KR20050099246A - Method of producing electronic grade tetraethoxysilane from tetrachlorosilane-trimethylchlorosilane azeotrope - Google Patents
Method of producing electronic grade tetraethoxysilane from tetrachlorosilane-trimethylchlorosilane azeotrope Download PDFInfo
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- KR20050099246A KR20050099246A KR1020040024486A KR20040024486A KR20050099246A KR 20050099246 A KR20050099246 A KR 20050099246A KR 1020040024486 A KR1020040024486 A KR 1020040024486A KR 20040024486 A KR20040024486 A KR 20040024486A KR 20050099246 A KR20050099246 A KR 20050099246A
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- South Korea
- Prior art keywords
- trimethylchlorosilane
- silicon tetrachloride
- tetraethoxysilane
- azeotrope
- ethoxychlorosilanes
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 23
- JDAVPOHISXMMSP-UHFFFAOYSA-N chloro(trimethyl)silane;tetrachlorosilane Chemical compound C[Si](C)(C)Cl.Cl[Si](Cl)(Cl)Cl JDAVPOHISXMMSP-UHFFFAOYSA-N 0.000 title 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 110
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 57
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 46
- SMRTZQCUWYSWJR-UHFFFAOYSA-N chloro(ethoxy)silane Chemical compound CCO[SiH2]Cl SMRTZQCUWYSWJR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- -1 monosilane compound Chemical class 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 15
- 239000002184 metal Substances 0.000 abstract description 15
- 238000004821 distillation Methods 0.000 abstract description 14
- 229910052710 silicon Inorganic materials 0.000 abstract description 13
- 239000010703 silicon Substances 0.000 abstract description 13
- 238000009835 boiling Methods 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 abstract description 7
- 239000005046 Chlorosilane Substances 0.000 abstract description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 4
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- JEZFASCUIZYYEV-UHFFFAOYSA-N chloro(triethoxy)silane Chemical compound CCO[Si](Cl)(OCC)OCC JEZFASCUIZYYEV-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- UFCXHBIETZKGHB-UHFFFAOYSA-N dichloro(diethoxy)silane Chemical compound CCO[Si](Cl)(Cl)OCC UFCXHBIETZKGHB-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- SELBPKHVKHQTIB-UHFFFAOYSA-N trichloro(ethoxy)silane Chemical compound CCO[Si](Cl)(Cl)Cl SELBPKHVKHQTIB-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material 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
- C07F7/04—Esters of silicic acids
-
- 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
- C07F7/12—Organo silicon halides
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
본 발명은 사염화규소와 트리메틸클로로실란의 공비혼합물로부터 전자급 테트라에톡시실란의 제조방법에 관한 것으로서, 더욱 상세하게는 금속규소와 염화메탄의 촉매반응으로 모노실란 화합물을 제조하는 공정에서 발생한 공비혼합물로 일반적인 증류법으로는 분리가 어려운 사염화규소와 트리메틸클로로실란의 공비혼합물에, 에탄올을 첨가량과 첨가속도를 조절하여 첨가함으로써 사염화규소를 에톡시클로로실란류로 전환시키는 과정과, 상기 공정에서 비점의 차이가 크게 전환된 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 증류하는 간단한 공정으로 트리메틸클로로실란 화합물을 분리제거하여 에톡시클로로실란류를 회수하는 과정 및 상기 분리 회수된 에톡시클로로실란류로부터 전자급 테트라에톡시실란을 제조하는 방법에 관한 것이다.The present invention relates to a method for producing an electronic tetraethoxysilane from an azeotrope of silicon tetrachloride and trimethylchlorosilane, and more particularly, an azeotrope produced in the process of preparing a monosilane compound by the catalytic reaction of metal silicon and methane chloride. The process of converting silicon tetrachloride to ethoxychlorosilane by adding ethanol to an azeotrope of silicon tetrachloride and trimethylchlorosilane, which is difficult to separate by a general distillation method, and the boiling point difference in the process Is a simple step of distilling a mixture of trimethylchlorosilane and ethoxychlorosilanes, which are highly converted, to recover ethoxychlorosilanes by separating and removing the trimethylchlorosilane compound, and from the separated and recovered ethoxychlorosilanes. Related to the process for preparing the grade tetraethoxysilane It is.
