JPH01302148A - Assay of oxide compound contained in organic metal compound - Google Patents
Assay of oxide compound contained in organic metal compoundInfo
- Publication number
- JPH01302148A JPH01302148A JP13153488A JP13153488A JPH01302148A JP H01302148 A JPH01302148 A JP H01302148A JP 13153488 A JP13153488 A JP 13153488A JP 13153488 A JP13153488 A JP 13153488A JP H01302148 A JPH01302148 A JP H01302148A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen
- tube
- hydrogen
- double
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 48
- 238000003556 assay Methods 0.000 title 1
- 150000002736 metal compounds Chemical class 0.000 title 1
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- -1 alkyl metal compound Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 claims description 16
- 238000001225 nuclear magnetic resonance method Methods 0.000 claims description 10
- 239000010421 standard material Substances 0.000 claims description 9
- 150000002902 organometallic compounds Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- 238000005259 measurement Methods 0.000 abstract description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011088 calibration curve Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 abstract description 2
- 238000005070 sampling Methods 0.000 abstract 3
- 239000013558 reference substance Substances 0.000 abstract 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000004445 quantitative analysis Methods 0.000 description 21
- 239000000126 substance Substances 0.000 description 10
- 239000004809 Teflon Substances 0.000 description 7
- 229920006362 Teflon® Polymers 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 3
- 238000011002 quantification Methods 0.000 description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000013076 target substance Substances 0.000 description 2
- HTDIUWINAKAPER-UHFFFAOYSA-N trimethylarsine Chemical compound C[As](C)C HTDIUWINAKAPER-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- ITYDTFJIORZBOA-UHFFFAOYSA-N methoxy(dimethyl)arsane Chemical compound C[As](OC)C ITYDTFJIORZBOA-UHFFFAOYSA-N 0.000 description 1
- AALDVTQHWKTGFN-UHFFFAOYSA-N methoxy(dimethyl)indigane Chemical compound CO[In](C)C AALDVTQHWKTGFN-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- WWVNWQJKWKSDQM-UHFFFAOYSA-N triethylarsane Chemical compound CC[As](CC)CC WWVNWQJKWKSDQM-UHFFFAOYSA-N 0.000 description 1
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
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 Application Field] The present invention utilizes two special configurations for quantitatively analyzing oxygen-containing compounds in organometallic compounds by hydrogen-nuclear magnetic resonance method (1H-NMR method). A heavy sample tube is used, and during its quantitative analysis, the peaks based on the protons in the alkyl groups of the alkyl metal compounds in the sample are eliminated by the homogated decoupling method, and the peaks that contain trace amounts of oxygenated compounds are eliminated using the homogated decoupling method. The present invention relates to a method for quantitatively analyzing "extremely trace amounts of oxygen-containing compounds" in a sample consisting of an alkyl metal compound, quickly and with high precision using simple operations.
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 materials used in the production of precision electronic materials, and if these alkyl metal compounds contain even trace amounts of oxygen-containing compounds, the production using them may be difficult. There has been a problem in that the original performance of electronic materials is significantly degraded.
すなわち、前記のアルキル金属化合物は、空気などと接
触すると、分解したり、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 alkyl metal compound mentioned above comes into contact with air, etc., it decomposes or ignites, and oxygen-containing compounds are easily generated. It was necessary to control the quality of alkyl metal compounds by measuring their content.
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のである。However, a practical quantitative analysis method for quantifying trace amounts of oxygen-containing compounds in alkyl metal compounds is extremely difficult because alkyl metal compounds are extremely unstable compounds even in the presence of trace amounts of air. It was.
Ｃ本発明の解決すべき問題点〕
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。C Problems to be Solved by the Present Invention] The purpose of the present invention is to develop a practical quantitative analysis method for easily quantifying trace amounts of oxygen-containing compounds in alkyl metal compounds, for which no precise measurement method has been established in the past. ” is to be newly provided.
