KR100778032B1 - Method for preparing of fluorinated alkoxysilane derivative - Google Patents
Method for preparing of fluorinated alkoxysilane derivative Download PDFInfo
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- KR100778032B1 KR100778032B1 KR1020060048195A KR20060048195A KR100778032B1 KR 100778032 B1 KR100778032 B1 KR 100778032B1 KR 1020060048195 A KR1020060048195 A KR 1020060048195A KR 20060048195 A KR20060048195 A KR 20060048195A KR 100778032 B1 KR100778032 B1 KR 100778032B1
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- fluorine
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- alkoxysilane derivative
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- 238000000034 method Methods 0.000 title claims abstract description 27
- -1 chlorosilane compound Chemical class 0.000 claims abstract description 57
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000005046 Chlorosilane Substances 0.000 claims abstract description 17
- 239000006227 byproduct Substances 0.000 claims abstract description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 3
- 239000011737 fluorine Substances 0.000 claims description 54
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 6
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 description 9
- AHVYPIQETPWLSZ-UHFFFAOYSA-N N-methyl-pyrrolidine Natural products CN1CC=CC1 AHVYPIQETPWLSZ-UHFFFAOYSA-N 0.000 description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- KGFLFWRAHYKYEA-UHFFFAOYSA-N trimethyl(2,2,2-trifluoroethoxy)silane Chemical compound C[Si](C)(C)OCC(F)(F)F KGFLFWRAHYKYEA-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OUKZCQQNMWXMNE-UHFFFAOYSA-N 1-hexylpyrrolidine Chemical compound CCCCCCN1CCCC1 OUKZCQQNMWXMNE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- JPVQCHVLFHXNKB-UHFFFAOYSA-N 1,2,3,4,5,6-hexamethyldisiline Chemical compound CC1=C(C)[Si](C)=[Si](C)C(C)=C1C JPVQCHVLFHXNKB-UHFFFAOYSA-N 0.000 description 1
- SQEMPDQYHLWOFE-UHFFFAOYSA-N 2,2,2-trifluoroethoxysilane Chemical compound FC(F)(F)CO[SiH3] SQEMPDQYHLWOFE-UHFFFAOYSA-N 0.000 description 1
- WXJFKAZDSQLPBX-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)F WXJFKAZDSQLPBX-UHFFFAOYSA-N 0.000 description 1
- PJRIQFXPYMVWOU-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,5-nonafluoropentan-1-ol Chemical compound OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)F PJRIQFXPYMVWOU-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- WZQSBCHNVPAYOC-UHFFFAOYSA-N chloro(trihexyl)silane Chemical compound CCCCCC[Si](Cl)(CCCCCC)CCCCCC WZQSBCHNVPAYOC-UHFFFAOYSA-N 0.000 description 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
- ACTAPAGNZPZLEF-UHFFFAOYSA-N chloro(tripropyl)silane Chemical compound CCC[Si](Cl)(CCC)CCC ACTAPAGNZPZLEF-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 238000011086 high cleaning Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene 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
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
Description
본 발명은 함불소알콕시실란 유도체의 제조방법에 관한 것으로서, 더욱 상세하게는 클로로실란 화합물과 함불소 알코올을 반응시켜 함불소알콕시실란 유도체를 제조할 때 3차 아민화합물을 첨가함으로써 보다 온화한 조건과 높은 수율로 함불소알콕시실란 유도체를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a fluorine-containing alkoxysilane derivative, and more particularly, when the chlorosilane compound is reacted with a fluorine-containing alcohol to prepare a fluorine-containing alkoxysilane derivative, by adding a tertiary amine compound, more mild conditions and higher A method for producing a fluorine-containing alkoxysilane derivative in yield.