본 발명에 의하면, 금속규소와 염화메탄의 촉매반응에서 모노실란 화합물 제조시 발생한 사염화규소와 트리메틸클로로실란의 공비혼합물로부터 간단한 방법으로 트리메틸클로로실란을 분리하여 재사용 가능하며, 사염화규소로부터 제조된 에톡시클로로실란으로 전자급 테트라에톡시실란을 90% 이상의 우수한 수율로 제조가 가능하므로 금속규소와 염화메탄의 촉매반응에서 얻어진 모노실란 화합물의 사용효율을 극대화할 수 있는 효과가 있다.According to the present invention, trimethylchlorosilane can be separated and reused by an azeotropic mixture of silicon tetrachloride and trimethylchlorosilane generated during the production of a monosilane compound in the catalytic reaction of metal silicon and methane chloride, and is prepared from silicon tetrachloride. Since chlorosilanes can be used to produce electronic grade tetraethoxysilanes in an excellent yield of more than 90%, there is an effect that can maximize the use efficiency of the monosilane compound obtained in the catalytic reaction of metal silicon and methane chloride.
Description
본 발명은 사염화규소와 트리메틸클로로실란의 공비혼합물로부터 전자급 테트라에톡시실란의 제조방법에 관한 것으로서, 더욱 상세하게는 금속규소와 염화메탄의 촉매반응으로 모노실란 화합물을 제조하는 공정에서 발생한 공비혼합물로서 일반적인 증류법으로는 분리가 어려운 사염화규소와 트리메틸클로로실란의 공비혼합물에, 에탄올을 첨가량과 첨가속도를 조절하여 첨가함으로써 사염화규소를 에톡시클로로실란류로 전환시키는 과정과, 상기 공정에서 비점의 차이가 크게 전환된 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 증류하는 간단한 공정으로 트리메틸클로로실란 화합물을 분리제거하여 에톡시클로로실란류를 회수하는 과정 및 상기 분리 회수된 에톡시클로로실란류로부터 전자급 테트라에톡시실란을 제조하는 방법에 관한 것이다. The present invention relates to a method for producing an electronic tetraethoxysilane from an azeotrope of silicon tetrachloride and trimethylchlorosilane, and more particularly, an azeotrope produced in the process of preparing a monosilane compound by the catalytic reaction of metal silicon and methane chloride. As an azeotrope of silicon tetrachloride and trimethylchlorosilane, which are difficult to be separated by a general distillation method, the process of converting silicon tetrachloride to ethoxychlorosilane by adding ethanol by adjusting the amount and rate of addition, and the difference in boiling point in the process Is a simple step of distilling a mixture of trimethylchlorosilane and ethoxychlorosilanes, which are highly converted, to recover ethoxychlorosilanes by separating and removing the trimethylchlorosilane compound, and from the separated and recovered ethoxychlorosilanes. In the method for producing a grade tetraethoxysilane It is about.
전자급(Electronic Grade) 테트라에톡시실란은 일반적으로 순도 99.8% 이상, 금속성분 함량 1 ppm 이하, 산 또는 염기도 0.001% 이하 및 수분함량이 100 ppm 이하의 규격을 만족하는 것으로, 상업적으로 광섬유, 코팅제의 첨가물 및 반도체 절연막 형성물질 등으로 널리 사용되고 있으며, 일반적으로 순수한 사염화규소에 에탄올을 첨가하여 제조된다. 상기한 방법 외에 금속규소를 에탄올과 직접 반응하여 제조하기도 하는데, 1979 년 영국특허 제2,017,129호에는 알코올과 금속규소를 촉매 하에서 직접 반응시켜 알콕시실란 화합물을 제조하는 방법이 기재되어 있어 상기와 같이 순수한 사염화규소 또는 금속규소로부터 전자급 테트라에톡시실란을 제조하는 방법은 잘 알려져 있다. Electronic grade tetraethoxysilane generally meets the specifications of purity of 99.8% or more, metal content of 1 ppm or less, acid or basicity of 0.001% or less, and water content of 100 ppm or less. It is widely used as an additive and a semiconductor insulating film forming material, and is generally prepared by adding ethanol to pure silicon tetrachloride. In addition to the above-described method, metal silicon may be prepared by directly reacting with ethanol. In 1979, British Patent No. 2,017,129 describes a method for producing an alkoxysilane compound by directly reacting alcohol and metal silicon under a catalyst. Processes for preparing electronic tetraethoxysilanes from silicon or metal silicon are well known.
