JP5764798B2 - Fluorinated hydrocarbon detection method and detection sensor - Google Patents

Description

  The present invention relates to a detection method and a detection sensor for fluorinated hydrocarbons, and in particular, a fluorinated hydrocarbon compound having an unsaturated bond of carbon in a molecule such as octafluorocyclopentene and hexafluorobutadiene, and at least hydrogen- The present invention relates to a detection method and a detection sensor for a fluorinated saturated hydrocarbon compound having a carbon portion and having an anionic leaving group bonded to the adjacent carbon bonded to the carbon of the hydrogen-carbon portion.

Fluorine-containing compounds have been required to be reduced since the discussion in the Kyoto Protocol as a global warming substance. For the preservation of the global environment and the survival of many species and humans, trace amounts are detected, removed, decomposed, and used. Reduction and recovery technology is required.
In particular, saturated fluorocarbons such as carbon tetrafluoride and octafluorocyclobutane, which have been used as dry etching gases, are restricted in use due to adverse effects on global warming. As an alternative to these, fluorocarbons such as octafluorocyclopentene (C ₅ F _8), hexafluorobutadiene (C ₄ F _6), fluorinated hydrocarbon compound having unsaturated carbon bonds have been developed in the molecule, such as Hekisafu Le Orosi black butene (C ₄ F _6). These fluorinated hydrocarbon compounds having unsaturated bonds of carbon (hereinafter referred to as “fluorinated unsaturated hydrocarbons”) are known as high-performance materials for microfabrication with high selectivity, and in each semiconductor process. Some are used. Although the global warming potential has been improved, the regulation of the control standard concentration of 2 ppm is originally distributed due to the problem of high vapor pressure and toxicity. Furthermore, from the viewpoint of the existing environmental load, and a gas contamination source in the environment at the process site, there is a demand for a technique for highly sensitive detection.

To date, a method using permanganate and a method using thermal decomposition have been developed as detection methods for fluorinated unsaturated hydrocarbons.
The former method is a method using decolorization of permanganate by reaction of C ₅ F ₈ or C ₄ F ₆ with permanganate (see, for example, Patent Document 1).
However, there are the following disadvantages.
(1) The reaction is slow and the concentration to be measured is difficult to detect unless the concentration is higher than 50 ppm. (2) The time until detection is 50 ppm and takes an average of about 19 minutes or longer. (3) Using inorganic substances Therefore, there are difficulties in processability, and the form for detection is limited. (4) Since permanganate, which is a strong oxidant, is used, it is eliminated by hydrides such as boron derivatives and complex reagents. Colors can cause false alarms.

The latter approach is a method using the thermal decomposition of C ₅ F ₈ or C ₄ F _6, a C ₅ F ₈ or C ₄ F ₆ present in the gas is thermally decomposed in the thermal decomposition furnace, in which This is a method for optically detecting the generated acid gas promptly (see, for example, Patent Document 2). However, there are the following disadvantages.
(1) A large amount of energy is consumed for thermal decomposition. (2) Since thermal decomposition is performed at high temperatures, the same acidic gas is generated from gases such as fluorine-based liquids frequently used in cleaning agents and insulators. (3) Because it decomposes at a high temperature, it generates a very dangerous acid gas HF. (4) Eventually, the extremely dangerous acid gas is detected. When other similar acid gas itself is mixed, this also causes false alarms.

JP 2001-324492 A JP 2001-324491 A

As described above, because there are various problems with the conventional detection methods for fluorinated unsaturated hydrocarbons, a high-performance, more economical method using a new method that is completely different in principle from the conventional methods. There is a need for an efficient detection method.
The present invention has been made in view of the actual situation in the above-described conventional technology, and can be detected near room temperature without using high-temperature thermal decomposition or a strong oxidizing agent, and can be easily performed with C ₅ F ₈ or C ₄ F _6. It aims at providing the detection method of fluorinated hydrocarbons, such as.

As a result of intensive studies in order to solve the above problems, the present inventors have made use of the selective reaction of fluorinated unsaturated hydrocarbons such as C ₅ F ₈ and C ₄ F ₆ , thereby The knowledge that the purpose can be achieved was obtained. That is, as a result of intensive investigations on selective reactions with fluorinated unsaturated hydrocarbons such as C ₅ F ₈ and C ₄ F ₆ , a reaction using a specific phosphorus-nitrogen compound group is found and targeted. It has been found that fluorinated unsaturated hydrocarbons can be identified and detected. Furthermore, selective with a fluorinated saturated hydrocarbon having at least a hydrogen-carbon moiety in the molecule and an anionic leaving group bonded to the adjacent carbon bonded to the carbon of the hydrogen-carbon moiety. Similarly, it has been found that it is possible to distinguish and detect the target fluorinated saturated hydrocarbons.

