JPH0769281B2 - Quantitative determination of oxygen-containing compounds in organometallic compounds - Google Patents
Quantitative determination of oxygen-containing compounds in organometallic compoundsInfo
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- JPH0769281B2 JPH0769281B2 JP63131534A JP13153488A JPH0769281B2 JP H0769281 B2 JPH0769281 B2 JP H0769281B2 JP 63131534 A JP63131534 A JP 63131534A JP 13153488 A JP13153488 A JP 13153488A JP H0769281 B2 JPH0769281 B2 JP H0769281B2
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Description
【発明の詳細な説明】 〔産業上の利用分野〕 この発明は、水素−核磁気共鳴法（1H−NMR法）によっ
て有機金属化合物中の含酸素化合物を定量分析するにあ
たって、特殊な構成の二重試料管を使用し、そして、そ
の定量分析の際に、試料中のアルキル金属化合物のアル
キル基中のプロトンに基づくピークを、ホモゲーテッド
デカップリング法で消去し、微量の含酸素化合物を含有
するアルキル金属化合物からなる試料中の「極めて微量
の含酸素化合物」を、簡単な操作で、迅速に、高い精度
の定量分析する方法に係る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention has a special structure for quantitatively analyzing an oxygen-containing compound in an organometallic compound by a hydrogen-nuclear magnetic resonance method ( 1 H-NMR method). A double sample tube was used, and during the quantitative analysis, the peak based on the proton in the alkyl group of the alkyl metal compound in the sample was eliminated by the homogated decoupling method, and a trace amount of the oxygen-containing compound was contained. The present invention relates to a method for quantitatively analyzing “an extremely small amount of oxygen-containing compound” in a sample composed of an alkyl metal compound by a simple operation, quickly and with high accuracy.
アルキル金属化合物は、精密な電子材料を製造する際に
使用される重要なものであり、そして、このアルキル金
属化合物中に含酸素化合物が微量でも含有されている
と、これを用いて製造された電子材料の本来の性能を著
しく低下させてしまうという問題があった。Alkyl metal compounds are important ones used in the production of precision electronic materials, and even if the alkyl metal compounds contain trace amounts of oxygen-containing compounds, they are produced using these compounds. There is a problem that the original performance of the electronic material is significantly reduced.
すなわい、前記のアルキル金属化合物は、空気などと接
触すると、分割したり、発火したりして、含酸素化合物
が容易に生成してしまうので、前記のアルキル金属化合
物中の微量の含酸素化合物の含有量を測定することによ
って、アルキル金属化合物の品質を管理する必要があっ
た。That is, when the above-mentioned alkyl metal compound is contacted with air or the like, it splits or ignites, and an oxygen-containing compound is easily generated. It was necessary to control the quality of the alkyl metal compound by measuring the content of the compound.
しかし、アルキル金属化合物中の微量の含酸素化合物を
定量する実用的な定量分析法は、アルキル金属化合物
が、微量の空気などに対しても極めて不安定な化合物で
あるために、極めて困難であったものである。However, a practical quantitative analysis method for quantifying a trace amount of oxygen-containing compound in an alkyl metal compound is extremely difficult because the alkyl metal compound is a compound that is extremely unstable even in a trace amount of air. It is a thing.
この発明の目的は、従来、精密な測定法が確立していな
かった「アルキル金属化合物中の微量の含酸素化合物を
容易に定量する実用的な定量分析法」を、新たに提供す
ることである。An object of the present invention is to newly provide "a practical quantitative analysis method for easily quantifying a trace amount of an oxygen-containing compound in an alkyl metal compound" which has not been established with a precise measurement method. .