한편, 금속규소와 염화메탄을 촉매하에서 반응시키면 여러 모노실란 화합물이 생성되고, 그 종류로는 메틸클로로실란(MH), 사염화규소(STC), 메틸트리클로로실란(M1), 디메틸디클로로실란(M2), 트리메틸클로로실란(M3) 등이 혼합물로 존재하게 된다. 이들 중 사염화규소는 끓는점이 57.6 ℃ 이고, 트리메틸클로로실란은 끓는점이 57.9 ℃로서 두 화합물의 비점이 서로 비슷하여 일반적인 증류방법으로는 완벽하게 분리하기 어려운 공비혼합물(불변 끓는점 54.7 ℃)의 상태로 존재하게 된다. 이와 같은 공비혼합물을 효과적으로 분리하기 위해서는 증류단수를 높여야 하고, 이 경우 장치 비용이 높아져 경제적으로 효과적이지 못한 단점이 있다.On the other hand, when metal silicon and methane chloride are reacted under a catalyst, various monosilane compounds are produced, and the types thereof include methylchlorosilane (MH), silicon tetrachloride (STC), methyltrichlorosilane (M 1 ), and dimethyldichlorosilane ( M 2 ), trimethylchlorosilane (M 3 ), and the like will be present in the mixture. Among them, silicon tetrachloride has a boiling point of 57.6 ° C. and trimethylchlorosilane has a boiling point of 57.9 ° C., and the boiling point of the two compounds is similar to each other, so it exists as an azeotrope (unstable boiling point of 54.7 ° C.) which is difficult to be completely separated by a general distillation method. Done. In order to effectively separate such an azeotrope, the number of distillation stages must be increased, and in this case, the apparatus cost is high and it is not economically effective.
또한 미국특허 제2,388,575호에는 공비혼합물로 존재하는 사염화규소와 트리메틸클로로실란을 분리하는 방법으로 니트릴이 포함된 용매를 사용하는데, 공비혼합물에 끓는점이 81.6 ℃인 아세토니트릴이나 79 ℃인 아크릴로니트릴을 일정량 첨가하여 증류하면 사염화규소-니트릴 공비혼합물과 트리메틸클로로실란-니트릴 공비혼합물의 끓는점 차이로 인하여 사염화규소와 트리메틸클로로실란을 분리할 수 있으나, 두 화합물은 니트릴 화합물과 또 다른 공비혼합물을 형성하므로 추가적인 분리공정이 필요한 단점이 있다.In addition, US Pat. No. 2,388,575 uses a solvent containing nitrile as a method of separating silicon tetrachloride and trimethylchlorosilane present as an azeotrope, and acetonitrile having a boiling point of 81.6 ° C. or acrylonitrile at 79 ° C. Distillation by addition of a certain amount can separate silicon tetrachloride and trimethylchlorosilane due to the difference in boiling point of the silicon tetrachloride-nitrile azeotrope and the trimethylchlorosilane-nitrile azeotrope, but the two compounds form another azeotrope with the nitrile compound. There is a disadvantage that a separation process is required.
즉, 메틸클로로실란(MH), 사염화규소(STC), 메틸트리클로로실란(M1), 디메틸디클로로실란(M2), 트리메틸클로로실란(M3) 등의 모노실란 화합물들은 다양한 특성을 갖는 실리콘 제품의 원료로 사용되고 있으나, 이중 사염화규소와 트리메틸클로로실란 공비혼합물은 그 분리가 어려워 활용도가 낮으므로 모노실란 화합물의 사용 효율이 저하될 뿐 아니라 폐기물 처리시 비용 및 환경오염 문제를 야기시킬 수 있다.That is, monosilane compounds such as methylchlorosilane (MH), silicon tetrachloride (STC), methyltrichlorosilane (M 1 ), dimethyldichlorosilane (M 2 ), trimethylchlorosilane (M 3 ), and the like have a variety of silicone properties. Although it is used as a raw material of the product, the double tetrachloride and trimethylchlorosilane azeotropes are difficult to separate and thus have low utilization, and thus, the use efficiency of the monosilane compound is not only lowered, but also may cause cost and environmental pollution problems in waste treatment.
이에 본 발명자들은 사염화규소와 트리메틸클로로실란의 공비혼합물로부터 효과적으로 트리메틸클로로실란을 선택적으로 분리할 수 있는 방법을 찾기 위해 연구 노력하였으며, 그 결과 상기 공비혼합물에 에탄올을 첨가량 및 첨가속도를 조절하여 첨가할 경우 에탄올과 사염화규소와의 반응이 훨씬 빠르게 이루어져 에톡시클로로실란 화합물을 생성하게 되며, 이 에톡시클로로실란 화합물은 상기한 트리메틸클로로실란보다 높은 비점을 가지고 있어 일반적인 증류법을 적용하여 쉽게 분리해낼 수 있음을 알게 되어 본 발명을 완성하였다. Accordingly, the present inventors have tried to find a method for effectively separating trimethylchlorosilane from an azeotrope of silicon tetrachloride and trimethylchlorosilane. As a result, ethanol is added to the azeotrope by adjusting the amount and rate of addition. In this case, the reaction between ethanol and silicon tetrachloride is much faster, producing an ethoxychlorosilane compound. The ethoxychlorosilane compound has a higher boiling point than the trimethylchlorosilane, and can be easily separated by applying a general distillation method. The present invention has been completed.
