KR102675267B1 - Method for preparing hexafluoropropylene oxide - Google Patents
Method for preparing hexafluoropropylene oxide Download PDFInfo
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- hexafluoropropylene
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- PGFXOWRDDHCDTE-UHFFFAOYSA-N hexafluoropropylene oxide Chemical compound FC(F)(F)C1(F)OC1(F)F PGFXOWRDDHCDTE-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000000034 method Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007800 oxidant agent Substances 0.000 claims abstract description 39
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 150000002170 ethers Chemical class 0.000 claims abstract description 16
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical group [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 90
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 21
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 15
- FHDQNOXQSTVAIC-UHFFFAOYSA-M 1-butyl-3-methylimidazol-3-ium;chloride Chemical compound [Cl-].CCCCN1C=C[N+](C)=C1 FHDQNOXQSTVAIC-UHFFFAOYSA-M 0.000 claims description 13
- CZIUVCSYOGFUPH-UHFFFAOYSA-M 1-hexyl-3-methylimidazol-3-ium;iodide Chemical compound [I-].CCCCCC[N+]=1C=CN(C)C=1 CZIUVCSYOGFUPH-UHFFFAOYSA-M 0.000 claims description 13
- 229910019093 NaOCl Inorganic materials 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- -1 perfluoroethylhexyl ether Chemical compound 0.000 claims description 12
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 8
- KSOCRXJMFBYSFA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,6,6,6-tridecafluoro-5-(1,1,1,2,3,3,4,4,5,5,6,6,6-tridecafluorohexan-2-yloxy)hexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(C(F)(F)F)OC(F)(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F KSOCRXJMFBYSFA-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 4
- OUXCFBWPMYMVRZ-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7-pentadecafluoro-7-(1,1,2,2,3,3,4,4,5,5,6,6,7,7,7-pentadecafluoroheptoxy)heptane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)OC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OUXCFBWPMYMVRZ-UHFFFAOYSA-N 0.000 claims description 3
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 claims description 3
- 150000004693 imidazolium salts Chemical group 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 27
- 230000001590 oxidative effect Effects 0.000 abstract description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010792 warming Methods 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 238000013467 fragmentation Methods 0.000 description 4
- 238000006062 fragmentation reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 2
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- 231100000357 carcinogen Toxicity 0.000 description 2
- 239000003183 carcinogenic agent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- NAMDIHYPBYVYAP-UHFFFAOYSA-N 1-methoxy-2-(2-methoxyethoxy)ethane Chemical compound COCCOCCOC.COCCOCCOC NAMDIHYPBYVYAP-UHFFFAOYSA-N 0.000 description 1
- JBOIAZWJIACNJF-UHFFFAOYSA-N 1h-imidazole;hydroiodide Chemical compound [I-].[NH2+]1C=CN=C1 JBOIAZWJIACNJF-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VBZWSGALLODQNC-UHFFFAOYSA-N hexafluoroacetone Chemical compound FC(F)(F)C(=O)C(F)(F)F VBZWSGALLODQNC-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- BCVXHSPFUWZLGQ-UHFFFAOYSA-N mecn acetonitrile Chemical compound CC#N.CC#N BCVXHSPFUWZLGQ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Epoxy Compounds (AREA)
Abstract
본 발명은 (a) 하기 화학식 1로 표시되는 불화에테르인 유기용매, 및 산화제의 수용액을 반응기에 투입하는 단계; (b) 상기 반응기에 상전이 촉매를 첨가하는 단계; 및 (c) 상기 반응기에 헥사플루오로프로필렌(Hexafluoropropylene)을 투입하고 반응시켜 헥사플루오로프로필렌 옥사이드(hexafluoropropylene oxide)을 제조하는 단계;를 포함하는 헥사플루오로프로필렌 옥사이드의 제조방법이 제공된다. 이에 의하여, 유기용매와 물이 혼재하는 이상계(two phase) 반응을 통해 상전이 촉매 하에서 헥사플루오로프로필렌(HFP)을 산화시켜 헥사플루오로프로필렌 옥사이드(HFPO)를 제조함에 있어 오존층 파괴와 지구 온난화 문제를 일으키는 CFC, HCFC 용매를 사용하지 않으면서도 고수율로 헥사플루오로프로필렌 옥사이드를 제조할 수 있다.
[화학식 1]
(CnF2n+1)O(CmH2m+1)
화학식 1에서,
n은 3 내지 6의 정수이고,
m은 1 내지 6의 정수이다.The present invention includes the steps of (a) introducing an organic solvent, which is a fluorinated ether represented by the following formula (1), and an aqueous solution of an oxidizing agent into a reactor; (b) adding a phase transfer catalyst to the reactor; and (c) adding hexafluoropropylene to the reactor and reacting to produce hexafluoropropylene oxide. A method for producing hexafluoropropylene oxide is provided. As a result, problems of ozone layer destruction and global warming are avoided in producing hexafluoropropylene oxide (HFPO) by oxidizing hexafluoropropylene (HFP) under a phase transfer catalyst through a two-phase reaction in which organic solvents and water are mixed. Hexafluoropropylene oxide can be produced in high yield without using CFC or HCFC solvents.
[Formula 1]
(C n F 2n+1 )O(C m H 2m+1 )
In Formula 1,
n is an integer from 3 to 6,
m is an integer from 1 to 6.
Description
본 발명은 헥사플루오로프로필렌 옥사이드의 제조방법에 관한 것으로, 더욱 상세하게는 헥사플루오로프로필렌의 산화에 의해 헥사플루오로프로필렌옥사이드(Hexafluoropropylene oxide, HFPO)를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing hexafluoropropylene oxide, and more specifically, to a method for producing hexafluoropropylene oxide (HFPO) by oxidation of hexafluoropropylene.
헥사플루오로프로필렌 옥사이드(hexafluoropropylene oxide, HFPO)는 퍼플루오로바이닐에테르, 헥사플루오로아세톤, 특히 플랙서블한 전자 제품에 사용되는 투명 폴리이미드 고분자의 원료물질이다. 헥사플루오로프로필렌 옥사이드(HFPO)는 헥사플루오로프로필렌(HFP)을 산화시켜 합성되는데 이에 대한 산화제로 과산화수소, 소듐하이포클로라이트(NaOCl), 산소 등을 사용한다. 이때 가장 폭넓게 사용되는 과산화수소나 NaOCl은 주로 물에 녹아있고, 원료인 HFP의 물에 대한 용해도는 매우 낮아 반응의 수율이 낮은 문제점이 있다.Hexafluoropropylene oxide (HFPO) is a raw material for perfluorovinyl ether, hexafluoroacetone, and transparent polyimide polymers, especially used in flexible electronic products. Hexafluoropropylene oxide (HFPO) is synthesized by oxidizing hexafluoropropylene (HFP), and hydrogen peroxide, sodium hypochlorite (NaOCl), and oxygen are used as oxidizing agents. At this time, hydrogen peroxide or NaOCl, which are the most widely used, are mainly dissolved in water, and the solubility of HFP, a raw material, in water is very low, resulting in a low reaction yield.
소듐하이포클로라이트 수용액에 아세토니트릴(Acetonitrile) 또는 디에틸렌글리콜디메틸에터(Diethyleneglycol dimethyl ether, diglyme) 등의 수용성 극성 용매를 첨가하여 HFP를 용해시키고 균일계 반응을 통해 HFPO를 합성하는 방법이 제안된 바 있다. 이때 HFPO의 선택율은 10%로 낮았는데 그 이유는 균일계 용매 내에서 물과의 반응을 통해 HFPO가 분해되기 때문이다.A method of dissolving HFP by adding a water-soluble polar solvent such as acetonitrile or diethylene glycol dimethyl ether (diglyme) to an aqueous solution of sodium hypochlorite and synthesizing HFPO through a homogeneous reaction was proposed. There is a bar. At this time, the selectivity of HFPO was low at 10% because HFPO decomposes through reaction with water in a homogeneous solvent.