この発明は、水素−核磁気共鳴法（1H−NMR法）によっ
て有機金属化合物中の含酸素化合物を定量分析するにあ
たって、 二重試料管の内管内に、微量の含酸素化合物を含有する
アルキル金属化合物からなる試料が入れられていると共
に、前記の二重試料管の外管と内管との間の空隙内に、
既知量の微量の軽水素を含有する重水素化ベンゼンから
なる代用標準物質を入れられており、さらに、各開口部
を密封した二重試料管を使用し、 前記二重試料管内の試料を水素−核磁気共鳴法により定
量する際に、 （ａ） 前記二重試料管内のアルキル金属化合物のアル
キル基中のプロトンに基づくピークを、ホモゲーテッド
デカップリング法で消去すると共に、 （ｂ） 前記二重試料管内のアルキル金属化合物中の微
量の含酸素化合物中の酸素に直接結合した炭素についた
水素を、高精度で定量することを特徴とする有機金属化
合物中の含酸素化合物の定量法に関する。This invention is intended to quantitatively analyze an oxygen-containing compound in an organometallic compound by a hydrogen-nuclear magnetic resonance method ( 1 H-NMR method), wherein an alkyl containing a trace amount of the oxygen-containing compound is contained in the inner tube of a double sample tube. A sample made of a metal compound is placed, and in the space between the outer tube and the inner tube of the double sample tube,
It contains a substitute standard substance consisting of deuterated benzene containing a known amount of trace amount of deuterium, and furthermore, using a double sample tube with each opening sealed, the sample in the double sample tube is filled with hydrogen. -When quantifying by a nuclear magnetic resonance method, (a) a peak based on a proton in an alkyl group of an alkyl metal compound in the double sample tube is eliminated by a homogated decoupling method, and (b) the double The present invention relates to a method for quantifying an oxygen-containing compound in an organometallic compound, which is characterized by highly accurately quantifying hydrogen attached to carbon directly bonded to oxygen in a trace amount of an oxygen-containing compound in an alkyl metal compound in a sample tube.
すなわち、この発明の定量法は、概略、前記の特殊な形
状の二重試料管内のアルキル金属化合物（試料）中の微
量の含酸素化合物の測定において、その含酸素化合物中
の酸素に直接結合した炭素についた水素（アルコキシ基
の水素）の含有量を高精度で定量することが、主な特長
である。That is, the quantitative method of the present invention is roughly, in the measurement of a trace amount of an oxygen-containing compound in an alkyl metal compound (sample) in a double sample tube having the above-mentioned special shape, directly bonded to oxygen in the oxygen-containing compound. The main feature is that the content of hydrogen on carbon (hydrogen of alkoxy group) can be quantified with high accuracy.
以下、この発明の定量法について、図面も参考にして、
さらに詳しく説明する。Hereinafter, regarding the quantification method of the present invention, with reference to the drawings,
This will be described in more detail.
第１図は、この発明の定量法に使用する二重試料管の概
略を示す断面図である。FIG. 1 is a sectional view showing an outline of a double sample tube used in the quantification method of the present invention.
この発明における水素−核磁気共鳴法（1H−NMR法）に
よって有機金属化合物中の含酸素化合物を定量分析する
にあたって使用する『二重試料管』は、例べば、第１図
に示すように、通常のガラス製、NMR用試料管などを用
いることができ、その二重試料管１の内管２の内部に、
微量の含酸素化合物を含有するアルキル金属化合物から
なる試料４を入れると共に、前記二重試料管１の外管３
と内管２との間の空隙部６内に、微量の軽水素を含有す
る重水素化ベンゼンからなる標準物質代用物５を入れ
る。The "double sample tube" used for quantitatively analyzing an oxygen-containing compound in an organometallic compound by the hydrogen-nuclear magnetic resonance method ( 1 H-NMR method) in the present invention is, for example, as shown in FIG. In addition, an ordinary glass sample tube for NMR, etc. can be used, and inside the inner tube 2 of the double sample tube 1,
A sample 4 made of an alkyl metal compound containing a trace amount of an oxygen-containing compound is put therein, and the outer tube 3 of the double sample tube 1 is placed.
A standard substance substitute 5 made of deuterated benzene containing a slight amount of light hydrogen is put in a space 6 between the inner tube 2 and the inner tube 2.
また、内管２の先端の熔封部を保護するために、テフロ
ン製チューブガード７をつけ、さらに内管２を外管に固
定するため、テフロン製固定具８、９を使用したものが
好ましい。Further, it is preferable to use a Teflon tube guard 7 in order to protect the sealed portion at the tip of the inner tube 2 and to use Teflon fixing tools 8 and 9 for fixing the inner tube 2 to the outer tube. .
