alkylmetal, alkyllithium, alkylsodium or alkylmagnesium halide having 1 to 8 carbon atoms can be used although not particularly limited.
또한, 본 발명의 방법은 Si-O 결합을 갖는 화합물을 알킬메탈로 2회 또는 그 이상으로 처리하여, 아미노실란으로부터 보다 분리가 용이한 화합물로 변경시킬 수 있다.
In addition, the method of the present invention can be changed to a compound that is more easily separated from aminosilane by treating the compound having Si-O bond with an alkyl metal two or more times.
이하, 실시예를 통하여 본 발명을 보다 상세하게 설명한다. 그러나, 본 발명의 범위가 이들 실시예로 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to these examples.
[[ 제조예Manufacturing example 1] - One] - 트리스디메틸아미노실란의Of trisdimethylaminosilane 제조 Produce
트리클로로실란(Trichlorosilane, MS가스) 140g을 용매인 에틸에테르(Ethyl Ether, 덕산약품) 900g 하에서 디메틸아민(Dimethylamine, Matheson) 460g을 시간당 200g의 속도로 반응시켰다. 반응온도는 5 ℃ 이하로 하여 디메틸아민이 기화되지 않도록 하였다. 다량의 흰색 염을 필터링한 후 생성된 트리스디메틸아미노실란(Tris-Dimethylaminosilane)을 기체크로마토그래피와 질량분석기로 분석하여 도 1에 나타내었다.140 g of trichlorosilane (MS gas) was reacted with 460 g of dimethylamine (Matheson) at a rate of 200 g per hour under 900 g of ethyl ether (Ethyl Ether, Duksan Chemical) as a solvent. The reaction temperature was kept at 5 DEG C or lower to prevent vaporization of dimethylamine. Tris-Dimethylaminosilane produced after filtering a large amount of white salt was analyzed by gas chromatography and mass spectrometry, and is shown in FIG.
[[ 실시예Example 1] One]
제조예 1의 트리스디메틸아미노실란 100g에 1.6 M 메틸리튬(Methyllithium in diethyl ether, Sigma-Aldrich) 2g을 투입한 후 5분간 교반하고, 가스크로마토그래피를 분석하여 도 1에 나타내었다 2 g of Methyllithium in diethyl ether (Sigma-Aldrich) was added to 100 g of trisdimethylaminosilane of Preparation Example 1, stirred for 5 minutes, analyzed by gas chromatography, and shown in Fig. 1
[[ 비교예Comparative Example 1] One]
제조예 1의 트리스디메틸아미노실란 100g에 소듐하이드라이드(Sodium Hidride, Sigma-Aldrich) 파우더를 1g을 투입한 후 5분간 교반하고, 가스크로마토그래피를 분석하여 도 1에 나타내었다. 1 g of sodium hydride (Sigma-Aldrich) powder was added to 100 g of trisdimethylaminosilane of Preparation Example 1, stirred for 5 minutes, and analyzed by gas chromatography.
[[ 비교예Comparative Example 2] 2]
제조예 1의 트리스디메틸아미노실란 100g에 소듐알루미늄하이드라이드 (Sodium Aluminum Hydride, Sigma-Aldrich) 1 g을 투입한 후 5분간 교반하고, 가스크로마토그래피를 분석하여 도 1에 나타내었다.
1 g of sodium aluminum hydride (Sigma-Aldrich) was added to 100 g of trisdimethylaminosilane of Production Example 1, stirred for 5 minutes, and analyzed by gas chromatography, as shown in Fig.
[[ 제조예Manufacturing example 2] - 2] - 비스디에틸아미노실란의Of bisdiethylaminosilane 제조 Produce
디에틸아민(Diethylamine, 덕산약품) 420g을 용매인 테트라하이드로퓨란 (Tetrahydrofuran, 덕산약품) 980g 하에서 디클로로실란(Dichlorosilane, MS가스) 120g을 시간당 50g의 속도로 반응시켰다. 반응온도는 5 ℃ 이하로 하여 디클로로실란이 기화되지 않도록 하였다. 다량의 흰색 염을 필터링한 후 생성된 비스디에틸아미노실란(Bis-Diethylaminosilane)을 기체크로마토그래피와 질량분석기로 분석하여 도 3에 나타내었다. 120 g of dichlorosilane (MS gas) was reacted at a rate of 50 g per hour under 980 g of tetrahydrofuran (Duksan Chemical) as a solvent, and 420 g of diethylamine (Duksan Chemical) was reacted. The reaction temperature was set to 5 DEG C or less so that the dichlorosilane was not vaporized. The resulting bis-diethylaminosilane after filtering a large amount of white salt was analyzed by gas chromatography and mass spectrometry, and is shown in FIG.
[[ 실시예Example 2] 2]
제조예 2의 비스디에틸아미노실란 100g에 1.6 M 메틸리튬(Methyllithium in diethyl ether, Sigma-Aldrich) 2g을 투입한 후 5분간 교반하고, 가스크로마토그래피를 분석하여 도 3에 나타내었다.2 g of 1.6 M methyllithium in diethyl ether (Sigma-Aldrich) was added to 100 g of bisdiethylaminosilane of Preparation Example 2, stirred for 5 minutes, and analyzed by gas chromatography.