함불소알콕시실란 유도체는 2세대형 염화불화탄소(Chlorofluorocarbon; CFC)계 물질인 수소불화탄소(Hydrofluorocarbon; HFC)에 비해 대기 중 수명이 짧으며, 오존층을 파괴하지 않고 지구온난화 영향력도 낮은 제3세대형 대체물질로 지목되고 있는 함불소 화합물 중의 하나이다. 또한, 함불소알콕시실란 유도체는 기존의 염소계 세정제나 탄화수소 세정제와 잘 혼합되고, 오염물과 피세척물 사이로의 침투력이 좋을 뿐만 아니라 세척효과 및 열안정성이 우수하고, 금속, 플라스틱, 일래스토머 등으로 되는 복합 부품을 침범하지 않는 특징을 가지고 있다. 그리고 함불소알콕시실란 유도체는 기존의 CFC-113과 유사한 용해력을 가지므로 염소계 세정제의 사용량을 줄이면서 세정효과가 높은 차세대 CFC 대체 혼합세정제용 물질로 기대되고 있다. 함불소알콕시실란 유도체는 또한 세정제 외에도 용매, 윤활제, 발포제, 수지 개질제, 절연 매체 등 다양한 용도를 가지고 있다.The fluorine-containing alkoxysilane derivative has a shorter lifetime in the air than a hydrofluorocarbon (HFC), which is a second generation chlorofluorocarbon (CFC) material, and has a low global warming influence without destroying the ozone layer. It is one of the fluorine-containing compounds that are considered as a large substitute. In addition, the fluorine-containing alkoxysilane derivative is well mixed with a conventional chlorine-based or hydrocarbon detergent, has a good penetration force between contaminants and to-be-cleaned materials, and has an excellent washing effect and thermal stability, and is suitable for metals, plastics and elastomers. It is characterized by not invading composite parts. In addition, since the fluorine-containing alkoxysilane derivative has a similar dissolving power as that of the existing CFC-113, it is expected to reduce the amount of the chlorine-based cleaner and to be a next generation CFC alternative mixed detergent having a high cleaning effect. The fluorine-containing alkoxysilane derivatives also have various uses, such as solvents, lubricants, blowing agents, resin modifiers, and insulating media, in addition to cleaning agents.
현재까지 알려져 있는 함불소알콕시실란 유도체의 제조방법은 크게 두 가지로 분류될 수 있다.Known methods for producing a fluorine-containing alkoxysilane derivative can be classified into two categories.
첫 번째 방법은, 클로로트리알킬실란과 불소를 함유한 함불소 알코올을 반응시켜 제조하는 방법이다[Collect. Czech. Chem. Commun. 44, 750, (1979)]. 그러나, 상기한 방법에서 부산물로 염화수소(HCl)가 함께 생기므로 염화수소(HCl)에 의한 반응기 부식문제, 생성물로부터의 분리문제 등을 유발할 수 있다. The first method is prepared by reacting chlorotrialkylsilane with a fluorine-containing alcohol containing fluorine [Collect. Czech. Chem. Commun. 44, 750, (1979). However, in the above method, since hydrogen chloride (HCl) is generated as a by-product, corrosion of a reactor by hydrogen chloride (HCl), a problem of separation from a product, and the like may be caused.
두 번째 방법은 헥사메틸디실라진과 불소를 함유한 함불소 알코올을 반응시켜 함불소알콕시실란 유도체을 합성하는 방법이다[일본특허 특개평 7-247293, 특개평 6-108096]. 이 방법에서는 높은 온도에서 장시간 반응을 통하여 함불소알콕시트리알킬실란을 합성하고 있고, 그 수율도 약 80% 정도로 낮을 뿐만 아니라 특히 반응의 부산물로 생성되는 암모니아를 반응 후 제거해야 하는 단점을 가지고 있다. The second method is a method for synthesizing a fluorine-containing alkoxysilane derivative by reacting hexamethyldisilazine with a fluorine-containing alcohol containing fluorine (Japanese Patent Laid-Open No. 7-247293, Japanese Patent Laid-Open No. 6-108096). In this method, a fluorine-containing alkoxytrialkylsilane is synthesized through a long reaction at a high temperature, and its yield is low as about 80%. In particular, the ammonia produced as a byproduct of the reaction has to be removed after the reaction.
이상에서 살펴본 바와 같이 함불소알콕시실란 유도체 제조를 위한 종래 방법은 개선의 여지가 있다.As described above, the conventional method for preparing a fluorine-containing alkoxysilane derivative has room for improvement.
