JP2780393B2 - Analysis method for molecular weight distribution of polyimide - Google Patents
Analysis method for molecular weight distribution of polyimideInfo
- Publication number
- JP2780393B2 JP2780393B2 JP1292797A JP29279789A JP2780393B2 JP 2780393 B2 JP2780393 B2 JP 2780393B2 JP 1292797 A JP1292797 A JP 1292797A JP 29279789 A JP29279789 A JP 29279789A JP 2780393 B2 JP2780393 B2 JP 2780393B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- molecular weight
- weight distribution
- dichloroacetic acid
- gpc
- 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.)
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明はポリイミドの分子量分布分析法に関する。さ
らに詳しくは、ゲルパーミエーションクロマトグラフィ
を用いた、ポリイミドの品質管理、性能評価等の好適な
分子量分布の分析法に関する。Description: TECHNICAL FIELD The present invention relates to a method for analyzing the molecular weight distribution of polyimide. More specifically, the present invention relates to a suitable molecular weight distribution analysis method such as quality control and performance evaluation of polyimide using gel permeation chromatography.
［従来の技術］ ポリイミドの特徴として、下記の点が挙げられる。[Prior art] Polyimide has the following features.
耐熱性に優れている。 Excellent heat resistance.
低温から高温まで特性の変化が少ない。 Little change in characteristics from low to high temperature.
耐衝撃性がよく、寸法安定性がよい。 Good impact resistance and good dimensional stability.
電気特性がよい。 Good electrical characteristics.
耐薬品性が良好である。 Good chemical resistance.
耐摩擦性が良好で、難燃性で、耐放射線も良好であ
る。It has good friction resistance, flame resistance, and good radiation resistance.
これらの特徴を生かして、ポリイミドは電気部品（た
とえばコネクタ、ソケット、IC基板、プリント回路基板
など）、自動車部品（ブレーキブリーダーなど）、その
他（ピストンリング、ブッシュなど）に使用される。使
用される形態もフィルム、成形体、塗料、ワニスなどさ
まざまである。これらの各用途に要求されるポリイミド
の品質も様々であり、これに応じてポリイミドの品質を
管理する必要がある。Taking advantage of these features, polyimide is used for electrical components (eg, connectors, sockets, IC boards, printed circuit boards, etc.), automotive components (eg, brake bleeders), and others (eg, piston rings, bushes, etc.). Various forms are used, such as films, molded articles, paints, and varnishes. The quality of polyimide required for each of these uses is also various, and it is necessary to control the quality of polyimide accordingly.
［発明が解決しようとする課題］ しかしながら、ポリイミドは上記のように耐薬品性に
優れており、今までのところポリイミドを溶解する溶媒
がなく、現状ではポリイミドの品質管理は不充分なまま
である。[Problems to be Solved by the Invention] However, polyimide has excellent chemical resistance as described above, and there is no solvent to dissolve polyimide so far, and at present, quality control of polyimide remains inadequate. .
前記従来技術の課題を解決するため、この発明はポリ
イミドの品質管理や性能評価が可能な分析法を提供しよ
うとするものである。In order to solve the problems of the prior art, the present invention aims to provide an analysis method capable of quality control and performance evaluation of polyimide.
すなわち、ポリイミドの溶離液としてジクロロ酢酸を
用い、ゲルパーミエーションクロマトグラフィ（以下GP
Cという）の移動相として、クロロホルムとジクロロ酢
酸の混合溶液（混合比9:1）を用い、検出手段として示
差屈折計を用いたGPCによって分析することにより、ポ
リイミドの分子量分布の測定を効率よく、正確に行う方
法を提供する。That is, gel permeation chromatography (hereinafter referred to as GP) uses dichloroacetic acid as an eluent for polyimide.
Efficiently measures the molecular weight distribution of polyimide by using a mixed solution of chloroform and dichloroacetic acid (mixing ratio 9: 1) as the mobile phase of C) and analyzing by GPC using a differential refractometer as the detection means. And provide a way to do it accurately.