前記の二重試料管は、内管の内径が２〜15mm、特に３〜
10mm程度であればよく、また、外管の内径が５〜20mm、
特に８〜15mm程度であり、さらに、前記内管と外管とが
同心円状に配置されていて、その際の内管と外管との間
の空隙部の間隔が0.5〜8mm、特に１〜5mm程度であるこ
とが好ましい。The double sample tube has an inner diameter of 2 to 15 mm, especially 3 to
It only needs to be about 10 mm, and the inner diameter of the outer tube is 5 to 20 mm,
In particular, it is about 8 to 15 mm, and the inner tube and the outer tube are concentrically arranged, and the space between the inner tube and the outer tube at that time is 0.5 to 8 mm, particularly 1 to It is preferably about 5 mm.
前記の固定具の材質としては、テフロンに限定されるも
のではなく、例えば、ポリエチレン、ポリプロピレ、ポ
リアセタール、ポリアミドなどの合成樹脂を挙げること
もできる。The material of the fixing device is not limited to Teflon, and examples thereof include synthetic resins such as polyethylene, polypropylene, polyacetal, and polyamide.
前記の試料はアルキル金属化合物を主成分であり、アル
キル金属化合物を約95重量％以上、特に98重量％以上、
さらに99.0重量％以上の割合で含有するものであって、
しかも、アルキル金属化合物が空気中の酸素と接触する
ことによって分解し生成する含酸素化合物、あるいは、
アルキル化合物を製造する際に副生する含酸素化合物な
ど（例えば、メトキシ基、エトキシ基、プロポキシ基、
ブトキシ基などのアルコキシ基を、１〜４個、特に１個
有する有機金属化合物である含酸素化合物）が、約20〜
2000ppm、特に25〜1000ppm程度の含有割合で含有されて
いる試料であればよい。The above-mentioned sample is mainly composed of an alkyl metal compound and contains about 95% by weight or more, particularly 98% by weight or more of an alkyl metal compound.
Furthermore, the content is 99.0% by weight or more,
Moreover, an oxygen-containing compound that is generated by decomposition of an alkyl metal compound when it contacts oxygen in the air, or
Oxygen-containing compounds and the like that are by-produced when producing an alkyl compound (for example, a methoxy group, an ethoxy group, a propoxy group,
An oxygen-containing compound, which is an organometallic compound having 1 to 4, especially 1 alkoxy group such as butoxy group, is about 20 to
A sample containing 2000 ppm, particularly 25 to 1000 ppm, may be used.
前記のアルキル金属としては、炭素数１〜６個のアルキ
ル基（飽和炭化水素基）を２〜４固有する、アルミニウ
ム、ガリウム、インジュウム、リン、ヒ素、アンチモ
ン、珪素、ゲルマニウム、錫、亜鉛、セレン、テルルな
どの周期律表のII〜VI族金属の化合物であればよく、例
えば、トリメチルアルミニウム、トリエチルアルミニウ
ム、トリプロピルアルミニウム、トリイソプロピルアル
ミニウムなどのトリアルキルアルニミウム、トリメチル
ガリウム、トリエチルガリウムなどのトリアルキルガリ
ウム、トリメチルアルシン、トリエチルアルシン、ジエ
チル亜鉛などを挙げることができる。Examples of the alkyl metal include aluminum, gallium, indium, phosphorus, arsenic, antimony, silicon, germanium, tin, zinc and selenium, which have 2 to 4 alkyl groups (saturated hydrocarbon groups) having 1 to 6 carbon atoms. , Compounds of Group II to VI metals of the Periodic Table such as tellurium, for example, trialkylaluminium such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trialkylgallium, triethylgallium and the like. Examples thereof include alkylgallium, trimethylarsine, triethylarsine, diethylzinc and the like.