이에 본 발명자들은 산업적으로 이용가치가 큰 함불소알콕시실란 유도체를 보다 효율적으로 제조하는 방법을 개발하고자 연구 노력하였고, 그 결과 클로로실란 화합물과 함불소 알코올의 반응이 3차 아민화합물을 매개체로 수행될 때 반응의 수율이 크게 증가하고 부산물의 생성이 적으며 생성물의 분리가 매우 간단하다는 것을 알게되어 본 발명을 완성하게 되었다.Therefore, the present inventors have tried to develop a method for producing industrially useful fluorine-containing alkoxysilane derivatives more efficiently, and as a result, the reaction between the chlorosilane compound and the fluorine-containing alcohol may be carried out using a tertiary amine compound as a medium. The present invention was completed when the yield of the reaction was greatly increased, the formation of by-products was low, and the separation of the product was very simple.
이러한 본 발명에 따른 제조방법에 의하면 반응 중 발생되는 부식성 물질의 발생 요인을 원천적으로 제거할 수 있어 공정의 안정성을 획기적으로 개선할 수 있다.According to the manufacturing method according to the present invention can remove the source of the corrosive substances generated during the reaction at the source can significantly improve the stability of the process.
또한, 본 발명에 따른 제조방법에 의하면 상기 반응 매개체로 사용되는 3차 아민 화합물이 반응 중 발생되는 염화수소와 결합하여 4차 아민염을 형성하는데, 생성된 함불소알콕시실란 유도체와 상기 아민염 등을 포함하는 부산물이 그 비중 등의 차이가 크므로 층분리 같은 간단한 정제방법으로 회수할 수 있다는 장점을 지닌다.In addition, according to the production method according to the present invention, the tertiary amine compound used as the reaction medium is combined with hydrogen chloride generated during the reaction to form a quaternary amine salt, and the resulting fluorine-containing alkoxysilane derivative and the amine salt Since the by-products include a large difference in their specific gravity, they can be recovered by a simple purification method such as layer separation.
따라서, 본 발명은 단시간 내에 높은 수율로 함불소알콕시실란 유도체를 제조하는 방법을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a method for preparing a fluorine-containing alkoxysilane derivative in a high yield in a short time.
본 발명은 클로로실란 화합물과 함불소 알코올을 반응시켜 함불소알콕시실란 유도체를 제조하는 방법에 있어서, 상기 반응에 아민 화합물을 첨가하여 함불소알콕시실란 유도체의 수율을 증대시키는 방법을 그 특징으로 한다.The present invention is characterized by a method of producing a fluorine-containing alkoxysilane derivative by reacting a chlorosilane compound with a fluorine-containing alcohol, by adding an amine compound to the reaction to increase the yield of the fluorine-containing alkoxysilane derivative.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 다음 화학식 1로 표시되는 함불소알콕시실란 유도체 제조를 위한 클로로실란 화합물과 함불소 알코올을 원료로 사용하는 반응에, 아민 화합물을 매체로 하여 반응 효율을 극대화한데 기술적 특징이 있다.The present invention has a technical feature in maximizing reaction efficiency by using an amine compound as a medium in a reaction using a chlorosilane compound and a fluorine-containing alcohol for preparing a fluorine-containing alkoxysilane derivative represented by the following formula (1).
상기 화학식 1에서, R1, R2 및 R3은 각각 탄소수 1 내지 6의 탄화수소기, 또는 페닐기이고, Rf는 불소원자가 1 내지 8개 포함된 탄소수 1 내지 6의 함불소탄화수소기이다.In Formula 1, R 1 , R 2 and R 3 are each a hydrocarbon group or a phenyl group having 1 to 6 carbon atoms, and R f is a 1 to 6 carbon atoms-containing hydrocarbon group containing 1 to 8 fluorine atoms.
본 발명에 따른 상기 화학식 1로 표시되는 함불소알콕시실란 유도체의 제조방법에서는, 다음 반응식 1에 나타낸 바와 같이 클로로실란 화합물과 함불소 알코올을 아민 화합물의 존재 하에서 반응시켜 제조한다. In the method for producing a fluorinated alkoxysilane derivative represented by Chemical Formula 1 according to the present invention, the chlorosilane compound and the fluorine-containing alcohol are prepared by reacting in the presence of an amine compound as shown in the following Scheme 1.