[[ 실시예Example 3] 3]
제조예 2의 비스디에틸아미노실란 100g에 1.6 M 에틸리튬(Ethyllithium in diethyl ether, Sigma-Aldrich) 2g을 투입한 후 5분간 교반하고, 가스크로마토그래피를 분석하여 도 3에 나타내었다.2 g of 1.6 M ethyl lithium (diethyl ethyl ether, Sigma-Aldrich) was added to 100 g of bisdiethylaminosilane of Preparation Example 2, stirred for 5 minutes, and analyzed by gas chromatography.
[[ 실시예Example 4] 4]
제조예 2의 비스디에틸아미노실란 100g에 1.6 M 부틸리튬(Buthyllithium in diethyl ether, Sigma-Aldrich) 2 g을 투입한 후 5분간 교반하고, 가스크로마토그래피를 분석하여 도 3에 나타내었다.
2 g of buthyllithium in diethyl ether (Sigma-Aldrich) was added to 100 g of bisdiethylaminosilane of Preparation Example 2, stirred for 5 minutes, and analyzed by gas chromatography.
도 1에서 알 수 있는 바와 같이, 제조예 1에서 아미노실란 제품인 8.5 min의 트리스디메틸아미노실란 주위에 불순물들이 여러 종류가 있고, 7.8 min과 같이 가까운 물질은 컬럼 증류에서도 제거가 어려우며, 불순물을 최소화하기 위해서는 컬럼 증류의 수율이 많이 떨어진다. 이에 실시예 1과 같이 메틸리튬을 소량 처리하는 경우 7.8 min 뿐만 아니라 그 주위의 불순물인 7.1 min, 6.7 min의 불순물까지 거의 제거 되며, 6.5 min와 9.5 min의 신규 피크가 생성된다. 이는 아미노실란 제품과 피크 간격이 멀어진 화합물이므로 증류를 통한 제거가 용이함을 알 수 있다. As can be seen from FIG. 1, there are many kinds of impurities around the trisdimethylaminosilane of 8.5 min, which is the product of aminosilane in Production Example 1. It is difficult to remove impurities near the 7.8 min even in the column distillation, The yield of the column distillation drops considerably. As shown in Example 1, when methyllithium is treated in a small amount, impurities of about 7.1 min and 6.7 min, which are impurities in the vicinity of 7.8 min, are almost removed, and new peaks of 6.5 min and 9.5 min are produced. It can be seen that it is easy to remove by distillation since it is a compound having a peak interval away from the aminosilane product.
도 2는 Si-O 결합을 갖는 화합물을 알킬메틸로 처리하여 얻어진 생성물을 나타낸 것으로서, 주요 불순물인 7.8 min 화합물은 비스디메틸아미노에톡시실란(Bis-dimethylaminoethoxysilane)으로 분석되는데, 상기 물질이 메틸리튬의 메틸과 반응하여 비스디메틸아미노메틸실란(Bis-dimethylaminomethylsilane) 6.5 min으로 바뀌고, 메틸과 더 반응하면 5.4 min인 비스디메틸아미노디메틸실란(Bis-dimethylaminodimethylsilane)으로 바뀌게 된다. 그러나 비교예 1 및 2에서 알 수 있는 바와 같이, Si-O 결합을 갖는 화합물에 소듐 하이드라이드(Sodium Hydride)와 소듐 알루미늄 하이드라이드(Sodium Aluminum Hydride)와는 반응하지 않음을 알 수 있었다. Figure 2 shows a product obtained by treating a compound having Si-O bonds with alkylmethyl, wherein the major impurity, 7.8 min, is analyzed by bis-dimethylaminoethoxysilane, Reacted with methyl to convert bis-dimethylaminomethylsilane to 6.5 min, and when it reacts with methyl, it becomes bis-dimethylaminodimethylsilane, which is 5.4 min. However, as can be seen from Comparative Examples 1 and 2, it was found that the compound having Si-O bond did not react with sodium hydride and sodium aluminum hydride.
또한 제조예 2 및 실시예 2 내지 4에서 알 수 있는 바와 같이, 비스디에틸아미노실란을 제조할 때 생성된 Si-O 결합을 갖는 화합물을 여러 가지 알킬리튬 시약으로 처리하여 아미노실란 제품 피크로부터 최대한 멀리 유도할 수 있다. 도 3에서 알 수 있는 바와 같이, 부틸리튬을 사용하는 경우의 생성물은 아미노실란 제품과 비교적 가까운 피크가 형성되었으나, 메틸리튬과 에틸리튬으로 처리한 경우의 생성물은 아미노실란 제품 피크에서 상당히 먼 피크가 형성됨을 알 수 있었다. 따라서, 제품의 사양 및 경제성 등에 따라 적절한 시약을 선택할 지를 검토하여 선택할 수 있음을 확인할 수 있었다. Further, as can be seen in Production Example 2 and Examples 2 to 4, the compound having Si-O bond produced in the production of bisdiethylaminosilane was treated with various alkyllithium reagents, Can be guided away. As can be seen from FIG. 3, the product with butyllithium formed a relatively close peak with the aminosilane product, but the product with methyllithium and ethyllithium had a significantly higher peak at the aminosilane product peak Respectively. Therefore, it has been confirmed that the choice of the appropriate reagent can be selected and selected according to the product specifications and economical efficiency.
Claims (5)
처리된 아미노실란을 증류하여 불순물을 제거하는 단계를 포함하는, 아미노실란으로부터 Si-O 결합을 갖는 화합물을 제거하는 방법.Treating an aminosilane containing a compound having Si-O bonds with an alkyl metal; And
And removing the impurities by distilling the treated aminosilane to remove the compound having an Si-O bond from the aminosilane.
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