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、（ロ）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
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。In quantitative analysis of oxygen-containing compounds in organometallic compounds by hydrogen-nuclear magnetic resonance method (1H-NMR method), this invention provides an alkyl metal containing a trace amount of oxygen-containing compound in the inner tube of a double sample tube. A sample consisting of a compound is placed in the gap between the outer tube and the inner tube of the double sample tube,
Using a double sample tube containing a substitute standard material consisting of deuterated benzene containing a known amount of trace amounts of light hydrogen and with each opening sealed, the sample in the double sample tube was filled with hydrogen. - When quantifying by nuclear magnetic resonance method, (a) the peak based on the proton in the alkyl group of the alkyl metal compound in the double sample tube is eliminated by the homogated decoupling method, and (b) the double This invention relates to a method for quantifying oxygen-containing compounds in organometallic compounds, which is characterized by quantifying with high precision the hydrogen attached to carbon directly bonded to the oxygen of trace amounts of oxygen-containing compounds in alkyl metal compounds 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 generally involves the measurement of trace amounts of oxygen-containing compounds in an alkyl metal compound (sample) in the above-mentioned special-shaped double sample tube. The main feature is that it can quantify the content of hydrogen attached to carbon (hydrogen in alkoxy groups) with high precision.
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。The quantitative method of this invention will be explained below with reference to the drawings.
I will explain 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
略を示す断面回である。FIG. 1 is a cross-sectional diagram schematically showing a double sample tube used in the quantitative 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ｒ二重試料管」は、例えば、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ｌ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ｌ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 in the quantitative analysis of oxygen-containing compounds in organometallic compounds by the hydrogen-nuclear magnetic resonance method (1H-NMR method) in this invention is, for example, usually as shown in FIG. A sample tube made of glass for NMR, etc. can be used, and a sample 4 made of an alkyl metal compound containing a trace amount of an oxygen-containing compound is placed inside the inner tube 2 of the double sample tube 1, and the A standard substance substitute 5 made of deuterated benzene containing a trace amount of light hydrogen is placed in the gap 6 between the outer tube 3 and the inner tube 2 of the heavy sample tube 1.
また、内管２の先端の溶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。In addition, it is preferable to attach a Teflon tube guard 7 to protect the welded part at the tip of the inner tube 2, and to use a Teflon fixture 8.9 to fix 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
〜２０ｆｆ１１、特に８〜１５ａ１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０．５〜８園、
特に１〜５ｍｍ程度であることが好ましい。The double sample tube described above may have an inner diameter of about 2 to 15 mm, particularly about 3 to 10 mm, and an inner diameter of about 5 to 10 mm.
~20ff11, especially about 8~15a1, and furthermore, the inner tube and the outer tube are arranged concentrically, and the gap between the inner tube and the outer tube is 0.5~ 8 gardens,
In particular, it is preferably about 1 to 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、ポリプロピレン、
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, but includes, for example, polyethylene, polypropylene,
Synthetic resins such as polyacetal and polyamide can also be mentioned.
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ずる含酸
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２５〜１１０００ｐ
ｐ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 sample contains an alkyl metal compound as a main component, and contains about 95% by weight or more, particularly 98% by weight of an alkyl metal compound.
An oxygen-containing compound containing the above in a proportion of 99.0% by weight or more, which is decomposed and produced when the alkyl metal compound comes into contact with oxygen in the air;
Alternatively, an oxygen-containing compound that is a by-product during the production of an alkyl compound (for example, an organometallic compound having 1 to 4, especially 1 alkoxy group such as a methoxy group, ethoxy group, propoxy group, or butoxy group) oxygen compounds)
However, about 20 to 2000 ppm, especially 25 to 11000 ppm
Any sample may be used as long as the content is about p.
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個有する、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■〜■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ミニウム、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 metals 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. , tellurium, and other group metals of the periodic table.For example, trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, and triisopropylaluminum, and trialkylaluminiums such as trimethylgallium and triethylgallium. Gallium, trimethylarsine, triethylarsine, diethylzinc, etc. can be mentioned.
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 compounds 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 a high-purity heavy hydrogen compound obtained by deuterating benzene without a substituent and containing a trace amount of light hydrogen in an atomic ratio, preferably 100 to 2000 ppm. Any substitute standard material 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°Ｃ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 for creating the double sample tube described above is, for example, by first placing an alkyl metal compound in a glass sample tube that will serve as the inner tube.
