TWI798518B - The production method of cyclobutane - Google Patents

The production method of cyclobutane Download PDF

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TWI798518B
TWI798518B TW109100254A TW109100254A TWI798518B TW I798518 B TWI798518 B TW I798518B TW 109100254 A TW109100254 A TW 109100254A TW 109100254 A TW109100254 A TW 109100254A TW I798518 B TWI798518 B TW I798518B
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江藤友亮
中村新吾
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日商大金工業股份有限公司
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00Preparation of halogenated hydrocarbons
    • C07C17/07Preparation of halogenated hydrocarbons by addition of hydrogen halides
    • C07C17/087Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated halogenated hydrocarbons
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    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C23/00Compounds containing at least one halogen atom bound to a ring other than a six-membered aromatic ring
    • C07C23/02Monocyclic halogenated hydrocarbons
    • C07C23/06Monocyclic halogenated hydrocarbons with a four-membered ring
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    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306Chemical or electrical treatment, e.g. electrolytic etching
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Abstract

本發明之目的係以高選擇率製造含氟原子之環丁烷。 該製造方法係一般式(1)所表示之環丁烷之製造方法,

Figure 109100254-A0101-11-0001-1
(式中,X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基),其包含 使一般式(2)所表示之環丁烯與氟化氫在觸媒的存在下,在氣相下反應之步驟,
Figure 109100254-A0101-11-0001-2
(式中,X1 、X2 、X3 、X4 、X5 及X6 係與前述相同)。The object of the present invention is to produce cyclobutane containing fluorine atoms with high selectivity. The production method is a production method of cyclobutane represented by the general formula (1),
Figure 109100254-A0101-11-0001-1
(wherein, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), which includes the general formula (2) The step of reacting cyclobutene and hydrogen fluoride in the gas phase in the presence of a catalyst,
Figure 109100254-A0101-11-0001-2
(In the formula, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are the same as above).

Description

環丁烷之製造方法The production method of cyclobutane

本發明有關環丁烷之製造方法。The present invention relates to a method for producing cyclobutane.

含鹵素原子之環丁烷除了作為半導體用乾蝕刻氣體以外,亦作為各種冷媒、發泡劑、熱移動介質等而有用之化合物。Cyclobutane containing a halogen atom is not only used as a dry etching gas for semiconductors, but also as a compound useful as various refrigerants, foaming agents, and heat transfer media.

非專利文獻1中,揭示自3,3,4,4-四氟環丁烯利用CoF3 、MnF3 、AgF2 、CeF4 或KCoF4 等之氟劑藉由氟化反應而製造1H-七氟環丁烷之方法。In Non - Patent Document 1 , it is disclosed that 1H - 7 The method of fluorocyclobutane.

非專利文獻2中,揭示自六氟環丁烯(cC4 F6 )使用溴化氫(HBr)藉由加成反應而製造1Br,2H-六氟環丁烷(cC4 F6 BrH)之方法。 [先前技術文獻] [非專利文獻]Non-Patent Document 2 discloses the production of 1Br,2H-hexafluorocyclobutane (cC 4 F 6 BrH) from hexafluorocyclobutene (cC 4 F 6 ) by addition reaction using hydrogen bromide (HBr). method. [Prior art literature] [Non-patent literature]

[非專利文獻1] Journal of Fluorine Chemistry, 2006, Vol.127, 79-84, “Fluorination of fluoro-cyclobutene with high-valency metal fluoride” [非專利文獻2] Journal of American Chemistry, 1949, Vol.71, 2339-2340, “The Addition of Hydrogen Bromide to Fluorinated Olefins”[Non-Patent Document 1] Journal of Fluorine Chemistry, 2006, Vol.127, 79-84, "Fluorination of fluoro-cyclobutene with high-valency metal fluoride" [Non-Patent Document 2] Journal of American Chemistry, 1949, Vol.71, 2339-2340, "The Addition of Hydrogen Bromide to Fluorinated Olefins"

[發明欲解決之課題][Problem to be solved by the invention]

本揭示之目的係以高選擇率製造含鹵素原子之環丁烷。 [用以解決課題之手段]The purpose of this disclosure is to produce cyclobutanes containing halogen atoms with high selectivity. [Means to solve the problem]

本揭示包含以下構成。This disclosure includes the following constitutions.

項1. 一種一般式(1)所表示之環丁烷之製造方法,Item 1. A method for producing cyclobutane represented by general formula (1),

Figure 02_image001
Figure 02_image001

(式中,X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基),其中, 包含使一般式(2)所表示之環丁烯與氟化氫在觸媒的存在下,在氣相下反應之步驟,(wherein, X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), wherein, including the general formula (2) Represents the step of reacting cyclobutene and hydrogen fluoride in the gas phase in the presence of a catalyst,

Figure 02_image003
Figure 02_image003

(式中,X1 、X2 、X3 、X4 、X5 及X6 係與前述相同)。(In the formula, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are the same as above).

項2. 如前述項1所記載之製造方法,其係對於前述一般式(2)所表示之環丁烯1莫耳,供給0.1莫耳~100莫耳之氟化氫使其反應。Item 2. The production method described in item 1 above is to supply 0.1 mol to 100 mol of hydrogen fluoride to 1 mol of cyclobutene represented by the aforementioned general formula (2) to react.

項3. 如前述項1或2所記載之製造方法,其中前述觸媒係由活性碳及鉻化合物所成之群所選出之至少1種觸媒。Item 3. The production method described in item 1 or 2 above, wherein the catalyst is at least one catalyst selected from the group consisting of activated carbon and chromium compounds.

項4. 一種含有一般式(1)所表示之環丁烷之組成物,Item 4. A composition containing cyclobutane represented by general formula (1),

Figure 02_image005
Figure 02_image005

(式中,X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基),其中, 將組成物全量定為100mol%,前述一般式(1)所表示之環丁烷之含量為99mol%以上。(wherein, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), wherein, the total amount of the composition is defined as 100mol% , the content of cyclobutane represented by the aforementioned general formula (1) is 99 mol% or more.

項5. 如前述項4所記載之組成物,其係作為清洗氣體、蝕刻氣體、沉積氣體或有機合成用建構組元使用。 [發明效果]Item 5. The composition described in item 4 above is used as a cleaning gas, etching gas, deposition gas, or a building block for organic synthesis. [Invention effect]

依據本揭示,可以高選擇率製造含鹵素原子之環丁烷。According to the present disclosure, cyclobutane containing a halogen atom can be produced with high selectivity.

本發明人等進行積極研究之結果,發現藉由對於原料化合物以氟化氫進行加成反應之步驟在觸媒存在下以氣相進行反應,可以高選擇率製造以上述一般式(1)表示之含氟原子之環丁烷。As a result of intensive research by the inventors of the present invention, it has been found that the compound represented by the above general formula (1) can be produced with high selectivity by performing the reaction in the gas phase in the presence of a catalyst in the step of carrying out the addition reaction of hydrogen fluoride to the raw material compound. Cyclobutane with fluorine atom.

本揭示係基於該見解進一步重複研究結果而完成者。This disclosure is based on further repetition of research results based on this knowledge.

本揭示包含以下實施形態。This disclosure includes the following embodiments.