상기 반응식 1에서, R1, R2, R3, 및 Rf는 각각 상기 화학식 1에서 정의한 바와 같다.In Scheme 1, R 1 , R 2 , R 3 , and R f are the same as defined in Chemical Formula 1, respectively.
상기 화학식 4로 표시되는 아민화합물은 구체적으로 다음 화학식 4a, 4b 및 4c로 나타낸 것을 사용할 수 있다.Specifically, the amine compound represented by Chemical Formula 4 may be one represented by the following Chemical Formulas 4a, 4b, and 4c.
상기 화학식 4a, 4b 및 4c에서, R4, R5 및 R6은 탄소수 1 내지 6의 알킬기, 또는 페닐기이다.In Formulas 4a, 4b, and 4c, R 4, R 5, and R 6 are an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
상기 반응식 1에 따른 본 발명의 제조방법을 좀 더 세분화하면, 다음 반응식 2에 나타낸 바와 같은 2단계 과정을 거쳐서 이루어진다.When the method of the present invention according to Scheme 1 is further subdivided, a two-step process as shown in Scheme 2 is performed.
상기 반응식 2에서, R1, R2, R3 및 Rf는 각각 상기 반응식 1에서 정의한 바와 같다.In Scheme 2, R 1 , R 2 , R 3 and R f are as defined in Scheme 1, respectively.
즉, 상기 화학식 2로 표시되는 클로로실란 화합물과 상기 화학식 4로 표시되는 아민 화합물이 반응하여, 상기 화학식 5로 표시되는 실릴아민염을 형성하게 되고, 이는 다시 상기 화학식 3으로 표시되는 함불소 알코올과 반응하여 본 발명에서 목적하는 상기 화학식 1로 표시되는 함불소알콕시실란 유도체를 제조하게 되며, 여기서 부생물로서 상기 화학식 6으로 표시되는 아민염이 형성된다.That is, the chlorosilane compound represented by the formula (2) and the amine compound represented by the formula (4) react to form a silylamine salt represented by the formula (5), which is again represented by the fluorine-containing alcohol represented by the formula (3) The reaction is to prepare a fluorine-containing alkoxysilane derivative represented by the formula (1) in the present invention, wherein the amine salt represented by the formula (6) is formed as a by-product.
상기한 바와 같이, 본 발명에서는 반응 매개체로서 상기 화학식 4로 표시되는 아민 화합물을 사용함으로써 반응 중간체로서 상기 화학식 5로 표시되는 실릴아민염을 생성하는 바, 중간체로 생성되는 실릴아민염은 독성이 없고 부식성을 띠지 않으므로 공정상의 위험부담을 줄일 수 있었다. 또한 상기 화학식 4로 표시되는 아민 화합물의 사용으로 기존의 함불소알콕시실란 유도체의 제조가 80 ℃의 고온에서 수행되던 것과는 달리 본원발명에서는 상온 부근의 낮은 온도 조건에서도 높은 수율로 목적 화합물을 제조하는 것이 가능하므로, 반응 조건을 크게 개선시킬 수 있었다.As described above, in the present invention, by using the amine compound represented by the formula (4) as a reaction medium to produce the silylamine salt represented by the formula (5) as a reaction intermediate, the silylamine salt formed as an intermediate is not toxic. Since it is not corrosive, the process risk can be reduced. In addition, unlike the conventional production of a fluorine-containing alkoxysilane derivative by the use of the amine compound represented by the formula (4) at a high temperature of 80 ℃ in the present invention it is to produce the target compound in high yield even at low temperature conditions near room temperature Since it was possible, the reaction conditions could be greatly improved.