［課題を解決するための手段］ 前記課題を解決するため、本発明方法は、GPCにより
ポリイミドの分子量分布を測定する方法であって、ポリ
イミドをジクロロ酢酸で加熱溶解し、クロロホルムとジ
クロロ酢酸の混合溶液を溶離液として用いたGPCに付し
て、示差屈折計で検出し、前記ポリイミド分子量分布を
測定することを特徴とするポリイミドの分子量分布分析
法である。[Means for Solving the Problems] In order to solve the above problems, the method of the present invention is a method for measuring the molecular weight distribution of polyimide by GPC, wherein the polyimide is heated and dissolved with dichloroacetic acid, and mixed with chloroform and dichloroacetic acid. This is a method for analyzing the molecular weight distribution of polyimide, wherein the solution is subjected to GPC using a solution as an eluent, detected by a differential refractometer, and the molecular weight distribution of the polyimide is measured.
GPCは、例えば多孔性スチレン−ジビニルベンゼン系
重合体球状微粒子を充填剤としたカラムに分析しようと
する試料を（移動相）溶媒に溶解させた溶液を付し、試
料分子の大きいものから順に分子のサイズ別に分離さ
せ、試料分子の量を分析するものである。そしてポリイ
ミドの溶解液についてのGPCからの溶離液を分画して補
集することにより、ポリイミドの分子量分布を得るので
ある。GPC, for example, attaches a solution prepared by dissolving a sample to be analyzed in a (mobile phase) solvent to a column using porous styrene-divinylbenzene-based polymer spherical fine particles as a packing material. And the amount of sample molecules is analyzed. Then, the molecular weight distribution of the polyimide is obtained by fractionating and collecting the eluate of the polyimide solution from the GPC.
次に、ポリイミドの溶解液としてジクロロ酢酸を用
い、GPCの移動相として、クロロホルムとジクロロ酢酸
の混合溶液を用いる。この場合、カラムの寿命を考慮し
てクロロホルムとジクロロ酢酸の混合溶液の混合比9:1
〜7:3が好ましい。GPCの移動相として、クロロホルムと
ジクロロ酢酸の混合溶液を使用するのは、ポリイミドの
分子量分布に対応した溶離をしやすいからである。とく
に好ましくは、クロロホルムとジクロロ酢酸の混合溶液
の混合比9:1の近辺である。Next, dichloroacetic acid is used as a polyimide solution, and a mixed solution of chloroform and dichloroacetic acid is used as a mobile phase of GPC. In this case, the mixing ratio of the mixed solution of chloroform and dichloroacetic acid is 9: 1 in consideration of the column life.
~ 7: 3 is preferred. The reason for using a mixed solution of chloroform and dichloroacetic acid as the mobile phase of GPC is that elution corresponding to the molecular weight distribution of polyimide is easy. Particularly preferably, the mixing ratio of the mixed solution of chloroform and dichloroacetic acid is around 9: 1.
次に、GPCの検出器として示差屈折計を用いる。これ
はポリイミドの分子量分布の検出に優れているからであ
る。Next, a differential refractometer is used as a GPC detector. This is because it is excellent in detecting the molecular weight distribution of polyimide.
［作用］ この発明によれば、ポリイミドのジクロロ酢酸溶液
を、クロロホルムとジクロロ酢酸の混合溶液（混合比9:
1）からなる移動相中に導入してGPCに付すことにより、
ポリイミドを効率良く分析できる。According to the present invention, a polyimide dichloroacetic acid solution is mixed with a mixed solution of chloroform and dichloroacetic acid (mixing ratio 9:
By introducing into the mobile phase consisting of 1) and attaching to GPC,
Polyimide can be analyzed efficiently.