また、前記の含酸素化合物としては、例えば、メトキシ
−ジメチルアルミニウム、エトキシジエチルアルミニウ
ム、メトキシジメチルガリウム、エトキシジエチルガリ
ウム、メトキシジメチルヒ素、メトキシジメチルインジ
ウムなどを挙げることができる。Examples of the oxygen-containing compound include methoxy-dimethylaluminum, ethoxydiethylaluminum, methoxydimethylgallium, ethoxydiethylgallium, methoxydimethylarsenic, and methoxydimethylindium.
前記代用標準物質は、置換基を有していないベンゼンが
重水素化されることによって得られた、微量の軽水素
を、原子比で、好ましくは100〜2000ppmの割合で含有す
る高純度の重水素化ベンゼンからなる代用標準物質であ
ればよい。The substitute standard substance is obtained by deuteration of benzene having no substituent, and a small amount of light hydrogen, in an atomic ratio, preferably a high-purity deuterium containing at a ratio of 100 to 2000 ppm. Any substitute standard substance consisting of hydrogenated benzene may be used.
前記の二重試料管を作成する方法は、例えば、まず、内
管となるガラス製の試料管内にアルキル金属化合物を、
比較的低温（特に25℃以下の温度）、及び不活性な雰囲
気で密封した封管サンプルを準備し、次いで、その封管
サンプルを、外管となる試料管内に配置して、さらに、
内管と外管との間の空隙部に代用標準物質となる重水素
化ベンゼンを入れる方法を挙げることができる。The method of creating the double sample tube is, for example, first, an alkyl metal compound in a glass sample tube to be an inner tube,
Prepare a sealed tube sample sealed in a relatively low temperature (especially a temperature of 25 ° C. or less) and an inert atmosphere, and then place the sealed tube sample in a sample tube to be an outer tube, and further,
A method in which deuterated benzene as a substitute standard substance is placed in the space between the inner tube and the outer tube can be mentioned.
この発明の定量法では、前述の二重試料管を使用して水
素−核磁気共鳴法（1H−NMR法）によって試料の定量分
析するにあたって、 （ａ）ホモゲーテッドデカップリング法で感度をさげて
前記内管の内部のアルキル金属化合物の『アルキル基
（メチル基など）中のプロトン』に基づく『郷土の大き
いシグナルピーク』を小さくし実質的に消去すると共
に、 （ｂ）前記の外管と内管との間の空隙部の代表標準物質
中の『プロトン』に基づく『基準ピーク』と前記の内管
内のアルキル金属化合物中の微量の『含酸素化合物』中
のアルコキシ基のα−水素に基づく『測定対象ピーク』
とを積算効率よく測定して、 アルキル金属化合物中の微量の含酸素化合物を高精度で
正確に定量するのである。In the quantitative method of the present invention, in the quantitative analysis of a sample by the hydrogen-nuclear magnetic resonance method ( 1 H-NMR method) using the double sample tube described above, (a) the sensitivity is reduced by the homogated decoupling method. And “substantially eliminates the“ large signal peak of the native region ”based on the“ proton in the alkyl group (methyl group etc.) ”of the alkyl metal compound inside the inner tube, and (b) with the outer tube. The "reference peak" based on the "proton" in the representative standard substance in the void between the inner tube and the α-hydrogen of the alkoxy group in the trace "oxygenated compound" in the alkyl metal compound in the inner tube Based on "peak to be measured"
By measuring and with high integration efficiency, trace amounts of oxygen-containing compounds in alkyl metal compounds can be accurately and accurately quantified.
この発明は定量法では、前記の水素−核磁気共鳴法は、
前述の二重試料管を、磁場強度４テスラー以上の超伝導
マグネットの中に入れて、1H−NMR測定を行うことが好
ましい。This invention is a quantitative method, the above-mentioned hydrogen-nuclear magnetic resonance method,
It is preferable to perform the 1 H-NMR measurement by putting the above-mentioned double sample tube in a superconducting magnet having a magnetic field strength of 4 Tesler or more.
前記ホモゲーテッドデカップリング法とは、溶媒、水分
などの信号を消去するための手法であり、観測パルスを
出す直前まで消去すべきプロトンを照射して飽和させる
ことによって信号消去を行うという方法である。The homogated decoupling method is a method for erasing signals such as solvent and water, and is a method for erasing signals by irradiating and saturating with protons to be erased until just before issuing an observation pulse. .