［式中において、Ｒ₁〜Ｒ₄は、一般的なアミン基、もしくは炭化水素基（すなわち、有機化学におけるすべての官能基；炭素をベースとしたアルキル、芳香族、ヘテロ原子、典型元素、遷移金属、アルカリ金属、アルカリ土類金属、およびそれらのイオンから選ばれるコンポーネントも含み、複素環の場合もある）やそれらを有するポリマーから形成される置換基が存在する場合も含む、またそれらの置換基が各Ｒの間で環状部分を形成する場合も含む。］
［２］ 前記反応による光学的変化を検出することを特徴とする［１］に記載の検出方法。
［３］ 前記一般式（Ｉ）で表される、リン−窒素二重結合を有する化合物以外の有機物が共存する態様を用いて検出することを特徴とする請求項［１］または［２］に記載の検出方法。
［４］ 前記フッ素化炭化水素が、Ｃ₅Ｆ₈又はＣ₄Ｆ₆或いはこれらの混合物であることを特徴とする請求項［１］〜［３］のいずれか一項に記載の検出方法。
［５］ 前記Ｃ₅Ｆ₈がオクタフルオロシクロペンテンである［４］に記載の検出方法。
［６］ 前記Ｃ₄Ｆ₆がヘキサフルオロブタジエン又はヘキサフルオロシクロブテン或いはこれらの混合物である［４］に記載の検出方法。
［７］ 前記フッ素化飽和炭化水素が、Ｃ₅Ｆ₈Ｈ₂であることを特徴とする［１］〜［３］のいずれか一項に記載の検出方法。
［８］ 前記Ｃ₅Ｆ₈Ｈ₂が、オクタフルオロシクロペンタンである［７］に記載の検出方法。
［９］ 前記Ｃ₅Ｆ₈Ｈ₂が、１Ｈ，２Ｈ−オクタフルオロシクロペンタン、１Ｈ，１Ｈ−オクタフルオロシクロペンタン、又は１Ｈ，３Ｈ−オクタフルオロシクロペンタン或いはこれらの混合物である［７］に記載の検出方法。
［１０］ 前記反応における、吸光度、反射率、赤外振動、発光、蛍光、燐光、屈折率、液晶状態、及びＸ線による光電子運動エネルギーの変化から選ばれる１つ又は２つ以上の光学的変化を検出することを特徴とする［１］〜［９］のいずれか一項に記載の検出方法。
［１１］ 前記光学的変化として、紫外可視光領域の吸光度変化又は反射率変化を用いることにより、濃度が０．１％以下のフッ素化炭化水素を検出することを特徴とする［１０］に記載の検出方法。
［１２] 前記反応による質量変化を検出することを特徴とする［１］に記載の検出方法。
［１３] 前記リン−窒素二重結合を有する化合物を一定の周波数で振動する表面に少なくとも吸着させ、それにより形成された膜表面と前記フッ素化不飽和炭化水素もしくは前記フッ素化飽和炭化水素との反応による質量変化を、当該表面における振動の一定の周波数からの変化でとらえることを特徴とする［１２］に記載の検出方法。
［１４］ フッ素化不飽和炭化水素、又は分子内に少なくとも水素−炭素部分を有し、かつその水素−炭素部分の炭素に結合している隣の炭素にアニオン性脱離基が結合しているフッ素化飽和炭化水素を検出する検出剤であって、下記一般式（Ｉ）で表される、リン−窒素二重結合を有する化合物を有効成分とすることを特徴とするフッ素化炭化水素の検出剤。

［式中において、Ｒ₁〜Ｒ₄は、一般的なアミン基、もしくは炭化水素基（すなわち、有機化学におけるすべての官能基；炭素をベースとしたアルキル、芳香族、ヘテロ原子、典型元素、遷移金属、アルカリ金属、アルカリ土類金属、およびそれらのイオンから選ばれるコンポーネントも含み、複素環の場合もある）やそれらを有するポリマーから形成される置換基が存在する場合も含む、またそれらの置換基が各Ｒの間で環状部分を形成する場合も含む。］
［１５］ フッ素化不飽和炭化水素、又は分子内に少なくとも水素−炭素部分を有し、かつその水素−炭素部分の炭素に結合している隣の炭素にアニオン性脱離基が結合しているフッ素化飽和炭化水素を検出するためのセンサーであって、検出部に、下記の一般式（Ｉ）で表される、リン−窒素二重結合を有する化合物を用いたことを特徴とするフッ素化炭化水素の検出センサー。

［式中において、Ｒ₁〜Ｒ₄は、一般的なアミン基、もしくは炭化水素基（すなわち、有機化学におけるすべての官能基；炭素をベースとしたアルキル、芳香族、ヘテロ原子、典型元素、遷移金属、アルカリ金属、アルカリ土類金属、およびそれらのイオンから選ばれるコンポーネントも含み、複素環の場合もある）やそれらを有するポリマーから形成される置換基が存在する場合も含む、またそれらの置換基が各Ｒの間で環状部分を形成する場合も含む。］
［１６］ 前記リン−窒素二重結合を有する化合物を含む液体が多孔質材に含浸されていることを特徴とする［１５］に記載のフッ素化炭化水素の検出センサー。
［１７］ 前記多孔質材が、セルロース又はポリマー又は多孔質アルミナである［１６］に記載のフッ素化炭化水素の検出センサー。
［１８］ 前記リン−窒素二重結合を有する化合物を含有するポリマーを用いることを特徴とする［１５］〜［１７］のいずれか一項に記載のフッ素化炭化水素の検出センサー。 The present invention has been completed based on these findings, and according to the present invention, the following inventions are provided.
[1] An anionic leaving group is bonded to a fluorinated unsaturated hydrocarbon or an adjacent carbon having at least a hydrogen-carbon moiety in the molecule and bonded to the carbon of the hydrogen-carbon moiety. A fluorinated carbonization characterized by detecting a fluorinated hydrocarbon using a reaction between a fluorinated saturated hydrocarbon and a compound having a phosphorus-nitrogen double bond represented by the following general formula (I): How to detect hydrogen.