HCFC-141b(CFCl2CH3)를 용매로 사용하여 HFP를 녹이고 NaOCl 수용액과 반응시키는 방법이 알려져있다. HFP와 NaOCl의 접촉을 증가시키기 위해 HFP가 녹아있는 유기용액과 NaOCl이 녹아있는 수용액을 1/16 인치 관에 고압으로 통과시키는 방법 혹은 상전이 촉매를 사용하는 방법이 있다. 특히 상전이 촉매를 사용하여 저온에서 반응시킨 경우 HFPO의 수율이 92%에 달했다. 그러나 특허에 사용된 HCFC-141b와 같은 HCFC계 유기용매의 경우 오존층 파괴로 인하여 국내에서는 2040년 이후 제조 및 사용이 완전히 금지되어 있는 물질이고, 또한 특수한 반응기 구조로 인하여 설비 비용이 증가하는 문제점을 가지고 있다.There is a known method of dissolving HFP using HCFC-141b (CFCl 2 CH3) as a solvent and reacting it with an aqueous NaOCl solution. To increase the contact between HFP and NaOCl, there is a method of passing an organic solution in which HFP is dissolved and an aqueous solution in which NaOCl is dissolved through a 1/16 inch tube at high pressure or using a phase transfer catalyst. In particular, when the reaction was carried out at low temperature using a phase transfer catalyst, the yield of HFPO reached 92%. However, in the case of HCFC-based organic solvents such as HCFC-141b used in the patent, the manufacture and use of them is completely prohibited in Korea after 2040 due to ozone layer destruction, and also has the problem of increased equipment costs due to the special reactor structure. there is.
세틸트라이메틸암모늄브로마이드(Cetyltrimethylammonium bromide, CTAB)와 불화세슘, 질산은으로부터 고체 촉매를 합성하고 HFP와 산소를 기상에서 반응시켜 HFPO를 합성하는 방법도 고안된 바 있고, 이때 사용된 촉매의 상태에 따라 약 93%의 전환율을 보였다. 그러나 고체 촉매의 특성상 촉매 제조 과정에서 은 함량과 메조 기공 구조의 균일성을 유지하는 것이 어렵다는 문제점이 있다.A method of synthesizing HFPO by synthesizing a solid catalyst from cetyltrimethylammonium bromide (CTAB), cesium fluoride, and silver nitrate and reacting HFP with oxygen in the gas phase has also been devised. Depending on the state of the catalyst used, a method of synthesizing HFPO has also been designed. It showed a conversion rate of 93%. However, due to the nature of the solid catalyst, there is a problem in that it is difficult to maintain uniformity of silver content and mesopore structure during the catalyst manufacturing process.
본 발명의 목적은 유기용매와 물이 혼재하는 이상계(two phase) 반응을 통해 상전이 촉매 하에서 헥사플루오로프로필렌(HFP)을 산화시켜 헥사플루오로프로필렌 옥사이드(HFPO)를 제조함에 있어 오존층 파괴와 지구 온난화 문제를 일으키는 CFC, HCFC 용매를 사용하지 않으면서도 고수율로 헥사플루오로프로필렌 옥사이드를 제조할 수 있는 헥사플루오로프로필렌 옥사이드의 제조방법을 제공하는 데 있다.The purpose of the present invention is to produce hexafluoropropylene oxide (HFPO) by oxidizing hexafluoropropylene (HFP) under a phase transfer catalyst through a two-phase reaction in which an organic solvent and water are mixed, thereby reducing ozone layer destruction and global warming. The aim is to provide a method for producing hexafluoropropylene oxide that can produce hexafluoropropylene oxide in high yield without using problematic CFC or HCFC solvents.
본 발명의 하나의 측면에 따르면,According to one aspect of the invention,
(a) 하기 화학식 1로 표시되는 불화에테르인 유기용매, 및 산화제의 수용액을 반응기에 투입하는 단계; (b) 상기 반응기에 상전이 촉매를 첨가하는 단계; 및 (c) 상기 반응기에 헥사플루오로프로필렌(Hexafluoropropylene)을 투입하고 반응시켜 헥사플루오로프로필렌 옥사이드(hexafluoropropylene oxide)을 제조하는 단계;를 포함하는 헥사플루오로프로필렌 옥사이드의 제조방법이 제공된다.(a) introducing an organic solvent, which is a fluorinated ether represented by the following formula (1), and an aqueous solution of an oxidizing agent into the reactor; (b) adding a phase transfer catalyst to the reactor; and (c) adding hexafluoropropylene to the reactor and reacting to produce hexafluoropropylene oxide. A method for producing hexafluoropropylene oxide is provided.
[화학식 1][Formula 1]
(CnF2n+1)O(CmH2m+1)(C n F 2n+1 )O(C m H 2m+1 )
화학식 1에서,In Formula 1,
n은 3 내지 6의 정수이고,n is an integer from 3 to 6,
m은 1 내지 6의 정수이다.m is an integer from 1 to 6.
상기 화학식 1로 표시되는 불화에테르는 퍼플루오로부틸에틸에테르(C4F9OC2H5), 퍼플루오로에틸헥실에테르(C2F5OC6H13), 퍼플루오로펜틸프로필에테르(C5F11OC3H7), 및 퍼플루오로헥실메틸에테르(C6F13OCH3) 중에서 선택된 어느 하나일 수 있다.The fluorinated ether represented by Formula 1 is perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), perfluoroethylhexyl ether (C 2 F 5 OC 6 H 13 ), and perfluoropentylpropyl ether ( C 5 F 11 OC 3 H 7 ), and perfluorohexylmethyl ether (C 6 F 13 OCH 3 ).
상기 산화제는 소듐 하이포클로라이트(Sodium hypochlorite, NaOCl), 과산화수소, 산소, 과산화황산염, 및 과산화망간산염 중에서 선택된 어느 하나일 수 있다.The oxidizing agent may be any one selected from sodium hypochlorite (NaOCl), hydrogen peroxide, oxygen, peroxysulfate, and manganese peroxide.
단계 (a)에서, 상기 산화제의 수용액은 5 내지 20% 농도일 수 있다.In step (a), the aqueous solution of the oxidizing agent may have a concentration of 5 to 20%.
단계 (a)에서, 상기 화학식 1로 표시되는 불화에테르인 유기용매 100중량부에 대하여, 상기 산화제의 수용액에 포함된 산화제 5 내지 20중량부가 되도록 투입할 수 있다.In step (a), 5 to 20 parts by weight of the oxidizing agent contained in the aqueous solution of the oxidizing agent may be added to 100 parts by weight of the organic solvent, which is a fluorinated ether represented by Formula 1.
단계 (b)에서, 상기 상전이 촉매는 하기 화학식 2로 표시되는 4차 암모늄할라이드계 화합물, 또는 하기 화학식 3으로 표시되는 4차 이미다졸륨계 화합물일 수 있다.In step (b), the phase transfer catalyst may be a quaternary ammonium halide-based compound represented by Formula 2 below, or a quaternary imidazolium-based compound represented by Formula 3 below.
[화학식 2][Formula 2]
R4N+X- R 4 N + X -
상기 화학식 2에서,In Formula 2,
R은 C2 내지 C8 알킬기이고,R is a C2 to C8 alkyl group,
X는 Cl, Br, 또는 I이다.X is Cl, Br, or I.