一種一般式(1)所表示之環丁烷之製造方法,A method for producing cyclobutane represented by general formula (1),

Figure 02_image007
Figure 02_image007

(式中,X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基),其中, 包含使一般式(2)所表示之環丁烯與氟化氫反應之步驟,(wherein, X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), wherein, including the general formula (2) The steps of the reaction of cyclobutene and hydrogen fluoride,

Figure 02_image009
Figure 02_image009

(式中,X1 、X2 、X3 、X4 、X5 及X6 係與前述相同)。(In the formula, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are the same as above).

本揭示中,前述反應係藉由氟化氫之加成反應,前述步驟係在觸媒存在下在氣相下反應。In the present disclosure, the aforementioned reaction is performed by the addition reaction of hydrogen fluoride, and the aforementioned steps are reacted in the gas phase in the presence of a catalyst.

本揭示中,藉由滿足上述要件,可以高選擇率製造含氟原子之環丁烷。In the present disclosure, by satisfying the above requirements, cyclobutane containing fluorine atoms can be produced with high selectivity.

本揭示中,所謂「選擇率」意指相對於自反應器出口之流出氣體中原料化合物以外之化合物(含氟原子之環丁烷等)之合計莫耳量的該流出氣體中所含之目的化合物(含氟原子之環丁烷)之合計莫耳量之比例(mol%)。In this disclosure, the so-called "selectivity" means the target contained in the effluent gas relative to the total molar amount of compounds other than the raw material compounds (cyclobutane containing fluorine atoms, etc.) in the effluent gas from the outlet of the reactor. The ratio (mol%) of the total molar amount of the compound (cyclobutane containing fluorine atom).

本揭示中,所謂「轉化率」意指相對於供給至反應器之原料化合物(環丁烯)之莫耳量的自反應器出口之流出氣體中所含之原料化合物以外之化合物(含氟原子之環丁烷)之合計莫耳量之比例(mol%)。In this disclosure, the so-called "conversion rate" means the compound (containing fluorine atom) other than the raw material compound (containing fluorine atom) contained in the effluent gas from the outlet of the reactor relative to the molar amount of the raw material compound (cyclobutene) supplied to the reactor. The ratio (mol%) of the total molar amount of cyclobutane).

本揭示之環丁烷之製造方法適於工業等級之生產。本揭示之環丁烷之製造方法係使用環丁烯及氟化氫作為原料,該等原料可以工業等級獲得。本揭示之環丁烷之製造方法於將1H-七氟環丁烷作為目的化合物時,可達成高選擇率。The manufacturing method of cyclobutane disclosed in this disclosure is suitable for industrial grade production. The method for producing cyclobutane of the present disclosure uses cyclobutene and hydrogen fluoride as raw materials, and these raw materials are available in industrial grade. The method for producing cyclobutane disclosed herein can achieve high selectivity when 1H-heptafluorocyclobutane is used as the target compound.

(1)原料化合物 以一般式(2)表示之環丁烯 本揭示中,原料化合物係以一般式(2)表示之環丁烯及氟化氫,(1) Raw material compound Cyclobutene represented by general formula (2) In this disclosure, the raw material compounds are cyclobutene and hydrogen fluoride represented by the general formula (2),

Figure 02_image011
Figure 02_image011

(式中,X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基)。(In the formula, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent hydrogen atom, halogen atom, or perfluoroalkyl group identically or differently).

X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基。X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are the same or different representations of a hydrogen atom, a halogen atom, or a perfluoroalkyl group.

X1 、X2 、X3 、X4 、X5 及X6 之鹵素原子舉例為氟原子、氯原子、溴原子及碘原子。The halogen atoms of X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are exemplified by fluorine atom, chlorine atom, bromine atom and iodine atom.

X1 、X2 、X3 、X4 、X5 及X6 之全氟烷基係全部氫原子經氟原子取代之烷基。全氟烷基例如為碳數1~20,較佳碳數1~12,更佳碳數1~6,又更佳碳數1~4,特佳碳數1~3之全氟烷基。全氟烷基較佳為直鏈狀或分支鏈狀之全氟烷基。作為前述全氟烷基較佳為三氟甲基(CF3 -)及五氟乙基(C2 F5 -)。The perfluoroalkyl groups of X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are alkyl groups in which all hydrogen atoms are replaced by fluorine atoms. The perfluoroalkyl group is, for example, a perfluoroalkyl group having 1 to 20 carbons, preferably 1 to 12 carbons, more preferably 1 to 6 carbons, more preferably 1 to 4 carbons, particularly preferably 1 to 3 carbons. The perfluoroalkyl group is preferably a linear or branched perfluoroalkyl group. As the aforementioned perfluoroalkyl group, trifluoromethyl (CF 3 -) and pentafluoroethyl (C 2 F 5 -) are preferable.

作為原料化合物之以一般式(2)表示之環丁烯,就可以高選擇率製造含氟原子之環丁烷之觀點,更佳X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氟原子或全氟烷基。The cyclobutene represented by the general formula (2) as a raw material compound is more preferably X 1 , X 2 , X 3 , X 4 , X 5 and X from the viewpoint of producing cyclobutane containing fluorine atoms with high selectivity. 6 represents a fluorine atom or a perfluoroalkyl group either identically or differently.

作為原料化合物之以一般式(2)表示之環丁烯,舉例為例如如下等之化合物。The cyclobutene represented by the general formula (2) as a raw material compound includes, for example, the following compounds.

Figure 02_image013
Figure 02_image013

該等以一般式(2)表示之環丁烯可單獨使用,亦可組合2種以上使用。此等環丁烯可採用習知或市售品。These cyclobutenes represented by the general formula (2) may be used alone or in combination of two or more. As these cyclobutenes, known or commercially available items can be used.

以一般式(2)表示之環丁烯,就可以高選擇率製造含氟原子之環丁烷之觀點,更佳X1 、X2 、X3 、X4 、X5 及X6 更佳為氟原子。The cyclobutene represented by the general formula (2) is more preferably X 1 , X 2 , X 3 , X 4 , X 5 and X 6 from the viewpoint of producing cyclobutane containing fluorine atoms with high selectivity. fluorine atom.

環丁烯與氟化氫之莫耳比 氟化氫(HF)通常較佳與一般式(2)表示之環丁烯(原料化合物)一起以氣相狀態供給至反應器。氟化氫之供給量較佳對於一般式(2)表示之環丁烯(原料化合物) 1莫耳為0.1莫耳~100莫耳左右反應。氟化氫之供給量更佳對於一般式(2)表示之環丁烯(原料化合物) 1莫耳為0.5莫耳~50莫耳左右,又更佳為1莫耳~30莫耳左右,特佳為1莫耳~20莫耳左右。藉由氟化氫之供給量為前述範圍,而可良好地進行氟化氫之加成反應,可減低雜質之生成,可提高生成物的含氟原子之環丁烷的選擇率,可以高收率回收。Molar ratio of cyclobutene to hydrogen fluoride Hydrogen fluoride (HF) is usually preferably supplied to the reactor in a gas phase state together with cyclobutene (raw material compound) represented by the general formula (2). The supply amount of hydrogen fluoride is preferably about 0.1 mol to 100 mol for 1 mol of cyclobutene (raw material compound) represented by the general formula (2). The supply amount of hydrogen fluoride is more preferably about 0.5 mol to 50 mol, more preferably about 1 mol to 30 mol, especially preferably 1 mol of cyclobutene (raw material compound) represented by the general formula (2). About 1 mole to 20 moles. When the supply amount of hydrogen fluoride is within the above-mentioned range, the addition reaction of hydrogen fluoride can proceed favorably, the formation of impurities can be reduced, the selectivity of cyclobutane containing fluorine atoms in the product can be increased, and high yield recovery can be achieved.