또한, 상기 화학식 4로 표시되는 아민 화합물과 부산물로 생성된 상기 화학식 6으로 표시되는 아민염은 모두 생성물인 상기 화학식 1로 표시되는 함불소알콕시실란 유도체 보다 비중이 크다. 따라서, 반응액 중 목적 생성물인 상기 화학식 1로 표시되는 함불소알콕시실란 유도체는 위쪽의 액상으로 존재하고, 반응 매개체 및 부산물은 아래층에 액상으로 존재하므로, 층분리 방법에 의해 목적 생성물을 쉽게 회수하는 것이 가능하다. 또한 상기 화학식 1로 표시되는 함불소알콕시실란 유도체는 반응매개체와 부산물들 보다 비점이 낮으므로 단순 증류를 통해서도 쉽게 목적 생성물을 고순도로 얻어질 수 있다. In addition, both the amine compound represented by the formula (4) and the amine salt represented by the formula (6) formed by by-products are greater in specific gravity than the fluorine-containing alkoxysilane derivative represented by the formula (1) as a product. Therefore, the fluorinated alkoxysilane derivative represented by Formula 1, which is the target product in the reaction solution, exists in the upper liquid phase, and the reaction medium and the by-product exist in the liquid phase in the lower layer, thereby easily recovering the desired product by a layer separation method. It is possible. In addition, since the fluorine-containing alkoxysilane derivative represented by Formula 1 has a lower boiling point than the reaction medium and by-products, the desired product can be easily obtained in high purity even through simple distillation.
그리고, 본 발명에 따른 제조방법에서 부산물로 생성되는 상기 화학식 6으로 표시되는 아민염의 경우, 다음 반응식 3에 나타낸 바와 같은 방법으로 반응용액에 적당한 염기를 추가하여 상기 화학식 4로 표시되는 아민 화합물로 전환하여 회수할 수도 있다. 상기 염기로는, 알칼리금속염을 사용할 수 있고, 구체적으로 알칼리금속의 수용성 염 예를 들면, 수산화나트륨, 탄소수 1 내지 6의 소듐알콕사이드 등을 사용할 수 있다.And, in the case of the amine salt represented by the formula (6) produced as a by-product in the production method according to the present invention, by converting the amine compound represented by the formula (4) by adding a suitable base to the reaction solution by the method shown in the following scheme It can also collect | recover. As the base, an alkali metal salt can be used, and specifically, a water-soluble salt of an alkali metal, for example, sodium hydroxide, sodium alkoxide having 1 to 6 carbon atoms, or the like can be used.
상기 반응식 3에서, M은 알칼리금속이고, X는 하이드록시기(OH), 또는 탄소수 1 내지 6의 알콕시기이다.In Scheme 3, M is an alkali metal, X is a hydroxy group (OH), or an alkoxy group having 1 to 6 carbon atoms.
본 발명에 따른 상기 화학식 1로 표시되는 함불소알콕시실란 유도체 제조시 반응물의 사용량은 상기 화학식 3으로 표시되는 함불소 알코올 1 몰에 대하여 상기 화학식 2로 표시되는 클로로실란 화합물이 1 내지 1.5 몰, 그리고 상기 화학식 4로 표시되는 아민 화합물이 1 내지 2 몰이 되도록 사용한다. 바람직하게는 상기 화학식 3으로 표시되는 함불소 알코올 1 몰에 대하여 상기 화학식 2로 표시되는 클로로실란 화합물과 상기 화학식 4로 표시되는 아민 화합물이 각각 1.2 몰이 되도록 사용하는 것이 좋다. 이때, 상기 화학식 3으로 표시되는 함불소 알코올 1 몰에 대하여, 상기 화학식 2로 표시되는 클로로실란 화합물과 상기 화학식 4로 표시되는 아민 화합물의 사용량이 1 몰 미만이면 반응원료인 클로로실란 화합물이 미반응물로 존재하게 되어 생성물의 분리 및 정제에 어려움이 생긴다. In the preparation of the fluorinated alkoxysilane derivative represented by Formula 1 according to the present invention, the amount of reactants used is 1 to 1.5 moles of the chlorosilane compound represented by Formula 2 to 1 mole of the fluorinated alcohol represented by Formula 3, and The amine compound represented by the formula (4) is used to 1 to 2 moles. Preferably, the chlorosilane compound represented by Chemical Formula 2 and the amine compound represented by Chemical Formula 4 may each be 1.2 moles with respect to 1 mol of the fluorine-containing alcohol represented by Chemical Formula 3. In this case, when the amount of the chlorosilane compound represented by the formula (2) and the amine compound represented by the formula (4) is less than 1 mole relative to 1 mole of the fluorine-containing alcohol represented by the formula (3), the chlorosilane compound as a reaction raw material is unreacted. It becomes difficult to separate and purify the product.