[화학식 3][Formula 3]
R1 및 R2는 각각 독립적으로 C2 내지 C8 알킬기이고,R 1 and R 2 are each independently a C2 to C8 alkyl group,
X는 Cl, Br, 또는 I이다.X is Cl, Br, or I.
단계 (b)에서, 상기 상전이 촉매는 테트라부틸암모늄클로라이드(Tetrabutyl ammonium chloride, TBAC), 트리옥틸메틸암모늄 클로라이드(trioctylmethylammonium chloride, TOMAC), 테트라메틸암모늄 브로마이드(tetramethylammonium bromide, (CH3)4NBr), 1-부틸-3-메틸이미다졸륨 클로라이드(1-Butyl-3-methylimidazolium chloride, BMImCl), 및 1-헥실-3-메틸이미다졸륨 아이오다이드(1-hexyl-3-methylimidazolium iodide, HMImI) 중에서 선택된 어느 하나일 수 있다.In step (b), the phase transfer catalyst is tetrabutyl ammonium chloride (TBAC), trioctylmethylammonium chloride (TOMAC), tetramethylammonium bromide (CH 3 ) 4 NBr), 1-Butyl-3-methylimidazolium chloride (BMmCl), and 1-hexyl-3-methylimidazolium iodide (HMImI) It may be any one selected from among.
단계 (b)에서, 상기 상전이 촉매는 상기 화학식 1로 표시되는 불화에테르인 유기용매 및 산화제의 수용액 총몰수에 대하여 0.5 내지 4 mol%로 첨가될 수 있다.In step (b), the phase transfer catalyst may be added in an amount of 0.5 to 4 mol% based on the total number of moles of the aqueous solution of the organic solvent and oxidizing agent, which is a fluorinated ether represented by Formula 1.
단계 (c)에서, 상기 반응기는 헥사플루오로프로필렌(Hexafluoropropylene, HFP) 투입 전에 반응기 내 공기를 배출시켜 진공이 형성되도록 할 수 있다.In step (c), a vacuum may be formed in the reactor by exhausting the air in the reactor before adding hexafluoropropylene (HFP).
단계 (c)에서, 상기 헥사플루오로프로필렌(Hexafluoropropylene, HFP)은 기체 상태일 수 있다.In step (c), the hexafluoropropylene (HFP) may be in a gaseous state.
단계 (c)에서, 상기 반응은 10 내지 60℃에서 수행되는 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.In step (c), the reaction is carried out at 10 to 60°C.
단계 (c)에서, 상기 반응은 10 내지 150분 동안 수행될 수 있다.In step (c), the reaction may be carried out for 10 to 150 minutes.
본 발명의 다른 하나의 측면에 따르면,According to another aspect of the present invention,
상기 헥사플루오로프로필렌 옥사이드의 제조방법을 포함하는 6FDA (4,4’-(Hexafluoroisopropylidene)diphthalic anhydride)의 제조방법이 제공된다.A method for producing 6FDA (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride) including the method for producing hexafluoropropylene oxide is provided.
본 발명의 헥사플루오로프로필렌 옥사이드의 제조방법은 유기용매와 물이 혼재하는 이상계(two phase) 반응을 통해 상전이 촉매 하에서 헥사플루오로프로필렌(HFP)을 산화시켜 헥사플루오로프로필렌 옥사이드(HFPO)를 제조함에 있어 오존층 파괴와 지구 온난화 문제를 일으키는 CFC, HCFC 용매를 사용하지 않으면서도 고수율로 헥사플루오로프로필렌 옥사이드를 제조할 수 있다.The method for producing hexafluoropropylene oxide of the present invention is to produce hexafluoropropylene oxide (HFPO) by oxidizing hexafluoropropylene (HFP) under a phase transfer catalyst through a two-phase reaction in which an organic solvent and water are mixed. In doing so, hexafluoropropylene oxide can be produced in high yield without using CFC or HCFC solvents, which cause ozone layer destruction and global warming problems.
도 1은 실시예 1의 반응 후 GC-MS 분석 결과이다.
도 2는 실시예 1의 반응 후 HFP의 질량 단편화 패턴(Mass fragmentation pattern)이다.
도 3은 실시예 1의 반응 후 HFPO의 질량 단편화 패턴(Mass fragmentation pattern)이다.
도 4는 실험예 1의 실시예 1에 따른 반응 후 용액(a)과 비교예 1에 따른 반응 후 용액(b)의 사진을 비교한 것이다.Figure 1 shows the results of GC-MS analysis after the reaction of Example 1.
Figure 2 shows the mass fragmentation pattern of HFP after the reaction of Example 1.
Figure 3 is a mass fragmentation pattern of HFPO after the reaction of Example 1.
Figure 4 compares photographs of the solution (a) after the reaction according to Example 1 of Experimental Example 1 and the solution (b) after the reaction according to Comparative Example 1.
본 발명은 다양한 변환을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 상세한 설명에 상세하게 설명하고자 한다. 그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변환, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. 본 발명을 설명함에 있어서 관련된 공지 기술에 대한 구체적인 설명이 본 발명의 요지를 흐릴 수 있다고 판단되는 경우 그 상세한 설명을 생략한다.Since the present invention can be modified in various ways and can have various embodiments, specific embodiments will be illustrated in the drawings and described in detail in the detailed description. However, this is not intended to limit the present invention to specific embodiments, and should be understood to include all transformations, equivalents, and substitutes included in the spirit and technical scope of the present invention. In describing the present invention, if it is determined that a detailed description of related known technologies may obscure the gist of the present invention, the detailed description will be omitted.
이하, 본 발명의 헥사플루오로프로필렌 옥사이드의 제조방법에 대해 설명하도록 한다.Hereinafter, the method for producing hexafluoropropylene oxide of the present invention will be described.
먼저, 하기 화학식 1로 표시되는 불화에테르인 유기용매, 및 산화제의 수용액을 반응기에 투입한다(단계 a).First, an organic solvent, which is a fluorinated ether represented by the following formula (1), and an aqueous solution of an oxidizing agent are introduced into the reactor (step a).
[화학식 1][Formula 1]
(CnF2n+1)O(CmH2m+1)(C n F 2n+1 )O(C m H 2m+1 )
화학식 1에서,In Formula 1,
n은 3 내지 6의 정수이고,n is an integer from 3 to 6,
m은 1 내지 6의 정수이다.m is an integer from 1 to 6.
종래 사용되는 유기용매인 염화불화탄소 계열 용매는 오존층 파괴와 지구온난화 등의 환경 문제로 인하여 산업적으로 규제되어 활용할 수 없다. 참고로, 본 발명에서 사용되는 불화에테르 화합물 중 하나인 퍼플루오로부틸에틸에테르(C4F9OC2H5), 염화불화탄소계 화합물인 CFC-113(C2Cl3F3), 사염화탄소(CCl4)의 특성에 대해 비교하여 표 1에 나타내었다.Conventionally used organic solvents, chlorofluorocarbon-based solvents, are regulated industrially and cannot be used due to environmental problems such as ozone layer destruction and global warming. For reference, perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), one of the fluorinated ether compounds used in the present invention, CFC-113 (C 2 Cl 3 F 3 ), a chlorofluorocarbon-based compound, and carbon tetrachloride. The characteristics of (CCl 4 ) are compared and shown in Table 1.