(2)加成反應 本揭示之使環丁烯與氟化氫反應之步驟係利用氟化氫之加成反應,在觸媒存在下於氣相下進行。本揭示之使環丁烯與氟化氫反應之步驟(加成反應)係以氣相進行,尤其較佳以使用固定床反應器之氣相連續流通式進行。以氣相連續流通式進行時,裝置、操作等可簡略化,同時經濟上有利。(2) Addition reaction The step of reacting cyclobutene and hydrogen fluoride in the present disclosure utilizes the addition reaction of hydrogen fluoride to be carried out in the gas phase in the presence of a catalyst. The step of reacting cyclobutene with hydrogen fluoride (addition reaction) in the present disclosure is carried out in the gas phase, and is particularly preferably carried out in a gas phase continuous flow method using a fixed bed reactor. When it is carried out in a gas-phase continuous flow system, the equipment and operation can be simplified, and it is also economically advantageous.

本揭示之使環丁烯與氟化氫反應之步驟例如作為原料化合物,更佳為以一般式(2)表示之環丁烯中,X1 、X2 、X3 、X4 及X6 為氟原子。The step of reacting cyclobutene and hydrogen fluoride in this disclosure is, for example, as a raw material compound, more preferably in cyclobutene represented by the general formula (2), X 1 , X 2 , X 3 , X 4 and X 6 are fluorine atoms .

較佳為依據以下反應式,利用氟化氫之加成反應。It is preferable to utilize the addition reaction of hydrogen fluoride according to the following reaction formula.

Figure 02_image015
Figure 02_image015

觸媒 本揭示之使環丁烯與氟化氫反應之步驟係於利用氟化氫之加成反應中,在觸媒存在下以氣相進行。catalyst The step of reacting cyclobutene with hydrogen fluoride in the present disclosure is carried out in the gas phase in the presence of a catalyst in the addition reaction using hydrogen fluoride.

本步驟所用之觸媒較佳為活性碳。The catalyst used in this step is preferably activated carbon.

本步驟所用之觸媒較佳為金屬觸媒。作為金屬觸媒較佳為氧化鉻、氟化氧化鉻、氟化鉻等之鉻觸媒、氧化鋁、氟化氧化鋁、氟化鋁等之鋁觸媒、氧化鐵、氟化氧化鐵、氟化鐵等之鐵觸媒、氧化鎳、氟化氧化鎳、氟化鎳等之鎳觸媒、氧化鎂、氟化氧化鎂、氟化鎂等之鎂觸媒等之金屬觸媒。觸媒較佳為自前述金屬觸媒所成之群中選擇之至少1種。The catalyst used in this step is preferably a metal catalyst. As metal catalysts, chromium catalysts such as chromium oxide, fluorinated chromium oxide, and chromium fluoride, aluminum catalysts such as aluminum oxide, fluorinated alumina, and aluminum fluoride, iron oxide, fluorinated iron oxide, and fluorine catalysts are preferred. Metal catalysts such as iron catalysts such as iron oxide, nickel catalysts such as nickel oxide, fluorinated nickel oxide, and nickel fluoride, and magnesium catalysts such as magnesium oxide, fluorinated magnesium oxide, and magnesium fluoride. The catalyst is preferably at least one selected from the group consisting of the aforementioned metal catalysts.

本步驟所用之觸媒較佳為自活性碳及前述金屬觸媒所成之群中選擇之至少1種。該等觸媒中,基於可以更高選擇率獲得目的化合物之觀點,更佳為活性碳、氧化鉻、氟化氧化鉻、氟化鉻等之鉻觸媒。又,亦可更提高原料化合物之轉化率。The catalyst used in this step is preferably at least one selected from the group consisting of activated carbon and the aforementioned metal catalysts. Among these catalysts, chromium catalysts such as activated carbon, chromium oxide, fluorinated chromium oxide, and chromium fluoride are more preferable from the viewpoint of obtaining the target compound with higher selectivity. In addition, the conversion rate of the raw material compound can be further improved.

本步驟中,以氣相使原料化合物與觸媒接觸時,觸媒較佳以固體狀態(固相)與原料化合物接觸。In this step, when the raw material compound is brought into contact with the catalyst in a gas phase, it is preferable that the catalyst is brought into contact with the raw material compound in a solid state (solid phase).

本步驟中,觸媒可為粉末狀,但為顆粒狀時就氣相連續流通式之反應較佳。In this step, the catalyst may be in the form of powder, but the reaction in the gas phase continuous flow mode is better when the catalyst is in the form of particles.

前述觸媒之藉由BET法測定之比表面積(以下亦稱為BET比表面積)通常為10~3,000m2 /g,較佳為10~2,500m2 /g,更佳為20~2,000 m2 /g,又更佳為30~1,500m2 /g。觸媒之BET比表面積為此等範圍內時,由於觸媒粒子之密度不會過小,故可以高選擇率獲得目的化合物。又,亦可提高原料化合物之轉化率。例如作為觸媒較佳使用BET比表面積為800~2,000m2 /g之活性碳。The specific surface area of the aforementioned catalyst measured by the BET method (hereinafter also referred to as the BET specific surface area) is usually 10~3,000m 2 /g, preferably 10~2,500m 2 /g, more preferably 20~2,000m 2 /g, more preferably 30~1,500m 2 /g. When the BET specific surface area of the catalyst is within these ranges, the target compound can be obtained with high selectivity because the density of the catalyst particles will not be too small. Moreover, the conversion rate of a raw material compound can also be improved. For example, activated carbon with a BET specific surface area of 800-2,000 m 2 /g is preferably used as a catalyst.

使用活性碳作為觸媒時,較佳使用破碎碳、成形碳、顆粒碳、球狀碳等之粉末活性碳。粉末活性碳較佳使用以JIS試驗顯示4網眼(4.76mm)~100網眼(0.149mm)之粒度的粉末活性碳。使用活性碳作為觸媒時,可使用自使用前於例如300~500℃之溫度條件流通氮氣一段時間進行處理者(經熱處理之活性碳)。When activated carbon is used as a catalyst, powdered activated carbon such as crushed carbon, formed carbon, granular carbon, spherical carbon, etc. is preferably used. As the powdered activated carbon, it is preferable to use the powdered activated carbon whose particle size is 4 meshes (4.76 mm) to 100 meshes (0.149 mm) according to the JIS test. When activated carbon is used as a catalyst, it can be treated by flowing nitrogen gas at a temperature of, for example, 300-500°C for a period of time before use (heat-treated activated carbon).

使用金屬觸媒作為觸媒時,較佳擔持於載體上。作為載體舉例為例如碳、氧化鋁(Al2 O3 )、氧化鋯(ZrO2 )、氧化矽(SiO2 )、氧化鈦(TiO2 )等。作為碳可使用活性碳、不定形碳、石墨、金剛石等。When using a metal catalyst as a catalyst, it is preferably supported on a carrier. Examples of the carrier include carbon, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), and the like. Activated carbon, amorphous carbon, graphite, diamond, etc. can be used as carbon.