この発明の定量法における水素−核磁気共鳴法では、得
られたスペクトルデータの一つである各ピークの面積強
度が測定される各化合物のモル数に比例した強度を示す
ので、代用標準物質中の微量のベンゼンと、試料のアル
キル金属化合物中の定量したい微量の含酸素化合物とに
基づく各ピーク面積強度を相対的に比較することによっ
て、前記含酸素化合物を定量することができる。In the hydrogen-nuclear magnetic resonance method in the quantification method of the present invention, the area intensity of each peak, which is one of the obtained spectral data, shows an intensity proportional to the number of moles of each compound to be measured. The oxygen-containing compound can be quantified by relatively comparing the respective peak area intensities based on the trace amount of benzene and the trace amount of the oxygen-containing compound to be quantified in the sample alkyl metal compound.
この発明の定量法では、水素−各磁気共鳴法を採用して
いるので、測定の操作が比較的簡単であり、測定する際
の前処理などの作業も短時間で行うことができると共
に、定量する際の精度は、相対誤差で通常１〜３％程度
であり、さらに、最も優れた利点としえは、熱的に、あ
るいは空気、各種溶媒などとの接触に不安定な試料化合
物であっても、安定に、直接、試料化合物の定量データ
を得ることができるという優れた点がある。In the quantification method of the present invention, since the hydrogen-each magnetic resonance method is adopted, the measurement operation is relatively simple, and the work such as pretreatment at the time of measurement can be performed in a short time. The relative error is usually about 1 to 3% in relative error, and the best advantage is that even if the sample compound is unstable thermally or in contact with air, various solvents, etc. However, there is an excellent point that quantitative data of the sample compound can be obtained stably and directly.
また、本発明の定量法では、既知量の軽水素を含有する
重水素化ベンゼンを代用標準物質として、特殊な二重試
料管の外管と内管との空隙部に入れ、また試料を前記二
重試料管の内管の内部に入れて測定に使用しているの
で、一般の機器分析において定量的な測定をする場合に
原則として必要とされる標準物質による検量線の作成を
行う必要がないと共に、標準物質の試料化合物への添加
による試料化合物の変質、分割などが生じないのであ
る。Further, in the quantification method of the present invention, deuterated benzene containing a known amount of deuterium is used as a substitute standard substance in the space between the outer tube and the inner tube of a special double sample tube, and the sample is Since it is used for measurement by putting it inside the inner tube of the double sample tube, it is necessary to create a calibration curve using standard substances that are required in principle for quantitative measurement in general instrumental analysis. In addition, there is no deterioration or division of the sample compound due to the addition of the standard substance to the sample compound.
以下に実施例を示す。 Examples will be shown below.
実施例１ 内管として使用される予定の「内径が5mmであり、長さ
が230mmである試料管」の中に、20℃および窒素ガスに
よる不活性な雰囲気で、トリアルキルアルミニウム（未
知量の含酸素化合物を微量含有している）を入れて熔封
し、テフロン製チューブガードを付け、次いで、外管と
して使用される予定の「内径が10mmであり、長さが180m
mである試料管」に、「重水素化率が99.93％である重水
素化ベンゼン」を代用標準物質」として加えて、そし
て、第１図に示すように、外管３の内部に内管２を配置
して二重管状態となし、その状態の二重管の上、下の二
箇所（開口部と低部）をテフロン製の固定具で密封およ
びガードして、密諷された二重試料管を形成した。Example 1 In a "sample tube having an inner diameter of 5 mm and a length of 230 mm" to be used as an inner tube, a trialkylaluminum (unknown amount of It contains a small amount of oxygen-containing compounds, is sealed, is fitted with a Teflon tube guard, and is then intended to be used as an outer tube "inner diameter is 10 mm, length is 180 m.
m "sample tube", "deuterated benzene with a deuteration rate of 99.93%" is added as a substitute reference material, and as shown in FIG. 2 is placed to form a double pipe state, and the upper and lower two places (opening and lower part) of the double pipe are sealed and guarded with Teflon fixtures, and the A heavy sample tube was formed.