상기 화학식 1로 표시되는 불화에테르는 퍼플루오로부틸에틸에테르(C4F9OC2H5), 퍼플루오로에틸헥실에테르(C2F5OC6H13), 퍼플루오로펜틸프로필에테르(C5F11OC3H7), 및 퍼플루오로헥실메틸에테르(C6F13OCH3) 중에서 선택된 어느 하나인 것이 바람직하고, 더욱 바람직하게는 퍼플루오로부틸에틸에테르(C4F9OC2H5) 또는 퍼플루오로에틸헥실에테르(C2F5OC6H13)일 수 있고, 더욱 더 바람직하게는 퍼플루오로부틸에틸에테르(C4F9OC2H5)일 수 있다. 상기 불화에테르 화합물을 사용하는 경우 헥사플루오로프로필렌 옥사이드(HFPO) 수율을 향상시키면서도 오존층 파괴, 지구 온난화, 발암물질로서 알려진 사염화탄소(CCl4)를 형성시키지 않으므로 환경적인 면에서도 바람직하다.The fluorinated ether represented by Formula 1 is perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), perfluoroethylhexyl ether (C 2 F 5 OC 6 H 13 ), and perfluoropentylpropyl ether ( C 5 F 11 OC 3 H 7 ), and perfluorohexylmethyl ether (C 6 F 13 OCH 3 ), and more preferably perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ) or perfluoroethylhexyl ether (C 2 F 5 OC 6 H 13 ), and even more preferably perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ). The use of the fluorinated ether compound improves the yield of hexafluoropropylene oxide (HFPO) and is also environmentally preferable because it does not form carbon tetrachloride (CCl 4 ), which is known to cause ozone layer destruction, global warming, and carcinogens.
상기 산화제는 소듐 하이포클로라이트(Sodium hypochlorite, NaOCl), 과산화수소, 산소, 과산화황산염, 및 과산화망간산염 중에서 선택된 어느 하나인 것이 바람직하고, 더욱 바람직하게는 소듐 하이포클로라이트(NaOCl) 또는 과산화수소일 수 있고, 더욱 더 바람직하게는 소듐 하이포클로라이트(NaOCl)일 수 있다.The oxidizing agent is preferably any one selected from sodium hypochlorite (NaOCl), hydrogen peroxide, oxygen, peroxysulfate, and manganese peroxide, more preferably sodium hypochlorite (NaOCl) or hydrogen peroxide. , and even more preferably sodium hypochlorite (NaOCl).
상기 산화제의 수용액은 5 내지 20% 농도인 것이 바람직하고, 더욱 바람직하게는 10 내지 15% 일 수 있다.The aqueous solution of the oxidizing agent preferably has a concentration of 5 to 20%, and more preferably has a concentration of 10 to 15%.
상기 화학식 1로 표시되는 불화에테르인 유기용매 100중량부에 대하여, 상기 산화제의 수용액에 포함된 산화제 5 내지 20중량부가 되도록 투입하는 것이 바람직하고, 더욱 바람직하게는 7 내지 15중량부가 되도록 투입하는 것이 바람직하다.It is preferable to add 5 to 20 parts by weight of the oxidizing agent contained in the aqueous solution of the oxidizing agent, and more preferably 7 to 15 parts by weight, based on 100 parts by weight of the organic solvent, which is a fluorinated ether represented by Formula 1. desirable.
이후, 상기 반응기에 상전이 촉매를 첨가한다(단계 b).Then, a phase transfer catalyst is added to the reactor (step b).
상기 상전이 촉매는 하기 화학식 2로 표시되는 4차 암모늄할라이드계 화합물, 또는 하기 화학식 3으로 표시되는 4차 이미다졸륨계 화합물일 수 있다. 상전이 촉매는 수용액상의 산화제와 유기용매상의 헥사플루오로프로필렌(Hexafluoropropylene)의 접촉이 원활하게 이루어지게 하기 위해 투입되는 것이다.The phase transfer catalyst may be a quaternary ammonium halide-based compound represented by Formula 2 below, or a quaternary imidazolium-based compound represented by Formula 3 below. The phase transfer catalyst is added to ensure smooth contact between the oxidizing agent in the aqueous solution and the hexafluoropropylene in the organic solvent.
[화학식 2][Formula 2]
R4N+X- R 4 N + X -
상기 화학식 2에서,In Formula 2,
R은 C2 내지 C8 알킬기이고,R is a C2 to C8 alkyl group,
X는 Cl, Br, 또는 I이다.X is Cl, Br, or I.
[화학식 3][Formula 3]
R1 및 R2는 각각 독립적으로 C2 내지 C8 알킬기이고,R 1 and R 2 are each independently a C2 to C8 alkyl group,
X는 Cl, Br, 또는 I이다.X is Cl, Br, or I.
바람직하게는, 상기 상전이 촉매는 테트라부틸암모늄클로라이드(Tetrabutyl ammonium chloride, TBAC), 트리옥틸메틸암모늄 클로라이드(trioctylmethylammonium chloride, TOMAC), 테트라메틸암모늄 브로마이드(tetramethylammonium bromide, (CH3)4NBr), 1-부틸-3-메틸이미다졸륨 클로라이드(1-Butyl-3-methylimidazolium chloride, BMImCl), 및 1-헥실-3-메틸이미다졸륨 아이오다이드(1-hexyl-3-methylimidazolium iodide, HMImI) 중에서 선택된 어느 하나일 수 있고, 더욱 바람직하게는 테트라부틸암모늄클로라이드(TBAC), 1-부틸-3-메틸이미다졸륨 클로라이드(1-Butyl-3-methylimidazolium chloride, BMImCl), 및 1-헥실-3-메틸이미다졸륨 아이오다이드(1-hexyl-3-methylimidazolium iodide, HMImI) 중에서 선택된 어느 하나일 수 있다. 상기 상전이 촉매를 사용하는 경우 헥사플루오로프로필렌 옥사이드(HFPO) 수율을 향상시킬 수 있다.Preferably, the phase transfer catalyst is tetrabutyl ammonium chloride (TBAC), trioctylmethylammonium chloride (TOMAC), tetramethylammonium bromide (CH 3 ) 4 NBr), 1- Selected from 1-Butyl-3-methylimidazolium chloride (BMmCl), and 1-hexyl-3-methylimidazolium iodide (HMImI) It may be any one, and more preferably tetrabutylammonium chloride (TBAC), 1-Butyl-3-methylimidazolium chloride (BMmCl), and 1-hexyl-3-methyl. It may be any one selected from imidazolium iodide (1-hexyl-3-methylimidazolium iodide, HMImI). When using the phase transfer catalyst, hexafluoropropylene oxide (HFPO) yield can be improved.
상기 상전이 촉매는 상기 화학식 1로 표시되는 불화에테르인 유기용매 및 산화제의 수용액 총몰수에 대하여 0.5 내지 4 mol%로 첨가되는 것이 바람직하고, 더욱 바람직하게는 1 내지 3 mol% 첨가될 수 있다. 0.5 mol% 미만으로 첨가되는 경우 헥사플루오로프로필렌 옥사이드(HFPO)의 수율이 지나치게 낮아질 수 있고, 4 mol% 초과되는 경우에는 촉매 상전이 촉매 사용량의 증가 대비 수율의 향상 효과가 나타나지 않거나 오히려 수율이 낮아질 수 있다. 또한, 상전이 촉매의 종류에 따라 상기 범위 내에서 적절한 사용량을 설정할 수 있다.The phase transfer catalyst is preferably added in an amount of 0.5 to 4 mol%, more preferably 1 to 3 mol%, based on the total moles of the aqueous solution of the organic solvent, which is a fluorinated ether represented by Formula 1, and the oxidizing agent. If added in less than 0.5 mol%, the yield of hexafluoropropylene oxide (HFPO) may be excessively low, and if added in excess of 4 mol%, the yield may not be improved compared to the increase in the amount of catalyst phase transfer catalyst used, or the yield may actually be lowered. there is. Additionally, an appropriate usage amount can be set within the above range depending on the type of phase transfer catalyst.