[In the formula, R _{1 to} R ₄ are general amine groups or hydrocarbon groups (that is, all functional groups in organic chemistry; carbon-based alkyls, aromatics, heteroatoms, typical elements, transition elements) Including components selected from metals, alkali metals, alkaline earth metals, and ions thereof, which may be heterocyclic) or in the presence of substituents formed from polymers having them This includes the case where a group forms a cyclic portion between each R. ]
[2] The detection method according to [1], wherein an optical change due to the reaction is detected.
[3] The detection according to [1] or [2], wherein the detection is performed using an aspect in which an organic substance other than the compound having a phosphorus-nitrogen double bond represented by the general formula (I) coexists. The detection method described.
[4] The fluorinated hydrocarbon, detection method according to any one of claims [1] to [3], which is a C ₅ F ₈ or C ₄ F ₆ or mixtures thereof.
[5] The detection method according to [4], wherein the C ₅ F ₈ is octafluorocyclopentene.
[6] The method according to the C ₄ F ₆ is hexafluoro butadiene or Hekisafu Le Orosi Clos butene or mixtures thereof [4].
[7] The detection method according to any one of [1] to [3], wherein the fluorinated saturated hydrocarbon is C ₅ F ₈ H ₂ .
[8] The detection method according to [7], wherein the C ₅ F ₈ H ₂ is octafluorocyclopentane.
[9] The [ ₅ ], wherein the C ₅ F ₈ H ₂ is 1H, 2H-octafluorocyclopentane, 1H, 1H-octafluorocyclopentane, or 1H, 3H-octafluorocyclopentane or a mixture thereof. Detection method.
[10] One or more optical changes selected from changes in absorbance, reflectance, infrared vibration, light emission, fluorescence, phosphorescence, refractive index, liquid crystal state, and photoelectron kinetic energy due to X-rays in the reaction. The detection method according to any one of [1] to [9], wherein:
[11] The fluorinated hydrocarbon having a concentration of 0.1% or less is detected by using a change in absorbance or a change in reflectance in the ultraviolet-visible light region as the optical change. Detection method.
[12] The detection method according to [1], wherein a change in mass due to the reaction is detected.
[13] The compound having a phosphorus-nitrogen double bond is at least adsorbed on a surface vibrating at a constant frequency, and the film surface formed thereby and the fluorinated unsaturated hydrocarbon or the fluorinated saturated hydrocarbon The detection method according to [12], wherein a mass change due to a reaction is detected by a change from a certain frequency of vibration on the surface.
[14] An anionic leaving group is bonded to a fluorinated unsaturated hydrocarbon or an adjacent carbon having at least a hydrogen-carbon moiety in the molecule and bonded to the carbon of the hydrogen-carbon moiety. A detection agent for detecting a fluorinated saturated hydrocarbon, comprising a compound having a phosphorus-nitrogen double bond represented by the following general formula (I) as an active ingredient: Agent.

[In the formula, R _{1 to} R ₄ are general amine groups or hydrocarbon groups (that is, all functional groups in organic chemistry; carbon-based alkyls, aromatics, heteroatoms, typical elements, transition elements) Including components selected from metals, alkali metals, alkaline earth metals, and ions thereof, which may be heterocyclic) or in the presence of substituents formed from polymers having them This includes the case where a group forms a cyclic portion between each R. ]
[15] An anionic leaving group is bonded to a fluorinated unsaturated hydrocarbon or an adjacent carbon having at least a hydrogen-carbon moiety in the molecule and bonded to the carbon of the hydrogen-carbon moiety. A sensor for detecting fluorinated saturated hydrocarbons, characterized in that a compound having a phosphorus-nitrogen double bond represented by the following general formula (I) is used for the detection part: Hydrocarbon detection sensor.

[In the formula, R _{1 to} R ₄ are general amine groups or hydrocarbon groups (that is, all functional groups in organic chemistry; carbon-based alkyls, aromatics, heteroatoms, typical elements, transition elements) Including components selected from metals, alkali metals, alkaline earth metals, and ions thereof, which may be heterocyclic) or in the presence of substituents formed from polymers having them This includes the case where a group forms a cyclic portion between each R. ]
[16] The fluorinated hydrocarbon detection sensor according to [15], wherein a porous material is impregnated with a liquid containing the compound having a phosphorus-nitrogen double bond.
[17] The fluorinated hydrocarbon detection sensor according to [16], wherein the porous material is cellulose, a polymer, or porous alumina.
[18] The fluorinated hydrocarbon detection sensor according to any one of [15] to [17], wherein a polymer containing a compound having the phosphorus-nitrogen double bond is used.

According to the present invention, fluorinated unsaturated hydrocarbons such as C ₅ F ₈ and C ₄ F ₆ , and / or at least a hydrogen-carbon moiety in the molecule can be easily and quickly near room temperature without using high temperatures. Fluorinated saturated hydrocarbons having an anionic leaving group bonded to the adjacent carbon bonded to the carbon of the hydrogen-carbon portion, and interference of interfering gases from the fluorinated liquid They can be detected without receiving them. In addition, the method of the present invention can be applied to sensors, alarm devices, measuring instruments, etc. that efficiently detect fluorinated unsaturated hydrocarbons such as C ₅ F ₈ and C ₄ F ₆ and the fluorinated saturated hydrocarbons, Furthermore, it can be applied to a selective removal and decomposition technique.