次いで、その二重試料管を使用して、水素−核磁気共鳴
測定装置（日本電子（株）製;FX−200）内に備えられた
「磁場強度4.7テスラーの超伝導マグネット」の中にフ
リップアングルを45゜として配置して、1H−NMR測定を
行った。Then, using the double sample tube, flip it into the "superconducting magnet with a magnetic field strength of 4.7 Tesler" provided in the hydrogen-nuclear magnetic resonance measurement device (JEOL Ltd. FX-200). 1 H-NMR measurement was performed with the angle of 45 °.
その結果、トリメチルアルミニウム中のメチル基の水素
に由来するシグナルピークの強度が大きく、観測したい
含酸素化合物（メトキシジメチルアルミニウム）のメト
キシ基の水素に由来するピークは非常に小さかったの
で、ホモゲーテッドでカップリング法で、トリメチルア
ルミニウムのメチル基の水素に由来するピーク強度を小
さくし、測定目的物である含酸素化合物の積算効率を向
上する方法を用いて、検出感度を上げた。As a result, the intensity of the signal peak derived from the hydrogen of the methyl group in trimethylaluminum was high, and the peak derived from the hydrogen of the methoxy group of the oxygen-containing compound (methoxydimethylaluminum) to be observed was very small. The coupling method was used to decrease the peak intensity derived from the hydrogen of the methyl group of trimethylaluminum, and to improve the detection efficiency by using the method of improving the integration efficiency of the oxygen-containing compound which is the object of measurement.
この際の1H−NMRスペクトルを第２図に示す。The 1 H-NMR spectrum at this time is shown in FIG.
第２図に示す結果によれば、測定の目的物である『含酸
素化合物』は3.65ppmにシグナルピーク11を有し、代用
標準物質中の軽水素に基づくシグナルは7.24ppmにピー
ク10を示している。両者のプロトンに由来するピーク強
度と、分析範囲内に存在する試料および代用標準物質の
量を比較することにより試料中の含酸素化合物を含酸素
化合物がすべてメトキシジメチルアルミニウムであると
見なして定量することができ、その値は200ppmであっ
た。According to the results shown in FIG. 2, the “oxygen-containing compound”, which is the target substance of the measurement, has a signal peak 11 at 3.65 ppm, and a signal based on light hydrogen in the substitute standard substance shows a peak 10 at 7.24 ppm. ing. By comparing the peak intensities derived from both protons with the amounts of the sample and the substitute standard substance present in the analytical range, the oxygen-containing compound in the sample is quantified assuming that all the oxygen-containing compounds are methoxydimethylaluminum. And the value was 200 ppm.
なお、前述の定量法を多数繰り返して、トリアルキルア
ルミニウム中の含酸素化合物の定量限界を求めた結果、
積算回数を56回でも約100ppmであることが判明した。In addition, as a result of repeating the above-described quantitative method a number of times and determining the quantitative limit of the oxygen-containing compound in the trialkylaluminum,
It was found that the number of times of integration was 56 times, but it was about 100 ppm.
実施例２1 H−NMR測定における測定条件のパラメーターである
「フリップアングル」を、20゜に代えたほかは、実施例
１と同様にして、定量分析を行った。Example 2 Quantitative analysis was performed in the same manner as in Example 1 except that the "flip angle", which is a parameter of the measurement conditions in 1 H-NMR measurement, was changed to 20 °.
その結果、80回の積算スペクトルから、トリアルキルア
ルミニウム中の含酸素化合物の定量限界が約50ppmであ
ることが判明した。As a result, it was found from the integrated spectrum of 80 times that the quantification limit of the oxygen-containing compound in the trialkylaluminum was about 50 ppm.
実施例３ 二重試料管の内管として、内径が7mmである試料管を使
用し、さらに、代用標準物質として重水素化率が99.9％
である重水素化ベンゼンを使用したほかは、実施例１と
同様にして、定量分析を行った。Example 3 A sample tube having an inner diameter of 7 mm was used as the inner tube of the double sample tube, and the deuteration rate was 99.9% as a substitute standard substance.