다음으로, 상기 반응기에 헥사플루오로프로필렌(Hexafluoropropylene)을 투입하고 반응시켜 헥사플루오로프로필렌 옥사이드(hexafluoropropylene oxide)을 제조한다(단계 c).Next, hexafluoropropylene is added to the reactor and reacted to produce hexafluoropropylene oxide (step c).
상기 반응기는 헥사플루오로프로필렌(Hexafluoropropylene, HFP) 투입 전에 반응기 내 공기를 배출시켜 진공이 형성되도록 하는 것이 바람직하다.It is desirable to form a vacuum in the reactor by discharging the air in the reactor before adding hexafluoropropylene (HFP).
상기 헥사플루오로프로필렌(Hexafluoropropylene, HFP)은 기체 상태로 투입될 수 있다.The hexafluoropropylene (HFP) may be introduced in a gaseous state.
본 단계에서, 상기 반응은 10 내지 60℃에서 수행될 수 있고, 더욱 바람직하게는 20 내지 50℃, 더욱 더 바람직하게는 25 내지 40℃에서 수행될 수 있고, 가장 바람직하게는 25℃ 내지 30℃에서 수행될 수 있다. 상기 온도 범위에서 반응시키는 경우 헥사플루오로프로필렌 옥사이드(HFPO)의 수율을 향상시킬 수 있다.In this step, the reaction may be carried out at 10 to 60°C, more preferably at 20 to 50°C, even more preferably at 25 to 40°C, and most preferably at 25°C to 30°C. It can be performed in When the reaction is performed in the above temperature range, the yield of hexafluoropropylene oxide (HFPO) can be improved.
또한, 상기 반응은 10 내지 150분 동안 수행될 수 있고, 바람직하게는 20 내지 120분 동안, 더욱 바람직하게는 30 내지 60분 동안 수행할 수 있고, 상기 시간 범위에서 헥사플루오로프로필렌 옥사이드(HFPO)의 수율을 향상시킬 수 있다.Additionally, the reaction may be performed for 10 to 150 minutes, preferably for 20 to 120 minutes, and more preferably for 30 to 60 minutes, and in this time range, hexafluoropropylene oxide (HFPO) The yield can be improved.
본 발명은 상술한 헥사플루오로프로필렌 옥사이드의 제조방법을 포함하는 6FDA (4,4’-(Hexafluoroisopropylidene)diphthalic anhydride)의 제조방법이 제공된다.The present invention provides a method for producing 6FDA (4,4'-(Hexafluoroisopropylidene)diphthalic anhydride), including the method for producing hexafluoropropylene oxide described above.
특히, 본 발명에 따른 헥사플루오로프로필렌 옥사이드의 제조방법에 있어서, 단계 (a)에서 화학식 1로 표시되는 불화에테르 화합물 종류, 산화제 종류, 산화제의 수용액 농도, 유기용매에 대한 산화제 중량비, 단계 (b)에서, 상전이 촉매 종류, 상전이 촉매 사용량, 단계 (c)에서, 반응 온도 및 시간을 달리하며, 이산화탄소 분리 실험을 수행한 결과 다른 조건과 달리 아래의 조건을 모두 만족하는 경우에 헥사플루오로프로필렌 옥사이드 수율이 가장 높다.In particular, in the method for producing hexafluoropropylene oxide according to the present invention, in step (a), the type of fluorinated ether compound represented by Formula 1, the type of oxidizing agent, the aqueous solution concentration of the oxidizing agent, the weight ratio of the oxidizing agent to the organic solvent, and step (b) ), the type of phase transfer catalyst, the amount of phase transfer catalyst used, and the reaction temperature and time in step (c) were varied, and as a result of performing a carbon dioxide separation experiment, unlike other conditions, if all of the conditions below are satisfied, hexafluoropropylene oxide It has the highest yield.
단계 (a)에서 화학식 1로 표시되는 불화에테르는 퍼플루오로부틸에틸에테르(C4F9OC2H5), 산화제는 소듐 하이포클로라이트(Sodium hypochlorite, NaOCl), 산화제의 수용액 농도는 10 내지 15%, 화학식 1로 표시되는 불화에테르인 유기용매 100중량부에 대하여, 상기 산화제의 수용액에 포함된 산화제 7 내지 15중량부, 단계 (b)에서, 상전이 촉매는 테트라부틸암모늄클로라이드(TBAC)는 유기용매 및 산화제의 수용액 총몰수에 대하여 2 내지 3 mol%, 1-부틸-3-메틸이미다졸륨 클로라이드(1-Butyl-3-methylimidazolium chloride, BMImCl), 및 1-헥실-3-메틸이미다졸륨 아이오다이드(1-hexyl-3-methylimidazolium iodide, HMImI) 중에서 선택된 어느 하나는 유기용매 및 산화제의 수용액 총몰수에 대하여 0.5 내지 1.5 mol%, 단계 (c)에서, 반응 온도 25 내지 30℃에서 30 내지 60분인 경우이다.In step (a), the fluorinated ether represented by Formula 1 is perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), the oxidizing agent is sodium hypochlorite (NaOCl), and the aqueous solution concentration of the oxidizing agent is 10 to 10. 15%, 7 to 15 parts by weight of an oxidizing agent contained in the aqueous solution of the oxidizing agent, based on 100 parts by weight of an organic solvent that is a fluorinated ether represented by Formula 1. In step (b), the phase transfer catalyst is tetrabutylammonium chloride (TBAC). 2 to 3 mol%, 1-Butyl-3-methylimidazolium chloride (BMImCl), and 1-hexyl-3-methylimida, based on the total moles of aqueous solution of organic solvent and oxidizing agent. Any one selected from zolium iodide (1-hexyl-3-methylimidazolium iodide, HMImI) is used in an amount of 0.5 to 1.5 mol% based on the total moles of the aqueous solution of the organic solvent and oxidizing agent, in step (c), at a reaction temperature of 25 to 30 ° C. This is the case for 30 to 60 minutes.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나, 이들 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이에 의하여 제한되지 않고, 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업계의 통상의 지식을 가진 자에게 자명할 것이다.Below, preferred embodiments are presented to aid understanding of the present invention. However, these examples are for illustrating the present invention in more detail, and the scope of the present invention is not limited thereto, and various changes and modifications are possible within the scope and technical idea of the present invention as is known in the art. It will be self-evident to those with knowledge.
[실시예][Example]
실시예 1: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 1: Preparation of hexafluoropropylene oxide (HFPO)
용적 100 ㎖의 유리 재질 내압 반응기에 용매 C4F9OC2H5 20 g과 산화제 12% NaOCl 수용액 20 ㎖를 투입하고 상전이 촉매로 테트라부틸암모늄클로라이드(Tetrabutyl ammonium chloride, TBAC)를 1 mol% 첨가하였다. 이후 반응기에 진공을 걸어 공기를 배출시킨 후 기체 상태의 헥사플루오로프로필렌(Hexafluoropropylene, HFP) 3 g을 투입하고 교반하여 상온 25℃에서 30 분 동안 반응시키고 기체를 포집하였다(수율 36.9%).Add 20 g of solvent C 4 F 9 OC 2 H 5 and 20 ml of oxidizing agent 12% NaOCl aqueous solution to a glass pressure-resistant reactor with a volume of 100 ml, and add 1 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst. did. Afterwards, a vacuum was applied to the reactor to expel air, and then 3 g of gaseous hexafluoropropylene (HFP) was added and stirred to react at room temperature 25°C for 30 minutes and gas was collected (yield 36.9%).