In the present invention, a fluorinated unsaturated hydrocarbon such as C ₅ F ₈ or C ₄ F ₆ is brought into contact with a compound represented by the following general chemical formula (I) to cause a reaction, and the fluorinated hydrocarbon Is detected.

In the compound represented by the above general formula (I), R _{1 to} R ₄ are general amine groups or hydrocarbon groups (that is, all functional groups in organic chemistry; carbon-based alkyl, aromatic Group, heteroatom, typical element, transition metal, alkali metal, alkaline earth metal, and components selected from those ions, which may be a heterocyclic ring) and substituents formed from polymers having them And the case where these substituents form a cyclic portion between each R.

That is, in the above general formula (I), each of R _{2 to} R ₄ represents a starting point for chemical bonding with the phosphorus atom in the general formula (I), and R ₁ is a starting point for chemical bonding with the nitrogen atom. Represents. Each of R _{1 to} R ₄ is basically a carbon having an SP ² orbital such as an amino group, a methylene group (CH ₂ ), or benzene, and may be substituted with another heteroatom.
A substituent formed from a general hydrocarbon group or a polymer having the same may be bonded or inserted at the end of R _{1 to} R ₄ , and a cyclic structure is formed between adjacent Rs. Including the case where these substituents form additional cyclic moieties.
Here, the general hydrocarbon group includes a component selected from general functional groups in organic chemistry; heteroatoms, typical elements, transition metals, alkali metals, alkaline earth metals, and ions thereof. It may be a ring. For example, alkyl, alkene, alkyne, phenyl, naphthyl, anthracenyl, hydroxy, alkoxy, aldehyde, ketone, ether, crown ael, polyethylene glycol, carboxylic acid ester, carboxylate, acetal, epoxy, amino, amide, imino, Nitro, cyano, isocyano, thioisocyano, azo, azoxy, porphyrin, thiol, sulfide, disulfide, sulfinate, sulfonate, salts of these acids, pyridine, pyrrole, pyrrolidine, piperidine, morpholine, piperazine, quinoline, arlysine, It means a group of compounds in which substituents such as thiophene, furan, transition metal complex and the like are bonded or bonded in the middle, and an organic polymer is bonded through them.

  Although the example of the compound which has a phosphorus-nitrogen double bond represented with general formula (I) is described in the Example, it is not limited to these. These compounds are those already known as basic reagents used in organic synthesis or the like, or compounds derived therefrom.

As described above, the general formula represented by the formula (I), the phosphorus - compounds with nitrogen double bond, may also have a polymer has been substituted skeleton in R ₁ to R _4, as an example, R ₂ Phosphazene base P2-t-Buon polystyrene having a dimethylamino group bonded to R ₄ and polystyrene in the R ₁ part, or 2-tert-butylimino-2-diethylamino-1,3-dimethylperhydro- There is 1,3,2-diazaphosphorine, polymer-supported (2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine, polymer-bound).

The fluorinated hydrocarbons to be detected in the present invention include fluorinated unsaturated hydrocarbons composed of at least carbon and fluorine and having at least a carbon-carbon double and / or carbon-carbon triple bond compound in the molecule. Some of these include compounds in which other atoms such as chlorine, bromine, iodine, oxygen, sulfur, nitrogen are substituted, and part of the series of fluorinated unsaturated hydrocarbons evaluated in the Kyoto Protocol.
For example, as an _{example, C 2 F 4, C 3} F 6, C 4 F 6, c-C 4 F 8, c-C 5 F 8, CF 3 OCF = CF 2, C 2 F 5 OCF = CF 2 (c -Represents cyclic: cyclic, c-C ₅ F ₈ is the same as C ₅ F ₈ described above, and C ₄ F ₆ has the two types described above. Some of these are often used as etching gases in semiconductor processes.

In addition, the fluorinated hydrocarbons to be detected in the present invention include other fluorinated hydrocarbons that react in the same manner as the above-mentioned fluorinated unsaturated hydrocarbons. The fluorinated hydrocarbon includes at least a hydrogen-carbon moiety in the molecule and an anionic leaving group (for example, fluorine, chlorine, etc.) adjacent to the carbon of the hydrogen-carbon moiety. Fluorinated saturated hydrocarbons to which a chalcogen group such as halogen, alkoxy, ether, sulfide, etc., or a substituent such as carboxylic acid or sulfonic acid) is bonded. These were evaluated in the Kyoto Protocol. Fluorinated unsaturated hydrocarbons that are a series of gaseous compounds partly belong.
For example, CF ₃ CHF ₂ , CHF ₂ CHF ₂ , CF ₃ CHFCF ₃ , CF ₃ CF ₂ CHF ₂ , CHF ₂ CF ₂ CHF ₂ , CF ₃ OCHFCF ₃ , c-C ₅ F ₈ H _2, etc. are examples. Some of these may be used as etching gases in semiconductor processes.
When these fluorides are brought into contact with a compound having a phosphorus-nitrogen double bond represented by the above general formula (I), a color reaction is caused and detection is performed using the optical change. Can do.