A sealed tube sample is prepared at a relatively low temperature (especially at a temperature of 25°C or less) and in an inert atmosphere, and then the sealed tube sample is placed inside a sample tube that will serve as an outer tube, and then the inner tube is placed inside the sample tube. One method is to introduce deuterated benzene, which serves as a substitute standard substance, into the gap between the tube and the outer tube.
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（ＩＨ−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「強度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用標準物質
中のｒプロトン１に基づくｒ基準ピーク１と前記の内管
内のアルキル金属化合物中の微量のｒ含酸素化合物１中
のアルコキシ基のα−水素に基づくｒ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 this invention, when quantitatively analyzing a sample by hydrogen-nuclear magnetic resonance method (IH-NMR method) using the aforementioned double sample tube, (a) the sensitivity is lowered by the homogated decoupling method. “Protons in alkyl groups (such as methyl groups)” of the alkyl metal compound inside the inner tube
(b) r reference peak 1 based on r proton 1 in the substitute standard material in the gap between the outer tube and the inner tube; and the peak to be measured based on the α-hydrogen of the alkoxy group in the trace amount of r-oxygen compound 1 in the alkyl metal compound in the inner tube.
It is possible to accurately quantify trace amounts of oxygen-containing compounds in alkyl metal compounds with high precision by measuring them with integrated efficiency.
この発明の定量法では、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テスラ一以上の超伝導
マグネットの中に入れて、ｌ）ｌ−ＮＭＲ測定を行うこ
とが好ましい。In the quantitative method of this invention, the hydrogen-nuclear magnetic resonance method is
It is preferable to place the above-mentioned double sample tube in a superconducting magnet with a magnetic field strength of 4 Tesla or more, and perform l) l-NMR measurement.
前記の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 above-mentioned homogated decoupling method is a method for erasing signals from solvents, water, etc., and is a method of erasing signals by irradiating and saturating the protons to be erased until just before the observation pulse is emitted. be.
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 used in the quantitative method of this 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 being measured. The oxygen-containing compound can be quantified by relatively comparing the peak area intensities based on the trace amount of benzene in the sample and the trace amount of the oxygen-containing compound to be determined in the alkyl metal compound of the sample.
この発明の定量法では、水素−核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ては、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。The quantitative method of this invention employs the hydrogen-nuclear magnetic resonance method, so the measurement operation is relatively simple, and work such as pretreatment can be done in a short time. The relative error is usually about 1 to 3%, and the most important advantage is that it can be used even with sample compounds that are unstable thermally or in contact with air, various solvents, etc. This method has the advantage of being able to stably and directly obtain quantitative data for sample compounds.
また、この発明の定量法では、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、分解などが生じないのである
。In addition, in the quantitative method of the present invention, deuterated benzene containing a known amount of light hydrogen is placed as a substitute standard substance in the gap between the outer tube and the inner tube of a special double sample tube, and the sample is Since it is used for measurements by placing it inside the inner tube of a double sample tube, it is necessary to create a calibration curve using standard materials, which is required in principle for quantitative measurements in general instrumental analysis. In addition, addition of the standard substance to the sample compound does not cause deterioration or decomposition of the sample compound.
以下に実施例を示す。 Examples are shown below.
実施例１
内管として使用される予定の「内径が５ｆｆＩＩｌであ
り、長さが２３０ｍｍである試料管ｊ中に、２０°Ｃ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蓋含有している
）を入れて爆射し、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１０ｍで
あり、長さが１８０閣である試料管」に、「重水素化率
が９９．９３％である重水素化ベンゼンｊ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ζ下の三箇所（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、密封された二重
試料管を形成した。Example 1 Trialkylaluminium (an unknown amount of (contains a small amount of oxygen-containing compounds), explode it, attach a Teflon tube guard,
Next, a sample tube with an inner diameter of 10 m and a length of 180 mm, which was scheduled to be used as an outer tube, was filled with deuterated benzene j with a deuteration rate of 99.93% as a substitute standard material. In addition, as shown in FIG. (lower section and lower section) were sealed and guarded with Teflon fixtures to form a sealed dual sample tube.