作為本揭示之觸媒之一例,針對氧化鉻及氟化氧化鉻加以說明。氧化鉻係於例如以Cr2 O3 ・nH2 O表示氧化鉻時較佳n之值為3以下,更佳為1~1.5。又,前述氧化鉻較佳於組成式:CrOm 中,m通常為1.5<m<3之範圍者。作為觸媒,氟化之氧化鉻可藉由使氧化鉻氟化而調製。作為氟化舉例為藉由氟化氫(HF)之氟化、藉由氟碳等之氟化。As an example of the catalyst of the present disclosure, chromium oxide and fluorinated chromium oxide will be described. For example, when chromium oxide is represented by Cr 2 O 3 ·nH 2 O, the value of n is preferably 3 or less, more preferably 1 to 1.5. In addition, the aforementioned chromium oxide is preferably the composition formula: CrO m , where m is usually in the range of 1.5<m<3. As a catalyst, fluorinated chromium oxide can be prepared by fluorinating chromium oxide. Examples of fluorination include fluorination with hydrogen fluoride (HF), fluorination with fluorocarbon, and the like.

作為觸媒之氟化氧化鉻可依據例如日本專利第3412165號中記載之方法獲得。氧化鉻藉由氟化氫而氟化(HF處理)而可獲得氟化氧化鉻。氟化溫度較佳為例如100~460℃。氟化之壓力較佳為供給於觸媒反應時之壓力。本揭示中,特佳使用氟含量較多之高氟化-氧化鉻觸媒。高氟化-氧化鉻觸媒可藉由將氧化鉻於比通常更高溫下長時間氟化而獲得。Fluorinated chromium oxide as a catalyst can be obtained by the method described in Japanese Patent No. 3412165, for example. Fluorinated chromium oxide can be obtained by fluorinating chromium oxide with hydrogen fluoride (HF treatment). The fluorination temperature is preferably, for example, 100 to 460°C. The pressure of fluorination is preferably the pressure supplied during the catalyst reaction. In this disclosure, it is particularly preferred to use a high fluorinated-chromium oxide catalyst with a high fluorine content. Highly fluorinated chromium oxide catalysts can be obtained by fluorinating chromium oxide at higher temperatures than usual for prolonged periods of time.

高氟化-氧化鉻觸媒較佳氟含量為30質量%以上,更佳為30~45質量%。氟含量可藉由觸媒之質量變化或一般鉻氧化物之定量分析法而測定。The high fluoride-chromium oxide catalyst preferably has a fluorine content of 30% by mass or more, more preferably 30-45% by mass. The fluorine content can be determined by the mass change of the catalyst or the quantitative analysis method of general chromium oxide.

氣相反應溫度 本揭示之使環丁烯與氟化氫反應之步驟,反應溫度之下限,基於可更有效率地進行藉由氟化氫之加成反應、可以更高選擇率獲得目的化合物之觀點,基於抑制轉化率降低之觀點,通常為50℃,較佳為200℃,更佳為250℃,又更佳為300℃。gas phase reaction temperature In the step of reacting cyclobutene and hydrogen fluoride in this disclosure, the lower limit of the reaction temperature is based on the view that the addition reaction by hydrogen fluoride can be carried out more efficiently and the target compound can be obtained with a higher selectivity, and based on the idea of suppressing the decrease in conversion rate From a viewpoint, it is usually 50°C, preferably 200°C, more preferably 250°C, and still more preferably 300°C.

使用活性碳作為觸媒時,反應溫度較佳為50℃~400℃,更佳為100℃~350℃,又更佳為150℃~300℃。When activated carbon is used as the catalyst, the reaction temperature is preferably 50°C-400°C, more preferably 100°C-350°C, and more preferably 150°C-300°C.

使用鉻觸媒作為觸媒時,反應溫度較佳為50℃以上,更佳為250℃以上,又更佳為300℃以上。When a chromium catalyst is used as the catalyst, the reaction temperature is preferably above 50°C, more preferably above 250°C, and more preferably above 300°C.

使環丁烯與氟化氫反應之反應溫度之上限值,基於可更有效率地進行藉由氟化氫之加成反應、可以更高選擇率獲得目的化合物之觀點,且基於抑制因反應生成物分解或聚合所致之選擇率降低之觀點,通常為500℃,較佳為450℃,更佳為400℃。The upper limit of the reaction temperature for the reaction of cyclobutene and hydrogen fluoride is based on the viewpoint that the addition reaction by hydrogen fluoride can be carried out more efficiently and the target compound can be obtained with a higher selectivity, and is based on the suppression of decomposition of the reaction product or From the viewpoint of selectivity reduction due to polymerization, it is usually 500°C, preferably 450°C, more preferably 400°C.

氣相反應時間 使環丁烯與氟化氫反應之反應時間,若使原料化合物對於觸媒之接觸時間(W/F0 )[W:金屬觸媒重量(g),F0 :原料化合物之流量(cc/sec)]增長則可提高原料化合物之轉化率,但觸媒量變多設備變大而不具效率。The gas phase reaction time is the reaction time for the reaction between cyclobutene and hydrogen fluoride, if the contact time of the raw material compound to the catalyst (W/F 0 ) [W: metal catalyst weight (g), F 0 : the flow rate of the raw material compound ( cc/sec)] increase can improve the conversion rate of raw material compounds, but the amount of catalyst increases and the equipment becomes larger and inefficient.

因此,使環丁烯與氟化氫反應之反應時間,基於提高原料化合物之轉化率之觀點,及抑制設備成本之觀點,原料化合物對於觸媒之接觸時間(W/F0 )較佳為1g・sec/cc~30g・sec/cc,更佳為1.5g・sec/cc~10g・sec/cc,又更佳為2.0g・sec/cc~5.0g・sec/cc。Therefore, the reaction time for reacting cyclobutene and hydrogen fluoride is preferably 1 g·sec for the contact time (W/F 0 ) of the raw material compound with the catalyst from the viewpoint of increasing the conversion rate of the raw material compound and suppressing the cost of equipment. /cc~30g·sec/cc, more preferably 1.5g·sec/cc~10g·sec/cc, more preferably 2.0g·sec/cc~5.0g·sec/cc.

上述原料化合物對於觸媒之接觸時間意指原料化合物及觸媒接觸之時間。The above-mentioned contact time of the raw material compound with the catalyst means the time during which the raw material compound and the catalyst are in contact.

環丁烯與氟化氫之莫耳比 氟化氫之供給量,於使用活性碳及鉻觸媒作為觸媒之情況下,基於反應成本及生產性之觀點,相對於以上述一般式(2)表示之環丁烯(原料化合物) 1莫耳,較佳為0.1莫耳~100莫耳左右,更佳為0.5莫耳~75莫耳左右,又更佳為1莫耳~50莫耳左右。Molar ratio of cyclobutene to hydrogen fluoride The supply amount of hydrogen fluoride, in the case of using activated carbon and chromium catalyst as a catalyst, is based on the viewpoint of reaction cost and productivity, relative to 1 mol of cyclobutene (raw material compound) represented by the above general formula (2) , preferably about 0.1 mol to 100 mol, more preferably about 0.5 mol to 75 mol, and more preferably about 1 mol to 50 mol.