The compound having a phosphorus-nitrogen double bond represented by the general formula (I) can be used as a mixture by coexisting with other organic substances.
Examples of organic substances to be mixed include general organic solvents (for example, alcohols such as ethanol, ethylene glycol and glycerin, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), and hexamethylphosphoric triamide (HMPA)). Amides such as tetrahydrofuran (THF) and ethers such as dioxane), diisopropylamine (for LDA), organic liquids such as triisobutylamine, dicyclohexylmethylamine and pentamethylpiperidone, organic solids such as ureas, cellulose and Examples thereof include organic polymers such as polyethylene, polybutadiene, polyethylene acrylate, and polyimide polybenzoic acid.
The content of the compound having a phosphorus-nitrogen double bond represented by the general formula (I) is in the range of 0.1 to 99.9% by mass. Preferably, it is the range of 10-80 mass%.

For the reaction for detection, the compound having a phosphorus-nitrogen double bond and the above-mentioned fluorinated hydrocarbon to be detected may be in contact with each other. The liquid may be applied to a substrate, the porous material may be impregnated with the liquid, or a polymer containing the compound may be applied to a substrate.
As a form of detection using these various forms, for example,
(1) A mode in which a fluorinated hydrocarbon to be detected is brought into contact with a liquid containing a compound having a phosphorus-nitrogen double bond,
(2) A mode in which a fluorinated hydrocarbon to be detected is brought into contact with a polymer film containing a compound having a phosphorus-nitrogen double bond,
(3) A mode in which a fluorinated hydrocarbon to be detected is brought into contact with cellulose containing a compound having a phosphorus-nitrogen double bond,
(4) A mode in which a fluorinated hydrocarbon to be detected is brought into contact with a tape or a sheet containing a compound having a phosphorus-nitrogen double bond,
(5) A mode in which a fluorinated hydrocarbon to be detected is brought into contact with the inside of a tube containing beads or particles containing a compound having a phosphorus-nitrogen double bond,
(6) There are embodiments in which the fluorinated hydrocarbon to be detected is brought into contact with a tape on which beads or particles containing a compound having a phosphorus-nitrogen double bond are fixed, and all embodiments are included. For example, a mode in which a fluorinated hydrocarbon to be detected is bubbled into a liquid containing a compound having a phosphorus-nitrogen double bond or a compound having a phosphorus-nitrogen double bond is used as a fluorinated hydrocarbon to be detected. As in the mode of passing through the contained cellulose, the fluorinated hydrocarbon to be detected may come into contact with any substrate or substance, and all modes are included. The polymer containing a compound having a phosphorus-nitrogen double bond refers to a case where a compound having a phosphorus-nitrogen double bond is physically mixed in an organic polymer, or a phosphorus-nitrogen double bond. This means that the compound having a chemical bonding form.
In the aspect in which the fluid to be detected is brought into contact, the speed at which the fluid to be detected is flowed, that is, the flow rate is set, but the present invention is not limited to this. From the viewpoint of promoting the reaction, the flow rate is preferably 800 mL / min or more. From the viewpoint of the apparatus, 200 to 2000 mL / min is preferable. From the viewpoint of energy saving, 20 to 500 mL / min is preferable.

  The present invention detects a target fluorinated hydrocarbon by a smoothly proceeding reaction using a compound having a phosphorus-nitrogen double bond. The set reaction temperature is 100 degrees Celsius or less, and preferably 0 to 60 degrees. Near room temperature (20 degrees Celsius ± 10 degrees Celsius) is most preferable.

In the present invention, the optical change can be any optical change accompanying a molecular reaction.
For example, the change in absorbance is caused by the change in the transmittance of light having a wavelength in the ultraviolet-visible light region, and the ultraviolet-visible light region in the present invention refers to the ultraviolet light region including vacuum ultraviolet light from purple, blue, green, yellow. , Orange and red, including visible light region, and the wavelength is preferably in the range of 200 to 800 nm. The range of 300 to 700 nm is most preferable from the viewpoint of the light source. In visible light, it can also be detected by visual colorimetry. Further, it is possible to detect an optical change using a machine in ultraviolet and visible light.

  The change in reflectance is caused by a change in the reflectance of the surface due to a change in transmittance of light having a wavelength in the ultraviolet-visible light region or a change in scattering, and is strongly related to a change in absorbance. Similar to the change in absorbance, the ultraviolet-visible light region means the light region from the ultraviolet light region including vacuum ultraviolet light to the visible light region including purple, blue, green, yellow, orange, and red, and has a wavelength of 200 to 800 nm. The range of is preferable. The range of 300 to 700 nm is most preferable from the viewpoint of the light source.

The change in infrared vibration is caused by a change in expansion and contraction in each bond in the molecule in the infrared region, and the infrared vibration in the present invention is a region from the near infrared region to the infrared region, and further to the far infrared region. It is vibration in. For Kaiser, a range of 10 to 4000 cm ⁻¹ is preferred. From the viewpoint of measurement, the range of 1000-1500 cm ⁻¹ is most preferable.