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■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。Next, using the double sample tube, flip it into a "superconducting magnet with a magnetic field strength of 4.7 Tesla" provided in a hydrogen-nuclear magnetic resonance measurement device (manufactured by JEOL Ltd.; FX-200). Place the angle at 45°, 1H-
NMR measurements were performed.
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 large, and the peak derived from the hydrogen of the methoxy group of the oxygen-containing compound (methoxydimethylaluminum) to be observed was very small. The detection sensitivity was increased by using a coupling method to reduce the peak intensity derived from the hydrogen of the methyl group of trimethylaluminum and improve the integration efficiency of the oxygen-containing compound, which is the target substance to be measured.
この際のＩＨ−ＮＭＲスペクトルを第２図に示す。The IH-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ｒ含酸
素化合物」は、３．６５ ｐ ｐ ｍ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７．２４ ｐ ｐ ｍにピーク１０を示している０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 target substance to be measured, "r-oxygen-containing compound," has a signal peak of 11 at 3.65 p.p.m., and the signal based on light hydrogen in the substitute standard material is 7.65 p.p.m. Oxygenated compounds in the sample can be determined by comparing the peak intensities derived from both protons with the amounts of the sample and substitute standard substance present within the analysis range. It was possible to quantify the amount by assuming that it was all 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-mentioned quantitative method many times and determining the limit of quantification of oxygen-containing compounds in trialkyl aluminum,
It was found that even when the number of integrations was 56, it was about 100 ppm.
実施例２
１Ｈ−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 measurement conditions in 1H-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５０ｐｐ
ｍであることが判明した。As a result, from 80 integrated spectra, the limit of quantification of oxygen-containing compounds in trialkyl aluminum was approximately 50 pp.
It turned out to be m.
実施例３
二重試料管の内管として、内径が７１１Ｉ１１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 with an inner diameter of 711I11 was used as the inner tube of the double sample tube, and deuterated benzene with a deuteration rate of 99.9% was used as a substitute standard material. Quantitative analysis was performed in the same manner as in Example 1.
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２５ｐ
ｐｍであることが判明した。As a result, from 256 integrated spectra, the limit of quantification of oxygen-containing compounds in trialkyl aluminum was approximately 25p.
It turned out to be pm.
本発明の定量法によれば、ｒ既知量の微量の軽巣井戸を
含有する重水素化ベンゼンｊ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 quantitative method of the present invention, deuterated benzene j containing a known amount of light pores is used as a substitute standard substance to detect the difference between the outer tube and the inner tube of a special double sample tube. Insert the sample into the cavity and place the sample to be measured inside the inner tube of the double sample tube to create a double sample tube, and then perform 1H-NMR measurement using the double sample tube. Since it is used for
There is no need to create a calibration curve using a standard substance, which is required in principle for quantitative measurements in general instrumental analysis, and there is no need to add standard substances to the sample compound, which can cause deterioration or decomposition of the sample compound. It does not occur.
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、ｔｏｏｐｐｍ程度まであり
、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 quantitative method of the present invention, the quantitative limit of oxygen-containing compounds in alkyl metal compounds is about tooppm, and if specific conditions are selected, it is an excellent quantitative method that can reach up to about 25 ppm.