실시예 1의 반응 후 GC-MS 분석 결과를 도 1에 나타내었고, HFP의 질량 단편화 패턴(Mass fragmentation pattern)을 도 2에 나타내었고, HFPO의 질량 단편화 패턴(Mass fragmentation pattern)을 도 3에 나타내었다.The results of GC-MS analysis after the reaction of Example 1 are shown in Figure 1, the mass fragmentation pattern of HFP is shown in Figure 2, and the mass fragmentation pattern of HFPO is shown in Figure 3. It was.
실시예 2: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 2: Preparation of hexafluoropropylene oxide (HFPO)
용매로 C4F9OC2H5 대신에 C2F5OC6H13을 사용한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 35.7%).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that C 2 F 5 OC 6 H 13 was used as a solvent instead of C 4 F 9 OC 2 H 5 (yield 35.7%).
실시예 3: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 3: Preparation of hexafluoropropylene oxide (HFPO)
용매로 C4F9OC2H5 대신에 C5F11OC3H7를 사용한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 33.9%).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that C 5 F 11 OC 3 H 7 was used as a solvent instead of C 4 F 9 OC 2 H 5 (yield 33.9%).
실시예 4: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 4: Preparation of hexafluoropropylene oxide (HFPO)
용매로 C4F9OC2H5 대신에 C6F13OCH3를 사용한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 34.5%).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that C 6 F 13 OCH 3 was used as a solvent instead of C 4 F 9 OC 2 H 5 (yield 34.5%).
실시예 5: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 5: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 2 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 32.6 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that 2 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst was added to the mixed solution of solvent and oxidant instead of 1 mol%. (yield 32.6%).
실시예 6: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 6: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 3 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 37.2 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that 3 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst was added to the mixed solution of solvent and oxidant instead of 1 mol%. (yield 37.2%).
실시예 7: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 7: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 트리옥틸메틸암모늄 클로라이드(trioctylmethylammonium chloride, TOMAC) 1 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 22.9 %).The same conditions as Example 1 except that instead of adding 1 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst to the mixed solution of solvent and oxidant, 1 mol% of trioctylmethylammonium chloride (TOMAC) was added. Hexafluoropropylene oxide (HFPO) was prepared (yield 22.9%).
실시예 8: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 8: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 트리옥틸메틸암모늄 클로라이드(trioctylmethylammonium chloride, TOMAC) 2 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 25.8 %).The same conditions as in Example 1, except that instead of adding 1 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst to the mixed solution of solvent and oxidant, 2 mol% of trioctylmethylammonium chloride (TOMAC) was added. Hexafluoropropylene oxide (HFPO) was prepared (yield 25.8%).
실시예 9: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 9: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 트리옥틸메틸암모늄 클로라이드(trioctylmethylammonium chloride, TOMAC) 3 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 18.1 %).The same conditions as in Example 1, except that instead of adding 1 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst to the mixed solution of solvent and oxidant, 3 mol% of trioctylmethylammonium chloride (TOMAC) was added. Hexafluoropropylene oxide (HFPO) was prepared (yield 18.1%).
실시예 10: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 10: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 테트라메틸암모늄 브로마이드(tetramethylammonium bromide, (CH3)4NBr) 1 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 26.4 %).Example, except that instead of adding 1 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst to the mixed solution of solvent and oxidant, 1 mol% of tetramethylammonium bromide ((CH 3 ) 4 NBr) was added. Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in 1 (yield 26.4%).
실시예 11: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 11: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 1-부틸-3-메틸이미다졸륨 클로라이드(1-Butyl-3-methylimidazolium chloride, BMImCl) 1 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 31.2 %).Instead of adding 1 mol% of tetrabutylammonium chloride (TBAC) as a phase transfer catalyst to the mixed solution of solvent and oxidant, 1 mol% of 1-Butyl-3-methylimidazolium chloride (BMimCl) was added. Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1 except for addition (yield 31.2%).
실시예 12: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 12: Preparation of hexafluoropropylene oxide (HFPO)
상전이 촉매로 테트라부틸암모늄클로라이드(TBAC)를 용매와 산화제 혼합용액에 1 mol% 첨가하는 대신에 1-헥실-3-메틸이미다졸륨 아이오다이드(1-hexyl-3-methylimidazolium iodide, HMImI) 1 mol% 첨가한 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 33.5 %).Instead of adding 1 mol% of tetrabutylammonium chloride (TBAC) to the mixed solution of solvent and oxidant as a phase transfer catalyst, 1-hexyl-3-methylimidazolium iodide (HMImI) 1 Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1 except that mol% was added (yield 33.5%).
실시예 13: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 13: Preparation of hexafluoropropylene oxide (HFPO)
30분 동안 반응시키는 대신 10분 동안 반응시키는 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 8.5 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed for 10 minutes instead of 30 minutes (yield 8.5%).
실시예 14: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 14: Preparation of hexafluoropropylene oxide (HFPO)
30분 동안 반응시키는 대신 20분 동안 반응시키는 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 13.2 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed for 20 minutes instead of 30 minutes (yield 13.2%).
실시예 15: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 15: Preparation of hexafluoropropylene oxide (HFPO)
30분 동안 반응시키는 대신 40분 동안 반응시키는 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 30.5 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed for 40 minutes instead of 30 minutes (yield 30.5%).
실시예 16: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 16: Preparation of hexafluoropropylene oxide (HFPO)
30분 동안 반응시키는 대신 50분 동안 반응시키는 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 31.4 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed for 50 minutes instead of 30 minutes (yield 31.4%).
실시예 17: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 17: Preparation of hexafluoropropylene oxide (HFPO)
30분 동안 반응시키는 대신 60분 동안 반응시키는 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 30.8 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed for 60 minutes instead of 30 minutes (yield 30.8%).
실시예 18: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 18: Preparation of hexafluoropropylene oxide (HFPO)
30분 동안 반응시키는 대신 120분 동안 반응시키는 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 26.9 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed for 120 minutes instead of 30 minutes (yield 26.9%).
실시예 19: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 19: Preparation of hexafluoropropylene oxide (HFPO)
25℃ 대신에 0℃ 온도에서 반응시킨 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 2.7 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed at 0°C instead of 25°C (yield 2.7%).
실시예 20: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 20: Preparation of hexafluoropropylene oxide (HFPO)
25℃ 대신에 40℃ 온도에서 반응시킨 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 24.3 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed at 40°C instead of 25°C (yield 24.3%).
실시예 21: 헥사플루오로프로필렌 옥사이드(HFPO) 제조Example 21: Preparation of hexafluoropropylene oxide (HFPO)
25℃ 대신에 60℃ 온도에서 반응시킨 것을 제외하고는 실시예 1과 동일한 조건으로 헥사플루오로프로필렌 옥사이드(HFPO)를 제조하였다(수율 17.6 %).Hexafluoropropylene oxide (HFPO) was prepared under the same conditions as in Example 1, except that the reaction was performed at 60°C instead of 25°C (yield 17.6%).
비교예 1Comparative Example 1
용매로 C4F9OC2H5를 사용하는 것 대신에 아세토나이트릴(acetonitrile)을 사용하는 것을 제외하고는 실시예 1과 동일한 조건으로 반응을 수행하였다.The reaction was performed under the same conditions as Example 1, except that acetonitrile was used instead of C 4 F 9 OC 2 H 5 as the solvent.