따라서, 본 발명은 사염화규소와 트리메틸클로로실란의 공비혼합물로부터 트리메틸클로로실란을 분리하고, 전자급 테트라에톡시실란을 제조함으로써 금속규소와 염화메탄의 촉매 반응에서 얻어진 모노실란 화합물, 특히 사염화규소 및 트리메틸클로로실란의 사용 효율을 극대화할 수 있는 사염화규소와 트리메틸클로로실란의 공비혼합물로부터 전자급 테트라에톡시실란의 제조방법을 제공하는데 그 목적이 있다. Accordingly, the present invention provides a monosilane compound, especially silicon tetrachloride and trimethyl, obtained in the catalytic reaction of metal silicon and methane by separating trimethylchlorosilane from an azeotrope of silicon tetrachloride and trimethylchlorosilane and preparing an electronic tetraethoxysilane. An object of the present invention is to provide a method for preparing an electronic tetraethoxysilane from an azeotrope of silicon tetrachloride and trimethylchlorosilane which can maximize the use efficiency of chlorosilane.
본 발명은 사염화규소와 트리메틸클로로실란을 포함하는 공비혼합물에, 상기 사염화규소와 에탄올을 첨가하며 반응시켜서 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 제조하는 제 1 단계, 상기 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 증류하여 트리메틸클로로실란을 분리제거 후, 잔류된 에톡시클로로실란류에 에탄올을 첨가하여 산성의 테트라에톡시실란을 제조하는 제 2 단계, 및 상기 산성의 테트라에톡시실란을 중화처리하여 전자급 테트라에톡시실란을 제조하는 제 3 단계를 포함하는 전자급 테트라에톡시실란의 제조방법을 특징으로 한다.The present invention provides a first step of preparing a mixture of trimethylchlorosilane and ethoxychlorosilanes by reacting an azeotrope containing silicon tetrachloride and trimethylchlorosilane by adding silicon tetrachloride and ethanol, the trimethylchlorosilane and Distilling the mixture of oxychlorosilanes to separate and remove trimethylchlorosilane, and then adding ethanol to the remaining ethoxychlorosilanes to produce acidic tetraethoxysilane, and the acidic tetraethoxysilane It characterized in that the method for producing an electronic tetraethoxysilane comprising a third step of neutralizing the production of an electronic tetraethoxysilane.
이와 같은 본 발명을 상세하게 설명하면 다음과 같다.The present invention will be described in detail as follows.
본 발명은 금속규소와 염화메탄의 촉매반응으로 모노실란 화합물을 제조하는 공정에서 발생한 공비혼합물로서 일반적인 증류법으로는 분리가 어려운 사염화규소와 트리메틸클로로실란의 혼합물에, 에탄올을 첨가량과 첨가속도를 조절하여 첨가함으로써 사염화규소를 에톡시클로로실란 화합물로 전환시킨 후 증류하는 간단한 공정으로 트리메틸클로로실란 화합물을 분리제거하고, 상기 에톡시클로로실란 화합물로부터 전자급 테트라에톡시실란을 제조하는 방법에 관한 것이다.The present invention is an azeotrope produced in the process of preparing a monosilane compound by the catalytic reaction of metal silicon and methane chloride, and ethanol is added to the mixture of silicon tetrachloride and trimethylchlorosilane, which is difficult to separate by a general distillation method, by adjusting the addition amount and the rate of A trimethylchlorosilane compound is separated and removed by a simple step of converting silicon tetrachloride to an ethoxychlorosilane compound by distillation by addition, and a method for producing an electronic tetraethoxysilane from the ethoxychlorosilane compound.
이하, 본 발명을 제조 단계별로 구체적으로 설명한다.Hereinafter, the present invention will be described in detail by production steps.
먼저, 사염화규소와 트리메틸클로로실란을 포함하는 공비혼합물에, 상기 사염화규소와 에탄올을 첨가하며 반응시켜서 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 제조하는 제 1 단계이다.First, the first step is to prepare a mixture of trimethylchlorosilane and ethoxychlorosilanes by reacting silicon tetrachloride and ethanol with an azeotrope containing silicon tetrachloride and trimethylchlorosilane.