［実施例］ この発明において、上記ポリイミドがジクロロ酢酸に
加熱溶解されて注入用溶液が調整された後、これがクロ
ロホルムとジクロロ酢酸の混合溶液（混合比9:1）を移
動相とするGPCに付される。前記においてポリイミド
は、ジクロロ酢酸に0.2W/V％程度加熱溶解される。[Example] In the present invention, after the polyimide is heated and dissolved in dichloroacetic acid to prepare an injection solution, the solution is subjected to GPC using a mixed solution of chloroform and dichloroacetic acid (mixing ratio 9: 1) as a mobile phase. Is done. In the above, the polyimide is heated and dissolved in dichloroacetic acid at about 0.2 W / V%.
一方、GPCで用いる分離カラムとしては、汎用の高分
子ゲルを充填したものが使用可能であり、例えばポリス
チレンゲルやスチレン−ジビニルベンゼン共重合体ゲル
の充填カラムが好適な例として挙げられる。On the other hand, as a separation column used in GPC, a column packed with a general-purpose polymer gel can be used, and for example, a column packed with a polystyrene gel or a styrene-divinylbenzene copolymer gel is a preferable example.
また、GPC自体は汎用のものを使用できる。 In addition, a general-purpose GPC can be used.
以下、図面および測定例により本発明方法を詳細に説
明する。なお、本発明は下記の実施例に限定されない。Hereinafter, the method of the present invention will be described in detail with reference to the drawings and measurement examples. Note that the present invention is not limited to the following examples.
第１図は、この発明の方法を実施する装置の一例の構
成説明図である。この図において、１は移動相貯留槽、
２は送液ポンプ、３はマニュアルインジェクタ、４はカ
ラム、５はカラムオーブン、６は示差屈折計、７はデー
タ処理装置である。移動相１からポンプ２によりあらか
じめ溶離液を流し、定常状態を作る。次にマニュアルイ
ンジェクタ３から試料を注入する。注入された試料は溶
離液によりカラムオーブン５中のカラム４に送られ、検
出器６（示差屈折計）により分子量分布が検出される。
このデータをデータ処理装置７で処理し、分子量分布の
計算を行う。FIG. 1 is an explanatory view of the configuration of an example of an apparatus for implementing the method of the present invention. In this figure, 1 is a mobile phase storage tank,
Reference numeral 2 denotes a liquid sending pump, 3 denotes a manual injector, 4 denotes a column, 5 denotes a column oven, 6 denotes a differential refractometer, and 7 denotes a data processing device. The eluent is flowed in advance from the mobile phase 1 by the pump 2 to establish a steady state. Next, a sample is injected from the manual injector 3. The injected sample is sent to the column 4 in the column oven 5 by the eluent, and the molecular weight distribution is detected by the detector 6 (differential refractometer).
This data is processed by the data processor 7 to calculate the molecular weight distribution.
以上装置を用いて、下記の分析条件により分析を行っ
た。Using the apparatus described above, analysis was performed under the following analysis conditions.
（１） 分析条件 カラム:Shodex×GPC Ｋ−80M×２ （昭和電工（株）製） （8.0mmI.D×300mmL） 移動相：クロロホルム／ジクロロ酢酸（9/1） 流 量:0.5ml/min 温 度:40℃ 検出器:RID−6A（示差屈折計） （（株）島津製作所製） 感度32×10-6RIUFS （２） 試料の前処理 試料10mgを5mlのジクロロ酢酸に加熱溶解し、メン
ブランフィルタ（孔径:0.45μｍで濾過する。(1) Analysis conditions Column: Shodex × GPC K-80M × 2 (manufactured by Showa Denko KK) (8.0 mm ID × 300 mmL) Mobile phase: chloroform / dichloroacetic acid (9/1) Flow rate: 0.5 ml / min Temperature: 40 ° C Detector: RID-6A (differential refractometer) (manufactured by Shimadzu Corporation) Sensitivity 32 × 10 -6 RIUFS (2) Sample pretreatment A sample of 10 mg was dissolved in 5 ml of dichloroacetic acid by heating. Filter through a membrane filter (pore size: 0.45 μm).