Quantitative analysis was performed in the same manner as in Example 1 except that deuterated benzene which was
その結果、256回の積算スペクトルから、トリアルキル
アルミニウム中の含酸素化合物の定量限界が約25ppmで
あることが判明した。As a result, it was found from the 256-time integrated spectrum that the quantification limit of the oxygen-containing compound in the trialkylaluminum was about 25 ppm.
本発明の定量法によれば、『既知量の微量の軽巣井戸を
含有する重水素化ベンゼン』を代用標準物質として特殊
な二重試料管の外管の外管と内管との間の空隙部に入
れ、また、測定すべき試料を前記二重試料管の内管の内
部に入れて、二重試料管を作成して、そして、その二重
試料管を使用して1H−NMR測定に使用しているので、一
般の機器分析において定量的な測定をする場合に原則と
して必要とされる標準物質による検量線の作成を行う必
要がないと共に、標準物質の試料化合物への添加による
試料化合物の変質、分解などが生じないのである。According to the quantification method of the present invention, “deuterated benzene containing a known amount of a trace amount of light nest well” is used as a substitute standard substance, and a special double sample tube is provided between the outer tube and the inner tube of the outer tube. The sample to be measured is placed in the cavity, and the sample to be measured is placed inside the inner tube of the double sample tube to prepare a double sample tube, and 1 H-NMR is used using the double sample tube. Since it is used for measurement, it is not necessary to create a calibration curve with standard substances, which is generally required for quantitative measurement in general instrumental analysis. The sample compound is not altered or decomposed.
また、この発明の定量法では、アルキル金属化合物中の
含酸素化合物の定量限界が、100ppm程度であり、さら
に、特定の条件を選べば、約25ppmまである優れた定量
法である。Further, in the quantification method of the present invention, the quantification limit of the oxygen-containing compound in the alkyl metal compound is about 100 ppm, and it is an excellent quantification method of about 25 ppm if specific conditions are selected.
第１図は、この発明の定量法に使用する二重試料管の概
略を示す断面図である。 第２図は、実施例１の定量分析の結果得られた、測定の
目的物である『含酸素化合物』の酸素に直接結合した炭
素についた水素のシグナルピークと、代用標準物質中の
『700ppmのベンゼン』のシグナルピークを示すものであ
る。 1;二重試料管、2;内管、3;外管、4;試料、5;代用標準物
質、7;テフロン製チューブガード、８、9;テフロン製固
定具、10;ベンゼンのシグナルピーク、11;含酸素化合物
のシグナルピーク。FIG. 1 is a sectional view showing an outline of a double sample tube used in the quantification method of the present invention. FIG. 2 shows a signal peak of hydrogen attached to carbon directly bonded to oxygen in the “oxygen-containing compound”, which is the object of measurement, obtained as a result of the quantitative analysis of Example 1, and “700 ppm in the substitute standard substance”. It shows the signal peak of "benzene". 1; Double sample tube, 2; Inner tube, 3; Outer tube, 4; Sample, 5; Substitute standard substance, 7: Teflon tube guard, 8, 9; Teflon fixture, 10: Benzene signal peak, 11; Signal peak of oxygen-containing compound.