  A change in light emission or phosphorescence is a change in light emitted during energy transfer from the excited state of the molecule to the ground state, which changes with the reaction of the molecule. In the present invention, the excited state is generated by the excited light. . Therefore, the region of light used is the same as the region used for changes in absorbance and reflectance. Changes in emission or phosphorescence may increase or decrease in intensity. The change in refractive index is caused by the change in the dielectric constant of the portion that changes with the reaction of the molecule. The measurement is often performed in air, and the light used is preferably in the ultraviolet and visible light region, and the value is preferably changed in the range of 0.1 to 3.2. The change in the liquid crystal state is caused by a change in the orientation state of the molecule that changes with the reaction of the molecule, and in particular, a change between the isotropic liquid state and the nematic liquid crystal or smectic liquid crystal is used. Polarized light in the UV-visible region is used.

  The change in photoelectron kinetic energy due to X-rays is caused by the change in the atomic state in the molecule that changes with the reaction of the molecule, and the change in the observed photoelectron kinetic energy is measured. As the light source, X-rays of MgKα and AlKα are preferably used. The change in photoelectron kinetic energy measured from the viewpoint of reaction is preferably measured in the range of 200 to 800 eV. By using the optical change of the above one or a combination of two or more, the fluorinated hydrocarbon to be detected can be detected with high sensitivity.

  In the present invention, mass change due to reaction can also be used, and a compound having a phosphorus-nitrogen double bond is placed on a surface that vibrates at a constant frequency, for example, on a QCM (Quarts Crystal Microbalance) substrate. By adsorbing and detecting the change in mass due to the reaction between the film surface and the fluorinated hydrocarbon by the change in the frequency of the QCM, the fluorinated hydrocarbon to be detected can be detected. The surface that vibrates at a constant frequency is not limited to the QCM, and may be in another form. The frequency of vibration can take any value. From the viewpoint of accuracy, the order of kHz to MHz is preferable. Furthermore, a balance capable of measuring mass change by other methods can also be used.

  By using the present invention, a fluorinated unsaturated hydrocarbon to be detected in a short time, or a molecule having at least a hydrogen-carbon portion in the molecule and bonded to the carbon of the hydrogen-carbon portion. It is possible to detect a fluorinated saturated hydrocarbon in which an anionic leaving group is bonded to carbon (hereinafter, both may be simply referred to as “a fluorinated hydrocarbon to be detected”).

  By using the present invention, fluorinated hydrocarbons to be detected can be detected with high sensitivity. For example, it is possible to detect gaseous fluorinated hydrocarbons to be detected at 50 to 1000 ppm. From the viewpoint of practical use, detection of a concentration of 5 ppm is desirable and possible. From the viewpoint of the control reference concentration, detection of a concentration of 2 ppm is desirable and possible. For commercialization and improvement of reliability, it is desirable to detect a concentration of 0.1 ppm or less within 1 minute.

  The present invention measures optical changes by a special reaction that proceeds smoothly around room temperature using a compound having a phosphorus-nitrogen double bond, but it uses a reaction group unique to organic molecules, Selectivity is demonstrated. That is, fluorinated liquids frequently used in cleaning agents, insulators, etc., such as Fluorinert (registered trademark) (fluorinated inert liquid component; perfluorocarbon), Galden (registered trademark) (fluorinated inert liquid component; perfluorocarbon) ), Novec (registered trademark) (component: HFE hydrofluoroether), and the like, it does not show reactivity despite the excessive presence of gaseous saturated hydrocarbon fluoride as an interfering gas, Fluorinated hydrocarbons to be selectively detected can be detected with high sensitivity without causing false alarms.

  In the present invention, optical changes are measured by a special reaction that proceeds smoothly around room temperature using a compound having a phosphorus-nitrogen double bond. The signal processing is performed by combining an apparatus, a personal computer, and software. It is not limited to those models, types, and forms, and can be measured sufficiently by devising and using existing or produced ones. An optical change can be grasped by a change in peak intensity at a specific wavelength in each spectrum, a change in an integrated value in a certain wavelength region, or a change in spectrum shape. At that time, a more accurate change can be captured by setting a peak intensity of a specific wavelength of each spectrum serving as a reference, an integral value of a certain wavelength region, or a spectrum shape. By these combinations, finally, the fluorinated hydrocarbon to be detected can be selectively detected with high sensitivity.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples. All modifications and other embodiments or examples within the scope of the technical idea of the present invention are included in the present invention.
Example 1
2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine) When 0.5 mL of a 20 mM C ₅ F ₈ THF solution was added to about 100 mg, a reddish brown change was confirmed at UV-visible absorption around 400 nm ± 200 nm. In particular, the change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable. The UV-visible light was measured using SpectraSuite from Ocean Optics. An Hg-Xe lamp was used as a light source for ultraviolet visible light. The same applies to the following embodiments.
As described above, C ₅ F ₈ , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.

(Example 2)
N-tert-butyl -N- hexamethylphosphorylamide Midi Tsu Kutoriamido (N-tert-Butyl-N -hexamethylphos p horimidic triamide) C to liquid dry nitrogen based gaseous concentration of about 0.1% ₅ F ₈ When 10 mL was taken with a syringe and sprayed on the solution, a change in ultraviolet-visible absorption could be confirmed at around ± 200 nm ± 200 nm. In particular, a change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable.
As described above, a mixed gas of C ₅ F ₈ , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.

(Example 3)
2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine) When about 4 μL is immersed in a filter paper having a diameter of about 7 mm, and C ₅ F ₈ having a gaseous concentration of about 2 ppm based on dry nitrogen is sprayed on the filter paper, the change in ultraviolet-visible absorption is about 200 nm ± 200 nm. It was confirmed in. In particular, the change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable.
As described above, C ₅ F ₈ , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.