즉, 에탄올의 사용량 및 투입속도를 조절하여 에탄올과 사염화규소의 반응성을 향상시키고, 트리메틸클로로실란의 반응성을 억제시킴에 본 발명의 특징이 있으며, 이때 에탄올의 사용량은 공비혼합물 내에 함유된 사염화규소 100 중량부에 대하여 49 ~ 54 중량부의 비율로 첨가한다. 이때, 에탄올 사용량이 49 중량부 미만이면 에탄올과 사염화규소의 반응이 완전하지 않아 과량의 사염화규소가 잔류하게 되고, 54 중량부를 초과하면 에탄올이 트리메틸클로로실란과 반응하여 트리메틸에톡시실란 등의 부 반응물의 생성이 많아진다. 또한, 에탄올의 첨가속도를 시간당 18 ~ 20 중량부가 되도록 조절하는데, 이때 첨가속도가 시간당 18 중량부 미만이면 에탄올 첨가 시간이 늘어나 공정상 효율이 감소하고 시간당 20 중량부를 초과하여 빠르게 되면 에탄올이 트리메틸클로로실란과 반응하여 부 반응물이 많이 생성되는 문제점이 있다.That is, the present invention is characterized by improving the reactivity of ethanol and silicon tetrachloride by adjusting the amount of ethanol used and the input rate, and inhibiting the reactivity of trimethylchlorosilane, wherein the amount of ethanol is used in the silicon tetrachloride 100 contained in the azeotrope. It is added in the ratio of 49-54 weight part with respect to a weight part. At this time, when the amount of ethanol is less than 49 parts by weight, the reaction between ethanol and silicon tetrachloride is not complete, and an excess of silicon tetrachloride remains. When the amount of ethanol exceeds 54 parts by weight, the ethanol reacts with trimethylchlorosilane to react with a side reaction such as trimethylethoxysilane. Will generate more. In addition, the rate of addition of ethanol is adjusted to 18 to 20 parts by weight per hour, wherein if the addition rate is less than 18 parts by weight per hour, the ethanol addition time increases and the process efficiency decreases. There is a problem that a lot of side reactants are generated by reacting with silane.
상기와 같은 에탄올의 첨가량 및 첨가 속도를 조절하여 첨가하면서 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 제조하는 반응은 10 ~ 30 ℃에서 30 ~ 120 분 동안 진행시킨다.The reaction for preparing a mixture of trimethylchlorosilane and ethoxychlorosilanes while controlling the addition amount and the addition rate of ethanol as described above is performed at 10 to 30 ° C. for 30 to 120 minutes.
상기와 같이 에탄올의 사용량과 첨가속도를 조절함으로써 공비 혼합물 중의 사염화규소를 디에톡시디클로로실란{(EtO)2SiCl2}, 트리에톡시클로로실란{(EtO)3SiCl} 및 에톡시트리클로로실란{EtOSiCl3} 등과 같은 에톡시클로로실란류로 전환시킬 수 있게 되는 것이다.By adjusting the amount of ethanol and the addition rate as described above, the silicon tetrachloride in the azeotropic mixture was converted to diethoxydichlorosilane {(EtO) 2 SiCl 2 }, triethoxychlorosilane {(EtO) 3 SiCl} and ethoxytrichlorosilane { EtOSiCl 3 } and the like can be converted to ethoxychlorosilanes.
두 번째로, 상기 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 증류하여 트리메틸클로로실란을 분리제거 후 잔류된 에톡시클로로실란류에 에탄올을 첨가하여 산성의 테트라에톡시실란을 제조하는 제 2 단계이다.Secondly, a second step of distilling the mixture of trimethylchlorosilane and ethoxychlorosilanes to separate and remove trimethylchlorosilane and adding ethanol to the remaining ethoxychlorosilanes to produce acidic tetraethoxysilane to be.
상기 단계에서 사염화규소와 에탄올의 반응으로 전환된 에톡시클로로실란류는 트리메틸클로로실란보다 높은 비점을 갖고 있으므로, 일반적인 증류방법에 의해 쉽게 에톡시클로로실란류와 트리메틸클로로실란을 분리해낼 수 있다. 상기 증류 온도는 58 ~ 60 ℃ 범위이며, 상기한 증류가 끝난 후 100 ~ 105 ℃에서 트리메틸클로로실란과 에톡시클로로실란의 중간혼합물을 추가로 증류하여 제거할 수 있다. 이와 같이 트리메틸클로로실란과 중간혼합물을 분리해 내고 잔류한 순수한 에톡시클로로실란류에 상기 1단계의 사염화규소 100 중량부에 대하여 50 ~ 60 중량부의 에탄올을 첨가하여 50 ~ 70 ℃에서 반응시킴으로써 산성의 테트라에톡시실란을 제조할 수 있으며, 이때 미반응 에탄올은 125 torr, 56 ~ 58 ℃에서 증류법으로 제거한다.Since the ethoxychlorosilanes converted by the reaction of silicon tetrachloride and ethanol in this step have a higher boiling point than trimethylchlorosilane, the ethoxychlorosilanes and trimethylchlorosilane can be easily separated by a general distillation method. The distillation temperature is in the range of 58 ~ 60 ℃, after the above-mentioned distillation can be further distilled off the intermediate mixture of trimethylchlorosilane and ethoxychlorosilane at 100 ~ 105 ℃. Thus, trimethylchlorosilane and the intermediate mixture are separated, and 50 to 60 parts by weight of ethanol is added to 100 parts by weight of silicon tetrachloride in the first step to the remaining pure ethoxychlorosilanes to react at 50 to 70 ° C. Tetraethoxysilane can be prepared, wherein unreacted ethanol is removed by distillation at 125 torr, 56-58 ° C.