Claims (1)
て有機金属化合物中の含酸素化合物を定量分析するにあ
たって、 二重試料管の内管内に、微量の含酸素化合物を含有する
アルキル金属化合物からなる試料が入れられていると共
に、前記の二重試料管の外管と内管との間の空隙内に、
既知量の微量の軽水素を含有する重水素化ベンゼンから
なる代用標準物質が入れられており、さらに、各開口部
を密封した二重試料管を使用し、 前記二重試料管内の試料を水素−核磁気共鳴法により定
量する際に、 （ａ） 前記二重試料管内のアルキル金属化合物のアル
キル基中のプロトンに基づくピークを、ホモゲーテッド
デカップリング法で消去すると共に、 （ｂ） 前記二重試料管内のアルキル金属化合物中の微
量の含酸素化合物中の酸素に直接結合した炭素についた
水素を、高精度で定量することを特徴とする有機金属化
合物中の含酸素化合物の定量法。1. When quantitatively analyzing an oxygen-containing compound in an organometallic compound by hydrogen-nuclear magnetic resonance method ( 1 H-NMR method), a trace amount of oxygen-containing compound is contained in the inner tube of a double sample tube. A sample consisting of an alkyl metal compound is contained, and in the space between the outer tube and the inner tube of the double sample tube,
A substitute standard substance consisting of deuterated benzene containing a known amount of a slight amount of deuterium is contained, and further, a double sample tube with each opening sealed is used, and the sample in the double sample tube is filled with hydrogen. -When quantifying by a nuclear magnetic resonance method, (a) a peak based on a proton in an alkyl group of an alkyl metal compound in the double sample tube is eliminated by a homogated decoupling method, and (b) the double A method for quantifying an oxygen-containing compound in an organometallic compound, characterized by highly accurately quantifying hydrogen on a carbon directly bonded to oxygen in a trace amount of an oxygen-containing compound in an alkyl metal compound in a sample tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63131534A JPH0769281B2 (en) | 1988-05-31 | 1988-05-31 | Quantitative determination of oxygen-containing compounds in organometallic compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63131534A JPH0769281B2 (en) | 1988-05-31 | 1988-05-31 | Quantitative determination of oxygen-containing compounds in organometallic compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01302148A JPH01302148A (en) | 1989-12-06 |
| JPH0769281B2 true JPH0769281B2 (en) | 1995-07-26 |
Family
ID=15060321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63131534A Expired - Lifetime JPH0769281B2 (en) | 1988-05-31 | 1988-05-31 | Quantitative determination of oxygen-containing compounds in organometallic compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0769281B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008051799A (en) * | 2006-07-24 | 2008-03-06 | Jeol Ltd | NMR apparatus and NMR measurement method |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040027054A (en) * | 2002-09-27 | 2004-04-01 | 한국화학연구원 | Apparatus for quantitative analysis of metal ion using nuclear magnetic resonance spectrometer and quantitative analysis method of sodium |
| KR100764892B1 (en) * | 2006-03-13 | 2007-10-09 | 한국화학연구원 | Chlorine Ion Determination Using Chlorine Nuclear Magnetic Resonance Spectroscopy |
| JP5117903B2 (en) * | 2008-03-26 | 2013-01-16 | 新日鐵住金株式会社 | Sample tube for solid-state NMR and magic angle adjustment mechanism |
| KR20120116953A (en) | 2010-01-06 | 2012-10-23 | 가부시키가이샤 시세이도 | Reference material for nmr, sample tube for nmr, capillary for nmr, and method for determining nmr spectrum of sample |
| JP4923112B2 (en) * | 2010-01-06 | 2012-04-25 | 株式会社 資生堂 | External standard for 1H NMR |
| JP5027891B2 (en) * | 2010-01-06 | 2012-09-19 | 株式会社 資生堂 | Analysis method |
| CN112986305A (en) * | 2019-12-16 | 2021-06-18 | 有研工程技术研究院有限公司 | Novel nuclear magnetic tube and application thereof |
| CN115825138A (en) * | 2022-12-20 | 2023-03-21 | 中轻技术创新中心有限公司 | Method for Determination of Deuterium in Ethanol by SNIF-NMR with Sealed Tube Embedded Method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2517828B1 (en) * | 1981-12-04 | 1985-08-09 | Martin Gerard | NEW PROCESS FOR THE QUALITATIVE AND QUANTITATIVE DETECTION AND DIFFERENTIATION OF NATURALLY DEUTERED MOLECULES, DEVICE FOR CARRYING OUT THIS METHOD AND APPLICATION, IN PARTICULAR, FOR DETECTION OF WINE CHAPTALIZATION |
| JPH07112139B2 (en) * | 1986-07-09 | 1995-11-29 | 松下電器産業株式会社 | Amplifier integrated circuit |
-
1988
- 1988-05-31 JP JP63131534A patent/JPH0769281B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008051799A (en) * | 2006-07-24 | 2008-03-06 | Jeol Ltd | NMR apparatus and NMR measurement method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01302148A (en) | 1989-12-06 |
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