氣相反應壓力 使環丁烯與氟化氫反應之反應壓力,基於更有效率地進行藉由氟化氫之加成反應之觀點,較佳為-0.05MPa~2MPa,更佳為-0.01MPa ~1MPa,又更佳為常壓~0.5MPa。又,本揭示中,針對壓力無記載時為表壓。gas phase reaction pressure The reaction pressure for reacting cyclobutene with hydrogen fluoride is preferably -0.05MPa~2MPa, more preferably -0.01MPa~1MPa, and more preferably normal Pressure ~0.5MPa. In addition, in this disclosure, when there is no description about pressure, it is gauge pressure.

環丁烯與氟化氫之反應中,作為使原料化合物與觸媒(活性碳、鉻觸媒等)接觸並反應之反應器,若為可耐受上述溫度及壓力者,則形狀及構造不特別限定。作為反應器舉例為例如縱型反應器、橫型反應器、多管型反應器等。作為反應器之材質舉例為例如玻璃、不鏽鋼、鐵、鎳、鐵鎳合金等。In the reaction between cyclobutene and hydrogen fluoride, the shape and structure of the reactor are not particularly limited as long as they can withstand the above-mentioned temperature and pressure as a reactor for contacting and reacting the raw material compound with a catalyst (activated carbon, chromium catalyst, etc.) . Examples of the reactor include, for example, a vertical reactor, a horizontal reactor, a multi-tubular reactor, and the like. Examples of materials for the reactor include glass, stainless steel, iron, nickel, iron-nickel alloy, and the like.

氣相反應之例示 環丁烯與氟化氫之反應(藉由氟化氫之加成反應)可藉由於反應器中連續饋入原料化合物,自該反應器連續抽出目的化合物之流通式及批式之任一方式而實施。目的化合物滯留於反應器時,由於可進而進行脫離反應,故較加以流通式實施。本揭示之使環丁烯與氟化氫反應之步驟係以氣相進行,特佳係以使用固定床反應器之氣相連續流通式進行。以氣相連續流通式進行時,裝置、操作等可簡略化,於經濟上有利。Example of gas phase reaction The reaction between cyclobutene and hydrogen fluoride (by the addition reaction of hydrogen fluoride) can be carried out by either a flow method or a batch method in which the raw material compound is continuously fed into the reactor and the target compound is continuously extracted from the reactor. When the target compound stays in the reactor, since it can further undergo detachment reaction, it is more carried out in a flow-through method. The step of reacting cyclobutene and hydrogen fluoride in the present disclosure is carried out in the gas phase, and is preferably carried out in a gas phase continuous flow method using a fixed bed reactor. When it is carried out in the gas phase continuous flow method, the equipment and operation can be simplified, which is economically advantageous.

關於進行環丁烯與氟化氫之反應之際的環境,基於抑制觸媒(活性碳、鉻觸媒等)之劣化之觀點,較佳在惰性氣體存在下及/或氟化氫存在下。該惰性氣體較佳為自氮、氦、氬及二氧化碳所成之群中選擇之至少1種。該等惰性氣體中,基於抑制成本之觀點,更佳為氮。該惰性氣體之濃度較佳為導入反應器之氣體成分的0~50mol%。The environment for the reaction between cyclobutene and hydrogen fluoride is preferably in the presence of an inert gas and/or in the presence of hydrogen fluoride from the viewpoint of suppressing degradation of catalysts (activated carbon, chromium catalyst, etc.). The inert gas is preferably at least one selected from the group consisting of nitrogen, helium, argon and carbon dioxide. Among these inert gases, nitrogen is more preferable from the viewpoint of cost suppression. The concentration of the inert gas is preferably 0-50 mol% of the gas components introduced into the reactor.

環丁烯與氟化氫之反應(藉由氟化氫之加成反應)結束後,根據需要,可依據常用方法進行精製處理,獲得以一般式(1)表示之含氟原子之環丁烷。After the reaction between cyclobutene and hydrogen fluoride (by the addition reaction of hydrogen fluoride), if necessary, it can be purified according to the usual method to obtain cyclobutane containing fluorine atoms represented by the general formula (1).

(3)目的化合物 本揭示之目的化合物係以一般式(1)表示之含氟原子之環丁烷:(3) Target compound The target compound of this disclosure is a fluorine-containing cyclobutane represented by the general formula (1):

Figure 02_image017
Figure 02_image017

(式中,X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基)。(In the formula, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent hydrogen atom, halogen atom, or perfluoroalkyl group identically or differently).

如所製造之以一般式(1)表示之含氟原子之環丁烷舉例為例如如下等之化合物。The fluorine atom-containing cyclobutane represented by the general formula (1) as produced is exemplified, for example, by the following compounds.

Figure 02_image019
Figure 02_image019

以一般式(1)表示之含氟原子之環丁烷中,X1 、X2 、X3 、X4 、X5 及X6 係相同或相異地表示氫原子、鹵素原子,或全氟烷基。In the cyclobutane containing fluorine atom represented by the general formula (1), X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent hydrogen atom, halogen atom, or perfluoroalkane identically or differently. base.

本揭示之環丁烷之製造方法中,原料化合物於以一般式(2)表示之環丁烯與氟化氫反應之步驟中,藉由氟化氫進行加成反應,例如作為原料化合物,以一般式(2)表示之環丁烯較佳係X1 、X2 、X3 、X4 及X6 為氟原子。In the method for producing cyclobutane disclosed in the present disclosure, in the step of reacting cyclobutene and hydrogen fluoride represented by the general formula (2), the raw material compound is subjected to an addition reaction by hydrogen fluoride, for example, as a raw material compound, the general formula (2) ) represents cyclobutene, preferably X 1 , X 2 , X 3 , X 4 and X 6 are fluorine atoms.

較佳係依據以下反應,藉由氟化氫之加成反應。Preferably, it is based on the following reaction, by addition reaction of hydrogen fluoride.

Figure 02_image021
Figure 02_image021

目的化合物,作為以一般式(1)表示之含氟原子之環丁烷,更佳係X1 、X2 、X3 、X4 、X5 及X6 為氟原子。The target compound is a fluorine atom-containing cyclobutane represented by the general formula (1), more preferably X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are fluorine atoms.

依據本揭示之製造方法,以一般式(1)表示之含氟原子之環丁烷作為目的化合物,可以工業等級,以高選擇率良好地製造。According to the production method of the present disclosure, the fluorine atom-containing cyclobutane represented by the general formula (1) can be produced satisfactorily at an industrial grade with high selectivity as the target compound.

(4)包含含氟原子之環丁烷之組成物 如以上,可獲得以一般式(1)表示之含氟原子之環丁烷,但如上述,亦有以含有以一般式(1)表示之含氟原子之環丁烷與以一般式(2)表示之環丁烯之組成物形態獲得之情況。(4) Compositions of cyclobutane containing fluorine atoms As above, the fluorine-containing cyclobutane represented by the general formula (1) can be obtained, but as mentioned above, there are also cyclobutanes containing the fluorine-containing atoms represented by the general formula (1) and the general formula (2) ) represents the state of cyclobutene composition obtained.

作為組成物中所含之以一般式(1)表示之含氟原子之環丁烷,較佳係X1 、X2 、X3 、X4 、X5 及X6 為氟原子。As the fluorine atom-containing cyclobutane represented by the general formula (1) contained in the composition, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are preferably fluorine atoms.