마지막으로, 상기 산성의 테트라에톡시실란을 중화처리하여 전자급 테트라에톡시실란을 제조하는 제 3 단계이다.Finally, the acidic tetraethoxysilane is neutralized to prepare an electronic tetraethoxysilane.
상기 제 2 단계에서 제조된 테트라에톡시실란은 산성을 나타내는데, 이를 소듐 에톡사이드를 사용하여 중화처리하며, 이때 생성된 염화나트륨 염은 여과하여 제거한 후 추가적인 증류공정(125 torr, 110 ~ 112 ℃)을 거쳐 무색의 중화된 전자급 테트라에톡시실란를 얻을 수 있다. The tetraethoxysilane prepared in the second step is acidic, which is neutralized using sodium ethoxide, and the sodium chloride salt produced is filtered off and then further distilled (125 torr, 110-112 ° C.). Through this, colorless neutralized electronic tetraethoxysilane can be obtained.
이하 본 발명을 실시예에 의거하여 구체적으로 설명하겠는바, 본 발명이 다음 실시예에 의하여 한정되는 것은 아니다. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.
실시예 Example
제 1 단계First step
반응기에 사염화규소 500 kg과 트리메틸클로로실란 500 kg을 포함하는 공비혼합물을 첨가하고 교반하면서 270 kg의 에탄올을 정량펌프를 이용하여 시간당 100 kg의 속도로 주입하였다. 반응기의 온도는 10 ~ 30 ℃로 유지하였으며 반응 중 발생하는 HCl 기체는 가스포집기로 포집하였다. 에탄올의 첨가가 끝난후 실온에서 1시간 추가 반응시켜 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 제조하였고, 반응기 내의 혼합물을 채취하여 가스 크로마토그래피를 이용하여 성분 및 함량 분석을 실시하였으며 그 결과를 다음 표 1에 나타내었다. An azeotrope containing 500 kg of silicon tetrachloride and 500 kg of trimethylchlorosilane was added to the reactor, and 270 kg of ethanol was injected at a rate of 100 kg per hour using a metering pump while stirring. Reactor temperature was maintained at 10 ~ 30 ℃ and HCl gas generated during the reaction was collected by the gas collector. After the addition of ethanol, the mixture was further reacted at room temperature for 1 hour to prepare a mixture of trimethylchlorosilane and ethoxychlorosilanes. The mixture in the reactor was taken, and the components and contents were analyzed by gas chromatography. It is shown in Table 1 below.
제 2 단계2nd step
상기 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 58 ~ 60 ℃로 증류하여 순도 99.0%의 트리메틸클로로실란 470 kg을 분리해내고, 100 ~ 105 ℃에서 트리메틸클로로실란-에톡시클로로실란의 중간혼합물 50 kg을 증류하였다. 잔류한 에톡시클로로실란류에 260 kg의 에탄올을 첨가하여 산성의 테트라에톡시실란을 제조하였으며, 반응중 발생하는 HCl 기체는 가스포집기로 포집하였다. 또한 미반응 에탄올은 125 torr, 56 ~ 58 ℃로 유지하며 증류하여 산성의 테트라에톡시실란 610 kg을 얻었다.The mixture of trimethylchlorosilane and ethoxychlorosilanes was distilled at 58-60 ° C. to separate 470 kg of trimethylchlorosilane with a purity of 99.0%, and an intermediate mixture of trimethylchlorosilane-ethoxychlorosilane at 100-105 ° C. 50 kg were distilled off. Acidic tetraethoxysilane was prepared by adding 260 kg of ethanol to the remaining ethoxychlorosilanes, and HCl gas generated during the reaction was collected by a gas collector. In addition, unreacted ethanol was maintained at 125 torr and 56 to 58 ° C. to distill to obtain 610 kg of acidic tetraethoxysilane.