濾液100μをHPLCに注入する。 Inject 100 μl of the filtrate into the HPLC.
上記分析条件で分析した結果を第２図に示す。この第
２図によりGPCを用いてポリイミドが分析できることが
わかる。FIG. 2 shows the results of analysis under the above analysis conditions. FIG. 2 shows that polyimide can be analyzed using GPC.
なお、第２図中の縦軸は信号強度、横軸は保持時間で
ある。The vertical axis in FIG. 2 is the signal intensity, and the horizontal axis is the holding time.
［発明の効果］ 本発明は、ポリイミドの溶解液としてジクロロ酢酸を
用い、GPCの移動相としてクロロホルムとジクロロ酢酸
の混合溶液を用い、検出手段として示差屈折計を用いた
GPCによって分析することにより、ポリイミドの分子量
分布の測定を効率よく、正確に行うことができた。[Effects of the Invention] The present invention uses dichloroacetic acid as a solution for dissolving a polyimide, uses a mixed solution of chloroform and dichloroacetic acid as a mobile phase of GPC, and uses a differential refractometer as a detection means.
By analyzing by GPC, it was possible to measure the molecular weight distribution of polyimide efficiently and accurately.
また、この分子量分布の品質管理、性能評価が簡単に
行えるという特別な効果を有する。In addition, there is a special effect that quality control and performance evaluation of the molecular weight distribution can be easily performed.
第１図は本発明方法を実施する装置の一例の構成説明
図、第２図は本発明ポリイミドの溶解液についての分子
量分布を表すクロマトグラムである。 1:移動相貯留槽、2:送液ポンプ 3:マニュアルインジェクタ 4:カラム、5:カラムオーブン 6:示差屈折計、7:データ処理装置FIG. 1 is an explanatory view of the structure of an example of an apparatus for carrying out the method of the present invention, and FIG. 2 is a chromatogram showing the molecular weight distribution of a solution of the polyimide of the present invention. 1: Mobile phase storage tank, 2: Liquid feed pump 3: Manual injector 4: Column, 5: Column oven 6: Differential refractometer, 7: Data processing device
Claims (1)
よりポリイミドの分子量分布を測定する方法であって、
ポリイミドをジクロロ酢酸で加熱溶解し、クロロホルム
とジクロロ酢酸との混合溶液を溶離液として用いたゲル
パーミエーションクロマトグラフィに付して、示差屈折
計で検出し、前記ポリイミドの分子量分布を測定するこ
とを特徴とするポリイミドの分子量分布分析法。1. A method for measuring the molecular weight distribution of a polyimide by gel permeation chromatography,
The polyimide is heated and dissolved with dichloroacetic acid, subjected to gel permeation chromatography using a mixed solution of chloroform and dichloroacetic acid as an eluent, detected with a differential refractometer, and measured for the molecular weight distribution of the polyimide. Molecular weight distribution analysis of polyimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1292797A JP2780393B2 (en) | 1989-11-10 | 1989-11-10 | Analysis method for molecular weight distribution of polyimide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1292797A JP2780393B2 (en) | 1989-11-10 | 1989-11-10 | Analysis method for molecular weight distribution of polyimide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03152459A JPH03152459A (en) | 1991-06-28 |
| JP2780393B2 true JP2780393B2 (en) | 1998-07-30 |
Family
ID=17786468
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1292797A Expired - Lifetime JP2780393B2 (en) | 1989-11-10 | 1989-11-10 | Analysis method for molecular weight distribution of polyimide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2780393B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11549920B2 (en) | 2017-11-20 | 2023-01-10 | Lg Chem, Ltd. | Method for quantitative analysis of monomers in polyimide film |
-
1989
- 1989-11-10 JP JP1292797A patent/JP2780393B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11549920B2 (en) | 2017-11-20 | 2023-01-10 | Lg Chem, Ltd. | Method for quantitative analysis of monomers in polyimide film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03152459A (en) | 1991-06-28 |
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