Example 4
2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3-dimethylperhydro-1,3-dimethylperhydro-1,3,2-diaza- Phosphorine) is immersed in a filter paper having a diameter of about 7 mm, and dry nitrogen-based gaseous concentration of C ₅ F ₈ and concentration of C ₄ F ₆ of about 0.1% are added thereto. When the mixture was mixed at 1: 1, taken with a syringe, and sprayed onto the filter paper, a change in UV-visible absorption was confirmed at around ± 200 nm ± 200 nm. In particular, the change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable.
As described above, a mixed gas of C ₅ F ₈ and C ₄ F ₆ , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.

(Example 5)
N '''- tert- butyl -N, N, N', N ', N'',N''- hexamethyl phosphoryl Midi Tsu Kutoriamido (N''' - tert- Butyl-N, N, N ' , N ′, N ″, N ″ -hexamethyphos p horimidic triamide) was mixed with about 1 mL of Nujol (liquid paraffin). When 0.1 mL of a 10 mM C ₅ F ₈ tetrahydrofuran (THF) solution cooled thereto was added thereto, a brown color change was confirmed at an ultraviolet-visible absorption around 400 nm ± 200 nm. In particular, the change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable. From the infrared absorption spectrum of this brown substance, a signal of 1100 to 1300 cm ⁻¹ peculiar to CF vibration can be observed. This change can also be detected in X-ray photoelectron spectroscopy observations. Specific to F1s, C ₅ F ₈ and N '''- tert- butyl -N, N, N', N ', N'',N''- optoelectronic motion by the reaction of hexamethylphosphorylamide Midi Tsu Kutoriamido A peak of about 690 eV corresponding to the energy is detected. For measurement of infrared absorption and X-ray photoelectron spectroscopy, BioRad and ESCA-KM were used, respectively. The same applies to the following.
As described above, C ₅ F ₈ , which is a kind of unsaturated hydrocarbon fluoride, can be detected by each method of optical change.

(Example 6)
2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine) About 4 μL is immersed in an alumina plate (neutral alumina, for TLC), and a dry nitrogen-based gaseous concentration of about 0.1% octafluorocyclopentane (C ₅ F ₈ H ₂ ) is applied to the surface. When sprayed on, a change in ultraviolet-visible absorption was confirmed at around 200 nm ± 200 nm. In particular, a change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable.
As described above, by using one of the optical change methods, an anionic leaving group is present on the adjacent carbon having at least a hydrogen-carbon portion in the molecule and bonded to the carbon of the hydrogen-carbon portion. C ₅ F ₈ H ₂ gas, which is a kind of bonded fluorinated hydrocarbon, could be detected.

(Example 7)
2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine) About 4μL is soaked in an alumina plate (neutral alumina, for TLC), and when a dry nitrogen-based gaseous C ₅ F ₈ of about 0.1% is blown onto the surface, the ultraviolet-visible absorption change Was confirmed at ± 200 nm around 400 nm. In particular, a change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable.
As described above, C ₅ F ₈ gas, which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.

(Example 8)
About 100 mg of phosphazene base (P2-t-Buon polystyrene) was mixed with 1.5 mL of N-methyl-2-pyrrolidone (NMP) which is one kind of organic solvent. When 10 mL of C ₅ F ₈ having a gaseous concentration of about 0.1% based on dry nitrogen was taken with a syringe and bubbled into the solution, an ultraviolet-visible absorption change could be confirmed at around 200 nm ± 200 nm. In particular, a change in UV-visible absorption at 250 to 300 nm having a peak in the vicinity of about 280 nm was remarkable.
As described above, C ₅ F ₈ gas, which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using one of the optical change methods.

Example 9
The surface of QCM (Quarts Crystal Microbalance) on which gold was deposited was immersed in an ethanol solution of 6-hydroxyhexanethiol. 2-tert-Butylimino-2-diethylamino-1.3-dimethyl-perhydro-1, 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphospholine (2-tert-Butylimino-2-diethylamino-1.3-dimethyl-perhydro-1, 3,2-diazaphosphorine) ethanol solution was cast and dried under nitrogen atmosphere. When the surface of the film is set in the QCM apparatus in the chamber and 0.1% C ₅ F ₈ gas is introduced, the change in the frequency of the QCM (reference and reference) is caused by the change in the mass of the film surface formed on the QVCM. Frequency = 6 MHz).
As described above, C ₅ F ₈ , which is a kind of fluorinated unsaturated hydrocarbon, can be detected by using a mass change due to a reaction of a compound having a phosphorus-nitrogen double bond.

(Example 10)
The surface of QCM (Quarts Crystal Microbalance) on which gold was deposited was immersed in an ethanol solution of 6-hydroxyhexanethiol. 2-tert-Butylimino-2-diethylamino-1.3-dimethyl-perhydro-1, 2-tert-butylimino-2-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphospholine (2-tert-Butylimino-2-diethylamino-1.3-dimethyl-perhydro-1, 3,2-diazaphosphorine) ethanol solution was cast and dried under nitrogen atmosphere. When the surface of the film is set in the QCM apparatus in the chamber and 0.1% C ₅ F ₈ H ₂ gas is introduced, the change in the frequency of the QCM (with the change in the mass of the film surface formed on the QVCM ( Reference frequency = 6 MHz) was confirmed.
As described above, C ₅ F ₈ H ₂ , which is a kind of fluorinated saturated hydrocarbon, can be detected using mass change due to the reaction of the compound having a phosphorus-nitrogen double bond.