제 3 단계3rd step
상기 산성의 테트라에톡시실란에 소듐에톡사이드 8 kg을 첨가하여 중화시킨 후 생성된 염화나트륨 염을 여과하여 제거하였다. 여과된 테트라에톡시실란을 125 torr, 110 ~ 112 ℃로 증류하여 전자급 테트라에톡시실란 560 kg을 얻었다.After neutralizing by adding 8 kg of sodium ethoxide to the acidic tetraethoxysilane, the resulting sodium chloride salt was filtered off. The filtered tetraethoxysilane was distilled at 125 torr and 110 to 112 ° C. to obtain 560 kg of electronic grade tetraethoxysilane.
상기 수득된 테트라에톡시실란이 전자급을 만족하는지 확인하기 위하여 국제반도체재료장비협회 규격서(SEMI C45-0301)의 분석조건에 따라 다음과 같은 방법으로 분석하였으며, 그 결과 순도는 99.95 %, 금속성분 함량 < 1 ppm, 산/염기도 0.0005 %, 수분함량 80 ppm 등으로 나타났다.In order to confirm that the obtained tetraethoxysilane satisfies the electronic grade, the analysis was carried out according to the analysis conditions of the International Semiconductor Materials Equipment Association Standard (SEMI C45-0301) as follows. As a result, the purity was 99.95%, the metal component. Contents <1 ppm, acid / base 0.0005%, water content 80 ppm and the like.
<실험방법>Experimental Method
1)순도 : 가스크로마토그래피(HP 6890, Hewlett Packard社)를 이용하여 측정.1) Purity: Measured using gas chromatography (HP 6890, Hewlett Packard).
2) 금속성분 함량: 유도결합플라즈마 질량분석기(ELAN DRC II, Perkin Elmer社)를 이용하여 나트륨, 알루미늄, 철 등의 25 개 금속성분 함량을 측정.2) Metal content: The content of 25 metals such as sodium, aluminum and iron was measured using an inductively coupled plasma mass spectrometer (ELAN DRC II, Perkin Elmer).
3) 산/염기도: 적정기(DL50, Mettler-Toledo社)를 사용하여 측정.3) Acid / base: measured using titrator (DL50, Mettler-Toledo).
4) 수분함량: Karl Fischer 수분측정기(756 KF coulometer, Metrohm社)를 이용하여 측정. 4) Moisture content: measured using Karl Fischer moisture meter (756 KF coulometer, Metrohm).
비교예 1Comparative Example 1
제 1 단계First step
에탄올의 첨가량을 135 kg, 투입속도를 시간당 150 kg으로 바꾼 것을 제외하고는 상기 실시예와 동일한 조건에서 실시하였으며, 성분 및 함량 분석결과를 다음 표 1에 나타내었다. Except that the amount of ethanol was added to 135 kg, the loading rate was changed to 150 kg per hour was carried out under the same conditions as in the above example, the components and the content analysis results are shown in Table 1 below.
비교예 2Comparative Example 2
제 1 단계First step
에탄올의 첨가량을 405 kg, 투입속도를 시간당 90 kg으로 바꾼 것을 제외하고는 상기 실시예와 동일한 조건에서 실시하였으며, 성분 및 함량 분석결과를 다음 표 1에 나타내었다. Except that the amount of ethanol was added to 405 kg, the feed rate was changed to 90 kg per hour, and was carried out under the same conditions as in the above example, and the results of the component and content analysis are shown in Table 1 below.
제 2 단계2nd step
상기 트리메틸클로로실란과 에톡시클로로실란류의 혼합물을 58 ~ 60 ℃로 증류하여 트리메틸에톡시실란 2.5 %와 헥사메틸디실록산 0.5 %를 포함하는 순도 97.0%의 트리메틸클로로실란 470 kg을 분리하였다. The mixture of trimethylchlorosilane and ethoxychlorosilanes was distilled at 58 to 60 ° C. to separate 470 kg of trimethylchlorosilane having a purity of 97.0% including 2.5% of trimethylethoxysilane and 0.5% of hexamethyldisiloxane.
상기 표 1에 나타낸 바와 같이, 비교예 1의 경우 미반응된 과량의 사염화규소가 남아 있을 뿐 아니라 트리메틸클로로실란과 에탄올의 반응으로 부반응물인 트리메틸에톡시실란 및 헥사메틸디실록산이 소량 생성되어 트리메틸클로로실란과 에톡시클로로실란류의 증류에 의한 분리가 어려웠으며, 테트라에톡시실란의 제조 또한 불가능하였다. 비교예 2의 경우 사염화규소는 존재하지 않아 트리메틸클로로실란의 증류로 인한 분리가 가능하였으나, 역시 부반응물인 트리메틸에톡시실란 및 헥사메틸디실록산이 다량 생성되어 트리메틸클로로실란의 순도가 떨어져 재활용이 불가능하였고, 잔존하는 부반응물로 인하여 전자급 테트라에톡시실란의 제조 또한 불가능하였다.As shown in Table 1, in Comparative Example 1, not only unreacted excess silicon tetrachloride remained but also trimethylethoxysilane and hexamethyldisiloxane, which were reactants of trimethylchlorosilane and ethanol, produced trimethyl. Separation of chlorosilanes and ethoxychlorosilanes by distillation was difficult, and the preparation of tetraethoxysilane was also impossible. In the case of Comparative Example 2, since silicon tetrachloride was not present, trimethylchlorosilane could be separated by distillation. However, trimethylethoxysilane and hexamethyldisiloxane, which are also side reactants, were formed in a large amount, and thus the trimethylchlorosilane could not be recycled. In addition, the preparation of electronic tetraethoxysilane was also impossible due to the remaining side reactants.