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ｒ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
ｒ７００ｐｐｍのベンゼン」のシグナルピークを示すも
のである。
ｌ；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、ｌＯ；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。
特許出願人 宇部興産株式会社
第１ 図
第２ 図
７２与 ０・”但し吐３FIG. 1 is a cross-sectional view schematically showing a double sample tube used in the quantitative method of the present invention. Figure 2 shows the signal peak of hydrogen attached to the carbon directly bonded to the oxygen of the measurement target, the r-oxygen-containing compound, obtained as a result of the quantitative analysis in Example 1, and the signal peak of r700ppm in the substitute standard material. This shows the signal peak of "benzene."l; double sample tube, 2; inner tube, 3: outer tube, 4; sample, 5;
Substitute standard substance, 7; Teflon tube guard, 8.9
; Teflon fixture, 1O; signal peak of benzene, 11; signal peak of oxygenated compounds. Patent applicant: Ube Industries, Ltd. Figure 1 Figure 2 Figure 72
Claims (1)
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。[Claims] In quantitatively analyzing oxygen-containing compounds in organometallic compounds by hydrogen-nuclear magnetic resonance method (^1H-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 placed in the gap between the outer tube and the inner tube of the double sample tube,
Using a double sample tube containing a substitute standard material consisting of deuterated benzene containing a known amount of trace amounts of light hydrogen, and each opening sealed, the sample in the double sample tube was filled with hydrogen. - When quantifying by nuclear magnetic resonance method, (a) the peak based on the proton in the alkyl group of the alkyl metal compound in the double sample tube is eliminated by the homogated decoupling method, and (b) the double A method for quantifying oxygen-containing compounds in organometallic compounds, which is characterized by quantifying with high precision hydrogen attached to carbon directly bonded to oxygen in a trace amount of oxygen-containing compounds 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 true JPH01302148A (en) | 1989-12-06 |
| JPH0769281B2 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 (6)
| 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 | Quantitative method of chloride ion by 35-Chloride Nuclear Magnetic Resonance |
| JP2009236512A (en) * | 2008-03-26 | 2009-10-15 | Nippon Steel Corp | Sample tube for solid nmr, and magic angle adjustment mechanism |
| WO2011083730A1 (en) | 2010-01-06 | 2011-07-14 | 株式会社資生堂 | Reference material for nmr, sample tube for nmr, capillary for nmr, and method for determining nmr spectrum of sample |
| JP2011141159A (en) * | 2010-01-06 | 2011-07-21 | Shiseido Co Ltd | External standard substance for 1hnmr |
| JP2011141160A (en) * | 2010-01-06 | 2011-07-21 | Shiseido Co Ltd | Nmr sample tube and analysis method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4933352B2 (en) * | 2006-07-24 | 2012-05-16 | 株式会社 Ｊｅｏｌ Ｒｅｓｏｎａｎｃｅ | NMR equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58154646A (en) * | 1981-12-04 | 1983-09-14 | サントル・ナシヨナ−ル・ドウ・ラ・ルシエルシユ・シアンテイフイ−ク | Method of detection and qualitative -quantitative analysis of natural deuterating molecule and device for executing said method |
| JPS6316705A (en) * | 1986-07-09 | 1988-01-23 | Matsushita Electric Ind Co Ltd | Integrated circuit for amplifier |
-
1988
- 1988-05-31 JP JP63131534A patent/JPH0769281B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58154646A (en) * | 1981-12-04 | 1983-09-14 | サントル・ナシヨナ−ル・ドウ・ラ・ルシエルシユ・シアンテイフイ−ク | Method of detection and qualitative -quantitative analysis of natural deuterating molecule and device for executing said method |
| JPS6316705A (en) * | 1986-07-09 | 1988-01-23 | Matsushita Electric Ind Co Ltd | Integrated circuit for amplifier |
Cited By (9)
| 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 | Quantitative method of chloride ion by 35-Chloride Nuclear Magnetic Resonance |
| JP2009236512A (en) * | 2008-03-26 | 2009-10-15 | Nippon Steel Corp | Sample tube for solid nmr, and magic angle adjustment mechanism |
| WO2011083730A1 (en) | 2010-01-06 | 2011-07-14 | 株式会社資生堂 | Reference material for nmr, sample tube for nmr, capillary for nmr, and method for determining nmr spectrum of sample |
| JP2011141159A (en) * | 2010-01-06 | 2011-07-21 | Shiseido Co Ltd | External standard substance for 1hnmr |
| JP2011141160A (en) * | 2010-01-06 | 2011-07-21 | Shiseido Co Ltd | Nmr sample tube and analysis method |
| CN102741700A (en) * | 2010-01-06 | 2012-10-17 | 株式会社资生堂 | Reference material for NMR, sample tube for NMR, capillary for NMR, and method for determining NMR spectrum of sample |
| EP2752677A1 (en) | 2010-01-06 | 2014-07-09 | Shiseido Company, Ltd. | Sample tube for NMR measurements |
| US9335388B2 (en) | 2010-01-06 | 2016-05-10 | Shiseido Company, Ltd. | Reference material for NMR, sample tube for NMR, capillary for NMR, and method for measuring NMR for a sample |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0769281B2 (en) | 1995-07-26 |
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