또한, 본 발명에 따른 상기 화학식 1로 표시되는 함불소알콕시실란 유도체의 제조방법은 기존의 방법에서 보다 온도 조건이 더욱 완화되었는데, 그 온도조건은 -20 내지 50 ℃, 바람직하게는 -10 내지 25 ℃ 범위에서도 반응은 완벽하게 수행할 수 있다. 특히 반응원료로 사용된 함불소 알코올과 클로로실란 화합물의 전환율이 각각 100 %가 될 수 있는 온도범위 조건 중에서도, 보다 낮은 온도조건을 선택하는 것이 좋다. 그러나, 반응 온도가 -20 ℃ 미만으로 너무 낮게 유지되면 반응 진행 속도가 너무 느려서 경제성이 없고, 50 ℃를 초과하여 고온을 유지하게 되면 반응 생성물이 분해될 수 있어 바람직하지 못하다.In addition, the manufacturing method of the fluorine-containing alkoxysilane derivative represented by the formula (1) according to the present invention, the temperature conditions are more relaxed than in the conventional method, the temperature conditions are -20 to 50 ℃, preferably -10 to 25 The reaction can be carried out perfectly even in the range of ℃. In particular, it is preferable to select a lower temperature condition among temperature range conditions in which the conversion rate of the fluorine-containing alcohol and the chlorosilane compound used as the reaction raw material can be 100%. However, if the reaction temperature is kept too low below -20 ℃ is not economical because the reaction progress rate is too slow, and maintaining the high temperature above 50 ℃ is not preferable because the reaction product may decompose.
또한, 본 발명에 따른 제조방법에서는 별도의 용매가 사용되지 않는 무용매 조건에서 반응을 시킬 수도 있고, 혹은 필요에 따라 적절한 비극성용매를 반응용매로 사용할 수도 있다. 용매의 양은 아민 화합물에 대한 중량비로 최고 300 부피% 미만 사용하는 것이 적당하고, 보다 바람직하게는 100 ∼ 200 부피%가 적당하다. 반응용매를 사용하는 조건에서 반응을 수행할 경우, 아민 화합물과 클로로실란 화합물과의 반응시 반응물을 희석하는 효과로 인해 반응열을 제어할 수 있어 상온에서 보다 안정적인 반응이 가능하고, 반응 생성물인 함불소알콕시실란 유도체와 아민염의 층분리가 보다 용이해진다.In addition, in the production method according to the present invention, the reaction may be carried out under solvent-free conditions in which no separate solvent is used, or an appropriate non-polar solvent may be used as the reaction solvent, if necessary. The amount of the solvent is suitably used up to 300% by volume and more preferably 100 to 200% by volume with respect to the amine compound by weight. When the reaction is carried out under the conditions using a reaction solvent, the reaction heat can be controlled due to the dilution of the reactants during the reaction between the amine compound and the chlorosilane compound, so that a more stable reaction is possible at room temperature, and the reaction product is fluorine-containing. Layer separation of the alkoxysilane derivative and the amine salt becomes easier.
이상에서 설명한 바와 같은 본 발명은 다음의 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 다음의 실시예에 의하여 본 발명이 한정되는 것은 아니다. The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited by the following examples.
실시예 1Example 1
2,2,2-트리플루오로에탄올 10 g (0.1 mol)을 1-메틸피롤리딘 9.8 g (0.12 mol)에 녹인 후 0 ℃에서 클로로트리메틸실란 12.9 g (0.12 mol)을 천천히 적가한 후 실온에서 1 시간 반응시켰다. 반응 후 위층을 분리해 캐필러리 컬럼이 부착된 가스-액체 크로마토그래피로 분석한 결과 함불소알코올의 전환율은 99.6% 이었다. 위층을 증류하여 무색 투명한 액체인 2,2,2-트리플루오로에톡시트리알킬실란을 96.4%의 수율로 얻었다. 10 g (0.1 mol) of 2,2,2-trifluoroethanol was dissolved in 9.8 g (0.12 mol) of 1-methylpyrrolidine, and then slowly added dropwise 12.9 g (0.12 mol) of chlorotrimethylsilane at 0 ° C, followed by room temperature. Reaction was carried out for 1 hour. After the reaction, the upper layer was separated and analyzed by gas-liquid chromatography with a capillary column. The conversion of fluorine-containing alcohol was 99.6%. The upper layer was distilled off to obtain 2,2,2-trifluoroethoxytrialkylsilane as a colorless transparent liquid in 96.4% yield.