비교예 2Comparative Example 2
용매로 C4F9OC2H5를 사용하는 것 대신에 사이클로헥산(cyclohexane)을 사용하는 것을 제외하고는 실시예 1과 동일한 조건으로 반응을 수행하였다.The reaction was performed under the same conditions as Example 1, except that cyclohexane was used instead of C 4 F 9 OC 2 H 5 as the solvent.
비교예 3Comparative Example 3
용매로 C4F9OC2H5를 사용하는 것 대신에 클로로포름(chloroform)을 사용하는 것을 제외하고는 실시예 1과 동일한 조건으로 반응을 수행하였다(수율 48.3%).The reaction was performed under the same conditions as Example 1, except that chloroform was used instead of C 4 F 9 OC 2 H 5 as the solvent (yield 48.3%).
비교예 4Comparative Example 4
용매로 C4F9OC2H5를 사용하는 것 대신에 메틸클로라이드(methylene chloride)을 사용하는 것을 제외하고는 실시예 1과 동일한 조건으로 반응을 수행하였다(수율 45.7%).The reaction was performed under the same conditions as Example 1, except that methylene chloride was used instead of C 4 F 9 OC 2 H 5 as a solvent (yield 45.7%).
[실험예][Experimental example]
실험예 1: 용매에 따른 헥사플루오로프로필렌 옥사이드(HFPO) 수율 비교Experimental Example 1: Comparison of hexafluoropropylene oxide (HFPO) yield according to solvent
용매에 따른 헥사플루오로프로필렌 옥사이드(HFPO) 수율을 비교하기 위하여 실시예 1 내지 4, 및 비교예 1 내지 4에 따라 제조된 헥사플루오로프로필렌 옥사이드(HFPO)의 수율을 비교하여 아래의 표 2에 정리하였다.In order to compare the yields of hexafluoropropylene oxide (HFPO) according to solvent, the yields of hexafluoropropylene oxide (HFPO) prepared according to Examples 1 to 4 and Comparative Examples 1 to 4 are compared and are shown in Table 2 below. Organized.
이에 따르면, 알킬플루오로알킬에터를 용매로 사용한 실시예 1 내지 4는 30% 이상의 헥사플루오로프로필렌 옥사이드(HFPO) 수율을 나타내었다.또한, 아세토나이트릴(Acetonitrile)을 사용한 비교예 1의 경우 수용성 유기용매로 HFP가 용해된 후 NaOCl 수용액과 동일상에 존재하므로 반응성은 좋지만 합성된 HFPO가 추가적인 반응을 통해 고분자 물질이 생성되는 문제점을 나타내었다. 또한, 사이클로헥산(Cyclohexane)을 사용한 비교예 2는 반응성은 낮으면서 고분자 물질이 생성되는 문제점을 나타내었다. According to this, Examples 1 to 4 using alkylfluoroalkyl ether as a solvent showed hexafluoropropylene oxide (HFPO) yield of 30% or more. In addition, in the case of Comparative Example 1 using acetonitrile (Acetonitrile) After HFP is dissolved in a water-soluble organic solvent, it exists in the same phase as the NaOCl aqueous solution, so the reactivity is good, but the synthesized HFPO presents a problem in that a polymer material is produced through an additional reaction. In addition, Comparative Example 2 using cyclohexane showed a problem in that a polymer material was produced with low reactivity.
한편, 클로로포름(chloroform)을 사용한 비교예 3과 메틸클로라이드(methylene chloride)의 경우 높은 헥사플루오로프로필렌 옥사이드(HFPO) 수율을 나타냈으나, 용매의 염소화 반응이 발생하여 CCl4가 형성되는 문제가 발생되었다. 사염화탄소(CCl4)는 오존층을 파괴하고, 지구온난화 지수가 높으며, 발암물질로 분류되기 때문에 생산이 금지된 물질이다. 따라서 반응 과정에서 용매의 염소화에 의해 CCl4가 형성되는 클로로포름이나 메틸클로라이드는 사용하는 것은 환경적인 면에서 부적합하다.On the other hand, Comparative Example 3 using chloroform and methylene chloride showed a high hexafluoropropylene oxide (HFPO) yield, but a chlorination reaction of the solvent occurred, resulting in the formation of CCl 4. It has been done. Carbon tetrachloride (CCl 4 ) is a substance whose production is prohibited because it destroys the ozone layer, has a high global warming potential, and is classified as a carcinogen. Therefore, it is environmentally unsuitable to use chloroform or methyl chloride, which forms CCl 4 by chlorination of the solvent during the reaction process.
또한, 실시예 1에 따른 반응 후 용액(a)과 비교예 1에 따른 반응 후 용액(b)의 사진을 비교하여 도 4에 나타내었다. 실시예 1의 용액은 투명하지만, 비교예 1의 용액은 불투명한 것으로 나타나 고분자가 형성되었음을 육안으로 확인할 수 있다.In addition, photos of the solution (a) after the reaction according to Example 1 and the solution (b) after the reaction according to Comparative Example 1 are compared and shown in FIG. 4. The solution of Example 1 was transparent, but the solution of Comparative Example 1 was opaque, allowing visual confirmation that a polymer was formed.
실험예 2: 상전이 촉매에 따른 헥사플루오로프로필렌 옥사이드(HFPO) 수율 비교Experimental Example 2: Comparison of hexafluoropropylene oxide (HFPO) yield according to phase transfer catalyst
상전이 촉매 종류와 촉매량에 따른 헥사플루오로프로필렌 옥사이드(HFPO) 수율을 비교하기 위하여 실시예 5 내지 12에 따라 제조된 헥사플루오로프로필렌 옥사이드(HFPO)의 수율을 비교하여 아래의 표 3에 정리하였다.In order to compare the yields of hexafluoropropylene oxide (HFPO) according to the type and amount of phase transfer catalyst, the yields of hexafluoropropylene oxide (HFPO) prepared according to Examples 5 to 12 were compared and summarized in Table 3 below.
실험예 3: 반응시간에 따른 헥사플루오로프로필렌 옥사이드(HFPO) 수율 비교Experimental Example 3: Comparison of hexafluoropropylene oxide (HFPO) yield according to reaction time
상전이 촉매 테트라부틸암모늄클로라이드(TBAC)를 동일한 양으로 사용하면서 반응시간을 달리하는 실시예 1, 및 실시예 13 내지 18에 따라 제조된 헥사플루오로프로필렌 옥사이드(HFPO)의 수율을 비교하여 아래의 표 4에 정리하였다.The yields of hexafluoropropylene oxide (HFPO) prepared according to Example 1 and Examples 13 to 18 using the same amount of the phase transfer catalyst tetrabutylammonium chloride (TBAC) and varying reaction times are compared in the table below. It is summarized in 4.
실험예 4: 반응온도에 따른 헥사플루오로프로필렌 옥사이드(HFPO) 수율 비교Experimental Example 4: Comparison of hexafluoropropylene oxide (HFPO) yield according to reaction temperature
상전이 촉매 테트라부틸암모늄클로라이드(TBAC)를 동일한 양으로 사용하면서 반응온도를 달리하는 실시예 1, 및 실시예 13 내지 18에 따라 제조된 헥사플루오로프로필렌 옥사이드(HFPO)의 수율을 비교하여 아래의 표 5에 정리하였다.The yields of hexafluoropropylene oxide (HFPO) prepared according to Example 1 and Examples 13 to 18 at different reaction temperatures while using the same amount of the phase transfer catalyst tetrabutylammonium chloride (TBAC) are compared in the table below. It is summarized in 5.