本揭示之包含以一般式(1)表示之含氟原子之環丁烷之組成物中,前述組成物全量定為100mol%時,以一般式(1)表示之含氟原子之環丁烷之含量較佳為99mol%以上。In the composition of the fluorine atom-containing cyclobutane represented by the general formula (1) of the present disclosure, when the total amount of the aforementioned composition is defined as 100 mol%, the amount of the fluorine atom-containing cyclobutane represented by the general formula (1) The content is preferably more than 99 mol%.

本揭示之包含以一般式(1)表示之含氟原子之環丁烷之組成物中,前述組成物全量定為100mol%時,以一般式(1)表示之含氟原子之環丁烷之含量較佳為1mol%~99.9mol%,更佳為5mol%~99.9mol%,又更佳為10mol%~99.9mol%。In the composition of the fluorine atom-containing cyclobutane represented by the general formula (1) of the present disclosure, when the total amount of the aforementioned composition is defined as 100 mol%, the amount of the fluorine atom-containing cyclobutane represented by the general formula (1) The content is preferably 1 mol%~99.9 mol%, more preferably 5 mol%~99.9 mol%, and more preferably 10 mol%~99.9 mol%.

依據本發明之製造方法,以包含以一般式(1)表示之含氟原子之環丁烷之組成物而獲得之情況下,可以特別高的選擇率獲得以一般式(1)表示之含氟原子之環丁烷,其結果,可使前述組成物中之以一般式(1)表示之含氟原子之環丁烷以外之成份減少。依據本揭示之製造方法,可消減為了獲得以一般式(1)表示之含氟原子之環丁烷之精製勞力。According to the production method of the present invention, when the composition of cyclobutane containing fluorine atoms represented by the general formula (1) is obtained, the fluorine-containing cyclobutane represented by the general formula (1) can be obtained with a particularly high selectivity. Atomic cyclobutane, as a result, can reduce the components other than the fluorine atom-containing cyclobutane represented by the general formula (1) in the aforementioned composition. According to the production method of the present disclosure, it is possible to reduce the purification effort for obtaining the fluorine atom-containing cyclobutane represented by the general formula (1).

本揭示之包含以一般式(1)表示之含氟原子之環丁烷之組成物,與以一般式(1)表示之含氟原子之環丁烷單獨之情況同樣,除可有效利用於半導體、液晶等之用以形成最先端之微細構造之蝕刻氣體以外,亦可有效利用於沉積氣體、有機合成用建構組元、清洗氣體等之各種用途。The composition of the present disclosure including the fluorine atom-containing cyclobutane represented by the general formula (1) is the same as the case of the fluorine atom-containing cyclobutane represented by the general formula (1) alone, except that it can be effectively used in semiconductors In addition to etching gases for forming the most advanced microstructures such as liquid crystals, etc., it can also be effectively used for various purposes such as deposition gases, building blocks for organic synthesis, and cleaning gases.

前述沉積氣體係使蝕刻耐性聚合物層堆積之氣體。The aforementioned deposition gas system is a gas for depositing an etch-resistant polymer layer.

有機合成用建構組元意指可成為具有反應性高之骨架的化合物前驅物之物質。例如本揭示之以一般式(1)表示之含氟原子之環丁烷及包含其之組成物與CF3 Si(CH3 )3 等之含氟有機矽化合物反應時,可導入CF3 基等之氟烷基而轉化成可成為洗淨劑或含氟醫藥中間體之物質。A building block for organic synthesis means a substance that can be a precursor of a compound having a highly reactive skeleton. For example, when the fluorine atom-containing cyclobutane represented by the general formula (1) of the present disclosure and the composition containing it react with a fluorine-containing organosilicon compound such as CF 3 Si(CH 3 ) 3 , CF 3 groups, etc. can be introduced The fluoroalkyl groups can be transformed into substances that can become detergents or fluorine-containing pharmaceutical intermediates.

以上說明本揭示之實施形態,但只要未脫離申請專利範圍之意旨及範圍,則形態及細節可有多種變更。 [實施例]The embodiments of the present disclosure have been described above, but various changes can be made in the embodiments and details as long as they do not deviate from the spirit and scope of the claims. [Example]

以下列舉實施例具體說明本發明,但本揭示並非限定於該等實施例。The following examples are given to illustrate the present invention in detail, but the present disclosure is not limited to these examples.

實施例 實施例之含氟原子之環丁烷之製造方法中,原料化合物係以一般式(2)表示之環丁烯中,X1 、X2 、X3 及X4 為氟原子。EXAMPLES In the method for producing cyclobutane containing fluorine atoms, the raw material compound is cyclobutene represented by the general formula (2), and X 1 , X 2 , X 3 and X 4 are fluorine atoms.

依據以下反應式,對環丁烯進行藉由氟化氫之加成反應。Addition reaction of cyclobutene by hydrogen fluoride is carried out according to the following reaction formula.

Figure 02_image023
Figure 02_image023

目的化合物,作為以一般式(1)表示之含氟原子之環丁烷,X1 、X2 、X3 、X4 、X5 及X6 為氟原子。The target compound is a fluorine atom-containing cyclobutane represented by general formula (1), wherein X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are fluorine atoms.

實施例1(1-1~1-5)、觸媒:活性碳 使用SUS配管(外徑:1/2吋)作為反應管,填充作為觸媒之活性碳10g。於藉由氟化氫之加成反應中使用前述觸媒。活性碳之BET比表面積為850m2 /g。反應器的SUS配管(外徑:1/2吋)中添加作為觸媒之活性碳10g。Example 1 (1-1~1-5), catalyst: activated carbon SUS piping (outer diameter: 1/2 inch) was used as a reaction tube, and 10 g of activated carbon as a catalyst was filled. The aforementioned catalyst is used in the addition reaction by hydrogen fluoride. The BET specific surface area of activated carbon is 850m 2 /g. 10 g of activated carbon as a catalyst was added to the SUS pipe (outer diameter: 1/2 inch) of the reactor.

氮氣環境下,於200℃乾燥2小時後,以使壓力為常壓,環丁烯cC4 F6 (原料化合物)與活性碳(觸媒)之接觸時間(W/F0 )為2.0g・sec/cc之方式,於反應器中流通原料化合物(cC4 F6 )。Under nitrogen atmosphere, after drying at 200°C for 2 hours, so that the pressure is normal pressure, the contact time (W/F 0 ) of cyclobutene cC 4 F 6 (raw material compound) and activated carbon (catalyst) is 2.0g・In the form of sec/cc, the raw material compound (cC 4 F 6 ) was circulated in the reactor.

氟化氫之供給量,相對於環丁烯cC4 F6 (原料化合物) 1莫耳,設為1莫耳或15莫耳。The supply amount of hydrogen fluoride was 1 mole or 15 moles relative to 1 mole of cyclobutene cC 4 F 6 (raw material compound).

以氣相連續流通式進行反應。The reaction was carried out in a gas-phase continuous flow-through system.

反應器於150℃、200℃、250℃或300℃加熱,開始藉由氟化氫之加成反應。開始藉由氟化氫之加成反應起之1小時後,收集通過除害塔之餾出分。The reactor is heated at 150°C, 200°C, 250°C or 300°C to start the addition reaction by hydrogen fluoride. One hour after the start of the addition reaction by hydrogen fluoride, the distillate passing through the detoxification tower was collected.