그리고, 반응원료로 사용된 함불소 알코올의 전환율 및 생성된 함불소알콕시트리알킬실란의 수율은 다음 수학식 1과 수학식 2와 같이 산출하였다.In addition, the conversion rate of the fluorine-containing alcohol used as the reaction raw material and the yield of the produced fluorine-containing alkoxytrialkylsilane were calculated as in Equations 1 and 2 below.
실시예 2 ∼ 6Examples 2-6
상기 실시예 1과 동일한 조건에서 수행하되, 다만 클로로트리알킬실란의 종 류만 변화시키면서 2,2,2-트리플루오로에톡시트리알킬실란을 합성하였으며, 그 결과는 다음 표 1에 나타내었다.The same procedure as in Example 1 was carried out except that only 2,2,2-trifluoroethoxytrialkylsilane was synthesized while changing the type of chlorotrialkylsilane, and the results are shown in Table 1 below.
실시예 7 ∼ 12Examples 7-12
상기 실시예 1과 동일한 조건에서 수행하되, 다만 함불소 알코올의 종류만 변화시키면서 함불소알콕시트리메틸실란을 합성하였으며, 그 결과는 다음 표 2에 나타내었다.Performed under the same conditions as in Example 1, except that the fluorine-containing alkoxytrimethylsilane was synthesized by changing only the type of fluorine-containing alcohol, the results are shown in Table 2 below.
실시예 13 ∼ 16Examples 13-16
상기 실시예 1과 동일한 조건에서 수행하되, 다만 아민 화합물의 종류만 변화시키면서 2,2,2-트리플루오로에톡시트리메틸실란을 합성하였으며, 그 결과는 다음 표 3에 나타내었다.Performed under the same conditions as in Example 1, except that 2,2,2-trifluoroethoxytrimethylsilane was synthesized while changing only the type of the amine compound, and the results are shown in Table 3 below.
실시예 17Example 17
상기 실시예 1에서 층분리로 얻어진 아래층 용액에 수산화나트륨 20.84 g (0.521 mole)을 상온에서 가한 후 1 시간 교반하였다. 생성된 NaCl을 여과한 후에 남아있는 용액을 감압 증류하여 97.6%의 1-메틸피롤리딘을 회수하였다.20.84 g (0.521 mole) of sodium hydroxide was added to the lower layer solution obtained by layer separation in Example 1 at room temperature, followed by stirring for 1 hour. The resulting solution was filtered, and the remaining solution was distilled under reduced pressure to recover 97.6% of 1-methylpyrrolidine.
실시예 18 ∼ 21Examples 18-21
상기 실시예 17과 동일한 방법으로, 상기 실시예 13 내지 16에서 사용된 1-메틸피롤리딘을 회수하였으며, 그 결과는 다음 표 4에 나타내었다.In the same manner as in Example 17, 1-methylpyrrolidine used in Examples 13 to 16 was recovered, and the results are shown in Table 4 below.
실시예 22Example 22
상기 실시예 17과 동일한 방법으로 1-메틸피롤리딘을 회수하되, 다만 수산화나트륨 대신 소듐 메톡사이드(NaOCH3)를 사용하였다. 그 결과 1-메틸피롤리딘의 회수율은 96.5%이었다.1-methylpyrrolidine was recovered in the same manner as in Example 17, except that sodium methoxide (NaOCH 3 ) was used instead of sodium hydroxide. As a result, the recovery of 1-methylpyrrolidine was 96.5%.