이상, 본 발명의 실시예들에 대하여 설명하였으나, 해당 기술 분야에서 통상의 지식을 가진 자라면 특허청구범위에 기재된 본 발명의 사상으로부터 벗어나지 않는 범위 내에서, 구성 요소의 부가, 변경, 삭제 또는 추가 등에 의해 본 발명을 다양하게 수정 및 변경시킬 수 있을 것이며, 이 또한 본 발명의 권리범위 내에 포함된다고 할 것이다.Although the embodiments of the present invention have been described above, those skilled in the art can add, change, delete or add components without departing from the spirit of the present invention as set forth in the patent claims. The present invention may be modified and changed in various ways, and this will also be included within the scope of rights of the present invention.
Claims (13)
(b) 상기 반응기에 상전이 촉매를 첨가하는 단계; 및
(c) 상기 반응기에 헥사플루오로프로필렌(Hexafluoropropylene)을 투입하고 반응시켜 헥사플루오로프로필렌 옥사이드(hexafluoropropylene oxide)을 제조하는 단계;를 포함하는 헥사플루오로프로필렌 옥사이드의 제조방법;
[화학식 1]
(CnF2n+1)O(CmH2m+1)
화학식 1에서,
n은 3 내지 6의 정수이고,
m은 1 내지 6의 정수이다.(a) introducing an organic solvent, which is a fluorinated ether represented by the following formula (1), and an aqueous solution of an oxidizing agent into the reactor;
(b) adding a phase transfer catalyst to the reactor; and
(c) adding hexafluoropropylene to the reactor and reacting to produce hexafluoropropylene oxide; a method for producing hexafluoropropylene oxide, including the step of producing hexafluoropropylene oxide;
[Formula 1]
(C n F 2n+1 )O(C m H 2m+1 )
In Formula 1,
n is an integer from 3 to 6,
m is an integer from 1 to 6.
상기 화학식 1로 표시되는 불화에테르는 퍼플루오로부틸에틸에테르(C4F9OC2H5), 퍼플루오로에틸헥실에테르(C2F5OC6H13), 퍼플루오로펜틸프로필에테르(C5F11OC3H7), 및 퍼플루오로헥실메틸에테르(C6F13OCH3) 중에서 선택된 어느 하나인 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
The fluorinated ether represented by Formula 1 is perfluorobutyl ethyl ether (C 4 F 9 OC 2 H 5 ), perfluoroethylhexyl ether (C 2 F 5 OC 6 H 13 ), and perfluoropentylpropyl ether ( A method for producing hexafluoropropylene oxide, characterized in that any one selected from C 5 F 11 OC 3 H 7 ) and perfluorohexylmethyl ether (C 6 F 13 OCH 3 ).
상기 산화제는 소듐 하이포클로라이트(Sodium hypochlorite, NaOCl), 과산화수소, 산소, 과산화황산염, 및 과산화망간산염 중에서 선택된 어느 하나인 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
A method for producing hexafluoropropylene oxide, wherein the oxidizing agent is any one selected from sodium hypochlorite (NaOCl), hydrogen peroxide, oxygen, peroxysulfate, and manganese peroxide.
단계 (a)에서, 상기 산화제의 수용액은 5 내지 20% 농도인 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
In step (a), the aqueous solution of the oxidizing agent is a method for producing hexafluoropropylene oxide, characterized in that the concentration is 5 to 20%.
단계 (a)에서, 상기 화학식 1로 표시되는 불화에테르인 유기용매 100중량부에 대하여, 상기 산화제의 수용액에 포함된 산화제 5 내지 20중량부가 되도록 투입하는 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
In step (a), the production of hexafluoropropylene oxide, characterized in that 5 to 20 parts by weight of the oxidizing agent contained in the aqueous solution of the oxidizing agent is added to 100 parts by weight of the organic solvent, which is a fluorinated ether represented by Formula 1. method.
단계 (b)에서, 상기 상전이 촉매는 하기 화학식 2로 표시되는 4차 암모늄할라이드계 화합물, 또는 하기 화학식 3으로 표시되는 4차 이미다졸륨계 화합물인 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법;
[화학식 2]
R4N+X-
상기 화학식 2에서,
R은 C2 내지 C8 알킬기이고,
X는 Cl, Br, 또는 I이다.
[화학식 3]
R1 및 R2는 각각 독립적으로 C2 내지 C8 알킬기이고,
X는 Cl, Br, 또는 I이다.According to paragraph 1,
In step (b), the phase transfer catalyst is a quaternary ammonium halide-based compound represented by Formula 2 below, or a quaternary imidazolium-based compound represented by Formula 3 below;
[Formula 2]
R 4 N + X -
In Formula 2,
R is a C2 to C8 alkyl group,
X is Cl, Br, or I.
[Formula 3]
R 1 and R 2 are each independently a C2 to C8 alkyl group,
X is Cl, Br, or I.
단계 (b)에서, 상기 상전이 촉매는 테트라부틸암모늄클로라이드(Tetrabutyl ammonium chloride, TBAC), 트리옥틸메틸암모늄 클로라이드(trioctylmethylammonium chloride, TOMAC), 테트라메틸암모늄 브로마이드(tetramethylammonium bromide, (CH3)4NBr), 1-부틸-3-메틸이미다졸륨 클로라이드(1-Butyl-3-methylimidazolium chloride, BMImCl), 및 1-헥실-3-메틸이미다졸륨 아이오다이드(1-hexyl-3-methylimidazolium iodide, HMImI) 중에서 선택된 어느 하나인 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to clause 6,
In step (b), the phase transfer catalyst is tetrabutyl ammonium chloride (TBAC), trioctylmethylammonium chloride (TOMAC), tetramethylammonium bromide (CH 3 ) 4 NBr), 1-Butyl-3-methylimidazolium chloride (BMmCl), and 1-hexyl-3-methylimidazolium iodide (HMImI) A method for producing hexafluoropropylene oxide, characterized in that any one selected from among.
단계 (b)에서, 상기 상전이 촉매는 상기 화학식 1로 표시되는 불화에테르인 유기용매 및 산화제의 수용액 총몰수에 대하여 0.5 내지 4 mol%로 첨가되는 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
In step (b), the phase transfer catalyst is added in an amount of 0.5 to 4 mol% based on the total number of moles of the aqueous solution of the organic solvent and oxidizing agent, which is a fluorinated ether represented by Formula 1. A method for producing hexafluoropropylene oxide.
단계 (c)에서, 상기 반응기는 헥사플루오로프로필렌(Hexafluoropropylene, HFP) 투입 전에 반응기 내 공기를 배출시켜 진공이 형성되도록 하는 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
In step (c), the reactor is a method of producing hexafluoropropylene oxide, characterized in that a vacuum is formed by discharging the air in the reactor before introducing hexafluoropropylene (HFP).
단계 (c)에서, 상기 헥사플루오로프로필렌(Hexafluoropropylene, HFP)은 기체 상태인 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
In step (c), the hexafluoropropylene (HFP) is a method of producing hexafluoropropylene oxide, characterized in that the hexafluoropropylene (HFP) is in a gaseous state.
단계 (c)에서, 상기 반응은 10 내지 60℃에서 수행되는 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
In step (c), the reaction is carried out at 10 to 60°C.
단계 (c)에서, 상기 반응은 10 내지 150분 동안 수행되는 것을 특징으로 하는 헥사플루오로프로필렌 옥사이드의 제조방법.According to paragraph 1,
In step (c), the reaction is performed for 10 to 150 minutes.
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