隨後,使用氣相層析儀(島津製作所公司製,商品名「GC-2014」)藉由氣體層析/質量分析法(GC-MS)進行質量分析,使用NMR (JEOL公司製,商品名「400YH」)進行利用NMR光譜之構造解析。Subsequently, mass analysis was performed by gas chromatography/mass spectrometry (GC-MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Corporation, trade name "GC-2014") was used for mass analysis. 400YH") for structural analysis using NMR spectroscopy.

由質量分析及構造解析之結果,確認產生cC4 F7 H作為目的化合物。實施例1-1中,自cC4 F6 (原料化合物)之轉化率為0.364mol%,cC4 F7 H(目的化合物)之選擇率(收率)為18.6mol%。From the results of mass analysis and structural analysis, it was confirmed that cC 4 F 7 H was produced as the target compound. In Example 1-1, the conversion from cC 4 F 6 (raw material compound) was 0.364 mol%, and the selectivity (yield) of cC 4 F 7 H (target compound) was 18.6 mol%.

實施例1-2係轉化率:11.6mol%,選擇率:96.2mol%。Embodiment 1-2 is conversion: 11.6mol%, selectivity: 96.2mol%.

實施例1-3係轉化率:4.57mol%,選擇率:84.9mol%。Embodiment 1-3 is conversion: 4.57mol%, selectivity: 84.9mol%.

實施例1-4係轉化率:2.30mol%,選擇率:38.8mol%。Embodiment 1-4 is conversion: 2.30mol%, selectivity: 38.8mol%.

實施例1-5係轉化率:0.6mol%,選擇率:94.2mol%。Embodiment 1-5 series conversion rate: 0.6mol%, selectivity: 94.2mol%.

實施例2(2-1~2-8)、觸媒:鉻觸媒 使用SUS配管(外徑:1/2吋)作為反應管,填充作為觸媒之以Cr2 O3 為主成分之氧化鉻10g。作為於脫離反應(脫氟化氫反應)中使用前述觸媒之前處理,於反應器中流通無水氟化氫,將反應器溫度設為200℃至300℃進行氟化處理。取出經氟化之氧化鉻,使用於脫氟化氫反應。經氟化之氧化鉻之BET比表面積為75m2 /g。反應器的SUS配管(外徑:1/2吋)中添加作為觸媒之經氟化之氧化鉻(氟化氧化鉻)10g。Example 2 (2-1~2-8), catalyst: chromium catalyst uses SUS pipe (outer diameter: 1/2 inch) as the reaction tube, filled with Cr2O3 as the main component of oxidation catalyst Chromium 10g. Anhydrous hydrogen fluoride is passed through the reactor as a pretreatment before using the above-mentioned catalyst in the dehydrogenation reaction (dehydrofluorination reaction), and the fluorination treatment is performed by setting the temperature of the reactor at 200°C to 300°C. The fluorinated chromium oxide is taken out and used for dehydrofluorination reaction. The BET specific surface area of fluorinated chromium oxide is 75 m 2 /g. To the SUS pipe (outer diameter: 1/2 inch) of the reactor, 10 g of fluorinated chromium oxide (fluorinated chromium oxide) was added as a catalyst.

氮氣環境下,於200℃乾燥2小時後,以使壓力為常壓,環丁烯cC4 F6 (原料化合物)與經氟化之氧化鉻(觸媒)之接觸時間(W/F0 )為3.0g・sec/cc、4.0g・sec/cc或5.0g・sec/cc之方式,於反應器中流通原料化合物(cC4 F6 H2 )。The contact time of cyclobutene cC 4 F 6 (raw material compound) and fluorinated chromium oxide (catalyst) (W/F 0 ) In the form of 3.0g·sec/cc, 4.0g·sec/cc or 5.0g·sec/cc, the raw material compound (cC 4 F 6 H 2 ) is circulated in the reactor.

氟化氫之供給量,相對於環丁烯cC4 F6 (原料化合物) 1莫耳,設為1莫耳、5莫耳或20莫耳。The supply amount of hydrogen fluoride was 1 mol, 5 mol or 20 mol with respect to 1 mol of cyclobutene cC 4 F 6 (raw material compound).

以氣相連續流通式進行反應。The reaction was carried out in a gas-phase continuous flow-through system.

反應器於50℃、200℃、250℃、300℃或350℃加熱,開始藉由氟化氫之加成反應。開始藉由氟化氫之加成反應起之1小時後,收集通過除害塔之餾出分。The reactor is heated at 50°C, 200°C, 250°C, 300°C or 350°C to start the addition reaction by hydrogen fluoride. One hour after the start of the addition reaction by hydrogen fluoride, the distillate passing through the detoxification tower was collected.

隨後,使用氣相層析儀(島津製作所公司製,商品名「GC-2014」)藉由氣體層析/質量分析法(GC-MS)進行質量分析,使用NMR (JEOL公司製,商品名「400YH」)進行利用NMR光譜之構造解析。Subsequently, mass analysis was performed by gas chromatography/mass spectrometry (GC-MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Corporation, trade name "GC-2014") was used for mass analysis. 400YH") for structural analysis using NMR spectroscopy.

由質量分析及構造解析之結果,確認產生cC4 F7 H作為目的化合物。實施例2-1中,自cC4 F6 (原料化合物)之轉化率為0.942mol%,cC4 F7 H(目的化合物)之選擇率(收率)為0.7mol%。From the results of mass analysis and structural analysis, it was confirmed that cC 4 F 7 H was produced as the target compound. In Example 2-1, the conversion from cC 4 F 6 (raw material compound) was 0.942 mol%, and the selectivity (yield) of cC 4 F 7 H (target compound) was 0.7 mol%.

實施例2-2係轉化率:0.183mol%,選擇率:1.6mol%。Embodiment 2-2 is conversion: 0.183mol%, selectivity: 1.6mol%.

實施例2-3係轉化率:0.506mol%,選擇率:2.4mol%。Embodiment 2-3 is conversion: 0.506mol%, selectivity: 2.4mol%.

實施例2-4係轉化率:0.396mol%,選擇率:0.7mol%。Embodiment 2-4 is conversion: 0.396mol%, selectivity: 0.7mol%.

實施例2-5係轉化率:0.924mol%,選擇率:4.2mol%。Embodiment 2-5 is conversion rate: 0.924mol%, selectivity: 4.2mol%.

實施例2-6係轉化率:1.37mol%,選擇率:3.0mol%。Embodiment 2-6 is conversion rate: 1.37mol%, selectivity: 3.0mol%.

實施例2-7係轉化率:1.62mol%,選擇率:2.0mol%。Embodiment 2-7 is conversion: 1.62mol%, selectivity: 2.0mol%.

實施例2-8係轉化率:2.87mol%,選擇率:0.2mol%。Embodiment 2-8 is conversion: 2.87mol%, selectivity: 0.2mol%.

比較例1及2 仿效前述實施例之實驗方法,不使用觸媒,對環丁烯cC4 F6 (原料化合物)供給氟化氫,進行反應。Comparative Examples 1 and 2 Following the experimental method of the previous examples, without using a catalyst, hydrogen fluoride was supplied to cyclobutene cC 4 F 6 (raw material compound) to react.