실시예 23 ∼ 26Examples 23-26
상기 실시예 1과 동일한 조건에서 수행하되, 다만 반응용매의 종류만 변화시키면서 2,2,2-트리플루오로에톡시트리메틸실란을 합성하였으며, 그 결과는 다음 표 5에 나타내었다.2,2,2-trifluoroethoxytrimethylsilane was synthesized under the same conditions as in Example 1 except changing only the kind of the reaction solvent, and the results are shown in Table 5 below.
실시예 28 ∼ 41Examples 28-41
상기 실시예 1과 동일한 조건에서 수행하되, 다만 2,2,2-트리플루오로에탄올에 대한 클로로트리메틸실란과 1-메틸피롤리딘의 몰비를 변화시키면서 2,2,2-트리플루오로에톡시트리메틸실란을 합성하였으며, 그 결과는 다음 표 6에 나타내었다.Performed under the same conditions as in Example 1, except changing the molar ratio of chlorotrimethylsilane to 1-methylpyrrolidine to 2,2,2-trifluoroethanol while changing to 2,2,2-trifluoroethoxy Trimethylsilane was synthesized and the results are shown in Table 6 below.
실시예 42 ∼ 47Examples 42-47
상기 실시예 1과 동일한 조건에서 수행하되, 다만 반응 온도를 변화시키면서 2,2,2-트리플루오로에톡시트리메틸실란을 합성하였으며, 그 결과는 다음 표 7에 나타내었다.Performed under the same conditions as in Example 1, except that 2,2,2-trifluoroethoxytrimethylsilane was synthesized while changing the reaction temperature, and the results are shown in Table 7 below.
상술한 바와 같이, 본 발명에 따르면 아민 화합물 존재 하에 클로로실란 화합물과 함불소 알코올을 반응시킴으로써, 기존 공정에서 부산물로 발생되는 부식성 물질의 발생 요인을 원천적으로 제거하여 공정의 안정성을 획기적으로 개선하였을 뿐만 아니라 반응 생성물의 분리 정제가 간편하여 공정을 매우 단순화시킬 수 있는 장점을 갖는다. As described above, according to the present invention, by reacting the chlorosilane compound and the fluorine-containing alcohol in the presence of the amine compound, the source of the caustic substances generated as a by-product in the existing process is eliminated at the source to significantly improve the stability of the process. In addition, the separation and purification of the reaction product is simple and has the advantage of greatly simplifying the process.
본 발명에 따른 제조방법에 의해 부산물로 생성되는 상기 화학식 6으로 표시되는 아민염은 실질적인 끓는점이 없으며 염의 상태이므로 부식성이 없을 뿐만 아니라 생성물인 함불소알콕시실란 유도체와 섞이지 않아 분리가 용이하다. 특히, 수산화나트륨 등의 적당한 염기를 처리하면 다시 처음의 이미다졸 화합물로 전환시켜 회수할 수 있어 재활용이 가능하므로 대량 반응은 물론 연속공정에도 적용할 수 있다는 장점을 갖는다. The amine salt represented by the formula (6) produced as a by-product by the production method according to the present invention has no substantial boiling point and is in a salt state, so it is not corrosive and is not easily mixed with a fluorine-containing alkoxysilane derivative, which is a product, to facilitate separation. In particular, by treating a suitable base such as sodium hydroxide can be converted back to the first imidazole compound to be recovered and can be recycled has the advantage that it can be applied to a continuous process as well as mass reaction.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522284A (en) | 1965-12-07 | 1970-07-28 | Dynamit Nobel Ag | Production for halogenated phenoxysilanes |
| WO1996012723A1 (en) | 1994-10-20 | 1996-05-02 | Fmc Corporation | Process for preparing alkylsilyl or arylsilyl ethers |
| JPH09157277A (en) * | 1995-12-06 | 1997-06-17 | Shin Etsu Chem Co Ltd | Production of alkoxysilane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3522284A (en) | 1965-12-07 | 1970-07-28 | Dynamit Nobel Ag | Production for halogenated phenoxysilanes |
| WO1996012723A1 (en) | 1994-10-20 | 1996-05-02 | Fmc Corporation | Process for preparing alkylsilyl or arylsilyl ethers |
| JPH09157277A (en) * | 1995-12-06 | 1997-06-17 | Shin Etsu Chem Co Ltd | Production of alkoxysilane |
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