Claims (18)

Fluorinated unsaturated hydrocarbon, or fluorinated saturated having an anionic leaving group bonded to the adjacent carbon having at least a hydrogen-carbon moiety in the molecule and bonded to the carbon of the hydrogen-carbon moiety Detection of a fluorinated hydrocarbon, characterized by detecting a fluorinated hydrocarbon using a reaction between a hydrocarbon and a compound having a phosphorus-nitrogen double bond represented by the following general formula (I) Method.

[In the formula, R _{1 to} R ₄ are general amine groups or hydrocarbon groups (that is, all functional groups in organic chemistry; carbon-based alkyls, aromatics, heteroatoms, typical elements, transition elements) Including components selected from metals, alkali metals, alkaline earth metals, and ions thereof, which may be heterocyclic) or in the presence of substituents formed from polymers having them This includes the case where a group forms a cyclic portion between each R. ]   The detection method according to claim 1, wherein an optical change due to the reaction is detected.   The detection method according to claim 1, wherein the detection is performed using an embodiment in which an organic substance other than the compound having a phosphorus-nitrogen double bond represented by the general formula (I) coexists. Said fluorinated unsaturated hydrocarbons, detection method according to claim 1, characterized in that the C ₅ F ₈ or C ₄ F ₆ or mixtures thereof. The detection method according to claim 4, wherein the C ₅ F ₈ is octafluorocyclopentene. The C ₄ F ₆ is, the detection method of claim 4 hexafluoro butadiene or Hekisafu Le Orosi Clos butene or mixtures thereof. Detection method according to any one of claims 1-3, wherein the fluorinated saturated hydrocarbon, characterized in that it is a C ₅ F ₈ H _2. The detection method according to claim 7, wherein the C ₅ F ₈ H ₂ is octafluorocyclopentane. The detection method according to claim 7, wherein the C ₅ F ₈ H ₂ is 1H, 2H-octafluorocyclopentane, 1H, 1H-octafluorocyclopentane, 1H, 3H-octafluorocyclopentane, or a mixture thereof.   Detects one or more optical changes selected from changes in absorbance, reflectance, infrared vibration, luminescence, fluorescence, phosphorescence, refractive index, liquid crystal state, and photoelectron kinetic energy due to X-rays in the reaction. The detection method according to any one of claims 1 to 9, wherein:   11. The detection method according to claim 10, wherein a fluorinated hydrocarbon having a concentration of 0.1% or less is detected by using an absorbance change or reflectance change in the ultraviolet-visible light region as the optical change. .   The detection method according to claim 1, wherein a change in mass due to the reaction is detected.   The compound having the phosphorus-nitrogen double bond is at least adsorbed on the surface vibrating at a certain frequency, and the mass resulting from the reaction between the film surface formed thereby and the fluorinated unsaturated hydrocarbon or the fluorinated saturated hydrocarbon The detection method according to claim 12, wherein the change is captured by a change from a constant frequency of vibration on the surface. Fluorinated unsaturated hydrocarbon, or fluorinated saturated having an anionic leaving group bonded to the adjacent carbon having at least a hydrogen-carbon moiety in the molecule and bonded to the carbon of the hydrogen-carbon moiety A detection agent for detecting a hydrocarbon, comprising a compound having a phosphorus-nitrogen double bond represented by the following general formula (I) as an active ingredient:

[In the formula, R _{1 to} R ₄ are general amine groups or hydrocarbon groups (that is, all functional groups in organic chemistry; carbon-based alkyls, aromatics, heteroatoms, typical elements, transition elements) Including components selected from metals, alkali metals, alkaline earth metals, and ions thereof, which may be heterocyclic) or in the presence of substituents formed from polymers having them This includes the case where a group forms a cyclic portion between each R. ] Fluorinated unsaturated hydrocarbon, or fluorinated saturated having an anionic leaving group bonded to the adjacent carbon having at least a hydrogen-carbon moiety in the molecule and bonded to the carbon of the hydrogen-carbon moiety A sensor for detecting hydrocarbons, wherein a compound having a phosphorus-nitrogen double bond represented by the following general formula (I) is used for the detection part: Detection sensor.

[In the formula, R _{1 to} R ₄ are general amine groups or hydrocarbon groups (that is, all functional groups in organic chemistry; carbon-based alkyls, aromatics, heteroatoms, typical elements, transition elements) Including components selected from metals, alkali metals, alkaline earth metals, and ions thereof, which may be heterocyclic) or in the presence of substituents formed from polymers having them This includes the case where a group forms a cyclic portion between each R. ]   The fluorinated hydrocarbon detection sensor according to claim 15, wherein a liquid containing the compound having a phosphorus-nitrogen double bond is impregnated in a porous material.   The fluorinated hydrocarbon detection sensor according to claim 16, wherein the porous material is cellulose, a polymer, or porous alumina.   The fluorinated hydrocarbon detection sensor according to any one of claims 15 to 17, wherein a polymer containing a compound having the phosphorus-nitrogen double bond is used.