氟化氫之供給量,相對於環丁烯cC4 F6 (原料化合物) 1莫耳,設為20莫耳。The supply amount of hydrogen fluoride was set at 20 mol with respect to 1 mol of cyclobutene cC 4 F 6 (raw material compound).

以氣相連續流通式進行反應。The reaction was carried out in a gas-phase continuous flow-through system.

反應器於200℃或350℃加熱,開始藉由氟化氫之加成反應。開始藉由氟化氫之加成反應起之1小時後,收集通過除害塔之餾出分。The reactor is heated at 200°C or 350°C to start the addition reaction by hydrogen fluoride. One hour after the start of the addition reaction by hydrogen fluoride, the distillate passing through the detoxification tower was collected.

隨後,使用氣相層析儀(島津製作所公司製,商品名「GC-2014」)藉由氣體層析/質量分析法(GC-MS)進行質量分析,使用NMR (JEOL公司製,商品名「400YH」)進行利用NMR光譜之構造解析。Subsequently, mass analysis was performed by gas chromatography/mass spectrometry (GC-MS) using a gas chromatograph (manufactured by Shimadzu Corporation, trade name "GC-2014"), and NMR (manufactured by JEOL Corporation, trade name "GC-2014") was used for mass analysis. 400YH") for structural analysis using NMR spectroscopy.

由質量分析及構造解析之結果,自cC4 F6 (原料化合物)之轉化率為0.801mol%(比較例1)或0.695mol%(比較例2),但未確認生成cC4 F7 H(目的化合物)。From the results of mass analysis and structural analysis, the conversion rate from cC 4 F 6 (raw material compound) was 0.801 mol% (comparative example 1) or 0.695 mol% (comparative example 2), but it was not confirmed that cC 4 F 7 H (objective compound).

各實施例之結果示於以下表1。表1中,所謂接觸時間(W/F0 )表示流通之原料氣體流動速度,亦即意指觸媒及原料氣體接觸之時間。所謂莫耳比HF/cC4 F6 係對於cC4 F6 1莫耳之HF使用量(莫耳)。The results of each example are shown in Table 1 below. In Table 1, the so-called contact time (W/F 0 ) represents the flow velocity of the raw material gas, which means the contact time between the catalyst and the raw material gas. The so-called molar ratio HF/cC 4 F 6 refers to the amount of HF used (in moles) for 1 mole of cC 4 F 6 .

Figure 02_image025
Figure 02_image025

Claims (7)

一種一般式(1)所表示之環丁烷之製造方法,
Figure 109100254-A0305-02-0027-1
(式中,X1、X2、X3、X4、X5及X6係相同或相異地表示氫原子、鹵素原子,或全氟烷基),其中,包含使一般式(2)所表示之環丁烯與氟化氫在觸媒的存在下,在氣相下反應之步驟,
Figure 109100254-A0305-02-0027-2
(式中,X1、X2、X3、X4、X5及X6係與前述相同),前述反應為將氟化氫進行加成之反應。
A method for producing cyclobutane represented by general formula (1),
Figure 109100254-A0305-02-0027-1
(wherein, X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 represent hydrogen atoms, halogen atoms, or perfluoroalkyl groups identically or differently), including the general formula (2) Represents the step of reacting cyclobutene and hydrogen fluoride in the gas phase in the presence of a catalyst,
Figure 109100254-A0305-02-0027-2
(In the formula, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are the same as above), and the above reaction is a reaction of adding hydrogen fluoride.
如請求項1所記載之製造方法,其係對於前述一般式(2)所表示之環丁烯1莫耳,供給0.1莫耳~100莫耳之氟化氫使其反應。 The production method as described in Claim 1 is to supply 0.1 mol to 100 mol of hydrogen fluoride to react with 1 mol of cyclobutene represented by the general formula (2). 如請求項1或2所記載之製造方法,其中,前述觸媒係擔持於由碳;氧化鋁(Al2O3);氧化鋯(ZrO2);氧化矽(SiO2);及氧化鈦(TiO2)所成之群所選出之載體之觸媒,且前述碳係由活性碳、不定形碳、石墨,及金剛石所成之群中所選出之碳。 The production method as described in claim 1 or 2, wherein the aforementioned catalyst is supported by carbon; alumina (Al 2 O 3 ); zirconia (ZrO 2 ); silicon oxide (SiO 2 ); and titanium oxide The catalyst of the carrier selected from the group consisting of (TiO 2 ), and the aforementioned carbon is carbon selected from the group consisting of activated carbon, amorphous carbon, graphite, and diamond. 如請求項1或2所記載之製造方法,其中,前述觸媒係由活性碳;由氧化鉻、氟化氧化鉻,及氟化鉻中所選出之鉻觸媒;由氧化鋁、氟化氧化鋁,及氟化鋁中所選出之鋁觸媒;由氧化鐵、氟化氧化鐵,及氟化鐵中所選出之鐵觸媒;由氧化鎳、氟化氧化鎳,及氟化鎳中所選出之鎳觸媒;及由氧化鎂、氟化氧化鎂,及氟化鎂中所選出之鎂觸媒所成之群中所選出之至少1種觸媒。 The manufacturing method as described in claim 1 or 2, wherein the aforementioned catalyst is activated carbon; a chromium catalyst selected from chromium oxide, fluorinated chromium oxide, and chromium fluoride; aluminum oxide, fluorinated oxidized Aluminum, and aluminum catalysts selected from aluminum fluoride; iron catalysts selected from iron oxide, fluorinated iron oxide, and iron fluoride; iron catalysts selected from nickel oxide, fluorinated nickel oxide, and nickel fluoride the selected nickel catalyst; and at least one catalyst selected from the group consisting of magnesium oxide, magnesia fluoride, and magnesium fluoride. 如請求項1或2所記載之製造方法,其中,前述觸媒係由活性碳;及由氧化鉻、氟化氧化鉻,及氟化鉻中所選出之鉻觸媒所成之群中所選出之至少1種觸媒。 The production method as described in claim 1 or 2, wherein the aforementioned catalyst is selected from the group consisting of activated carbon; and a chromium catalyst selected from chromium oxide, fluorinated chromium oxide, and chromium fluoride of at least one catalyst. 一種含有一般式(1)所表示之環丁烷之組成物之用途,
Figure 109100254-A0305-02-0028-3
(式中,X1、X2、X3、X4、X5及X6係相同或相異地表示氟原子,或全氟烷基),其中,將組成物全量定為100mol%,前述一般式(1)所表示之環丁烷之含量為99mol%以上,且其係作為清洗氣體或蝕刻氣體使用。
A use of a composition containing cyclobutane represented by general formula (1),
Figure 109100254-A0305-02-0028-3
(wherein, X 1 , X 2 , X 3 , X 4 , X 5 and X 6 represent fluorine atoms or perfluoroalkyl groups identically or differently), wherein the total amount of the composition is defined as 100 mol%, and the aforementioned general The content of cyclobutane represented by the formula (1) is 99 mol% or more, and it is used as a cleaning gas or an etching gas.
如請求項6所記載之組成物之用途,其中,前述一般式(1)所表示之環丁烷係由
Figure 109100254-A0305-02-0029-4
中所選出之包含氟原子之環丁烷。
As the use of the composition described in claim 6, wherein the cyclobutane represented by the aforementioned general formula (1) is composed of
Figure 109100254-A0305-02-0029-4
Cyclobutanes containing fluorine atoms selected from .
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