반면, 실시예의 경우 사염화규소가 잔류하지 않았고 트리메틸클로로실란과 에톡시클로로실란류 외에는 부반응물이 생성되지 않아 고순도(99.0 %)의 트리메틸클로로실란을 분리하여 재활용이 가능하였고, 잔류하는 에톡시클로로실란류는 전자급 테트라에톡시실란으로 제조가 가능하였으며, 그 수율 또한 92 %로 우수함을 알 수 있었다. On the other hand, in the example, silicon tetrachloride did not remain, and no side reactions were produced except for trimethylchlorosilane and ethoxychlorosilanes. Thus, high-purity (99.0%) trimethylchlorosilane was separated and recycled, and the remaining ethoxychlorosilane It was found that the kind can be produced with an electronic grade tetraethoxysilane, the yield was also excellent as 92%.
상술한 바와 같이, 본 발명에 의하면 비점이 유사한 사염화규소와 트리메틸클로로실란을 포함하는 공비혼합물에 에탄올의 첨가량과 첨가속도를 조절함으로써, 사염화규소를 에톡시클로로실란류로 전환시킨 후 증류하는 간단한 공정으로 트리메틸클로로실란 화합물을 분리 제거하여 재활용이 가능하고, 상기 에톡시클로로실란류로부터 전자급 테트라에톡시실란을 90 % 이상의 우수한 수율로 제조할 수 있으므로 금속규소와 염화메탄의 촉매반응에서 얻어진 모노실란 화합물의 사용 효율을 극대화할 수 있는 효과가 있다.As described above, according to the present invention, a simple process of converting silicon tetrachloride to ethoxychlorosilanes and distilling by controlling the amount and rate of addition of ethanol to an azeotrope containing silicon tetrachloride and trimethylchlorosilane having similar boiling points It is possible to recycle by separating and removing the trimethylchlorosilane compound, and since the electronic grade tetraethoxysilane can be produced in an excellent yield of 90% or more from the ethoxychlorosilanes, the monosilane obtained from the catalytic reaction of metal silicon and methane chloride There is an effect to maximize the use efficiency of the compound.
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| KR1020040024486A KR20050099246A (en) | 2004-04-09 | 2004-04-09 | Method of producing electronic grade tetraethoxysilane from tetrachlorosilane-trimethylchlorosilane azeotrope |
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| KR1020040024486A KR20050099246A (en) | 2004-04-09 | 2004-04-09 | Method of producing electronic grade tetraethoxysilane from tetrachlorosilane-trimethylchlorosilane azeotrope |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903149A (en) * | 2017-11-03 | 2018-04-13 | 广东中科天元新能源科技有限公司 | A kind of coproduction absolute ethyl alcohol, the devices and methods therefor of electronic grade anhydrous ethanol |
| CN109021006A (en) * | 2018-09-08 | 2018-12-18 | 杨秀莲 | A kind of pollution-free method for preparing diphenyl diethoxy silane |
| CN109796484A (en) * | 2019-02-02 | 2019-05-24 | 苏州金宏气体股份有限公司 | A kind of method and system for abolishing ethyl orthosilicate azeotropic distillation |
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2004
- 2004-04-09 KR KR1020040024486A patent/KR20050099246A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107903149A (en) * | 2017-11-03 | 2018-04-13 | 广东中科天元新能源科技有限公司 | A kind of coproduction absolute ethyl alcohol, the devices and methods therefor of electronic grade anhydrous ethanol |
| CN109021006A (en) * | 2018-09-08 | 2018-12-18 | 杨秀莲 | A kind of pollution-free method for preparing diphenyl diethoxy silane |
| CN109796484A (en) * | 2019-02-02 | 2019-05-24 | 苏州金宏气体股份有限公司 | A kind of method and system for abolishing ethyl orthosilicate azeotropic distillation |
| CN109796484B (en) * | 2019-02-02 | 2020-04-07 | 苏州金宏气体股份有限公司 | Method and system for breaking azeotropic distillation of tetraethoxysilane |
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