JP2006003265A - Determination method - Google Patents
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本発明は、分子鎖末端が変性された変性共重合体と、分子鎖末端が変性されていない非変性共重合体との混合物から、変性共重合体と非変性共重合体とを液体クロマトグラフィーにより分離して、それらの比を定量する方法に関する。 In the present invention, a modified copolymer and a non-modified copolymer are subjected to liquid chromatography from a mixture of a modified copolymer with a molecular chain terminal modified and a non-modified copolymer with a molecular chain terminal unmodified. And the ratio thereof is quantified.
高分子材料の分子鎖末端に官能基を導入することで、これまでにない特性をもたせる分子鎖末端変性技術があるが、この技術により得られる高分子材料において、全ての分子鎖末端に官能基が導入されている場合は少なく、むしろ分子鎖末端に官能基が導入されていない分子、即ち、変性されていない分子が共存していることがほとんどである。そのため、分子鎖末端変性技術により高分子材料の特性を制御し、調整するためには、分子鎖末端に官能基が導入された分子の割合、即ち、変性効率を測定する技術が必要である。 There is a molecular chain end modification technology that introduces a functional group at the molecular chain end of the polymer material, which has unprecedented characteristics. In the polymer material obtained by this technology, functional groups are added to all molecular chain ends. In many cases, a molecule having no functional group introduced at the end of the molecular chain, that is, an unmodified molecule coexists. Therefore, in order to control and adjust the characteristics of the polymer material by the molecular chain terminal modification technique, a technique for measuring the ratio of molecules having functional groups introduced at the molecular chain terminals, that is, modification efficiency is required.
このような変性効率測定技術としては、例えば紫外光を用いた分光分析により官能基の特性ピークを利用して定量する方法がある。しかしながら、この方法では低分子量のものであれば官能基置換部分の特性ピークが、ある程度の検出強度で測定可能であるが、高分子量のものでは、特性ピークの検出強度が弱くなってしまうため、変換効率の測定は極めて困難である。また、予めモデル化合物を用いて検量線を作成する必要もある。 As such a modification efficiency measurement technique, for example, there is a method of quantifying using a characteristic peak of a functional group by spectroscopic analysis using ultraviolet light. However, in this method, if the molecular weight is low, the characteristic peak of the functional group-substituted moiety can be measured with a certain degree of detection intensity. However, if the molecular weight is high, the detection intensity of the characteristic peak becomes weak. Measurement of conversion efficiency is extremely difficult. It is also necessary to create a calibration curve using a model compound in advance.
また、パテントブルー（Ｐａｔｅｎｔ Ｂｌｕｅ）等の置換官能基と反応して発色する試薬を用い、この試薬を置換官能基と反応させて発色させ、その反応生成物の吸光度により変換効率を測定する方法（非特許文献１：Ｊ． Ｍａｃｒｏｍｏｌ． Ｓｃｉ． Ｒｅｖｓ． Ｍａｃｒｏｍｏｌ． Ｃｈｅｍ． Ｃ２（２），２２５−２７７（１９６８））もあるが、この方法では、測定試料の調製が煩雑である上、発色試薬と置換官能基と反応率を考慮しなければならず、変性効率を算出するためには絶対分子量も必要であるため、分子量の換算による誤差や測定のバラツキも大きい。更に、この方法においてもまた、予めモデル化合物を用いて検量線を作成する必要がある。 In addition, a reagent that develops color by reacting with a substituted functional group such as Patent Blue and the like, reacts this reagent with the substituted functional group to develop color, and measures the conversion efficiency by the absorbance of the reaction product ( Non-Patent Document 1: J. Macromol. Sci. Revs. Macromol. Chem. C2 (2), 225-277 (1968)), this method requires complicated preparation of a measurement sample and a coloring reagent. The substituted functional group and the reaction rate must be taken into account, and the absolute molecular weight is also required to calculate the denaturation efficiency. Therefore, errors due to conversion of the molecular weight and variations in measurement are large. Furthermore, also in this method, it is necessary to prepare a calibration curve using a model compound in advance.
一方、薄層クロマトグラフィー（ＴＬＣ）により変性共重合体と非変性共重合体とを分離し、イアトロスキャンと呼ばれる専用の測定器で測定してクロマトグラムを得、これにより変換効率を測定する方法（非特許文献２：Ｍａｃｒｏｍｏｌｅｃｕｌｅｓ，２３，９３９−９４５（１９９０））もあるが、この方法はＴＬＣによる分離後に測定器で測定するものであって、ＴＬＣに３０分〜１時間、更にその後に測定器での所定の分析時間が必要であり、分析に時間と工数を必要とする。また、ＴＬＣでは分子量が１０万以上の高分子量のものは分離が困難である。 On the other hand, a modified copolymer and a non-modified copolymer are separated by thin layer chromatography (TLC) and measured with a dedicated measuring instrument called Iatroscan to obtain a chromatogram, thereby measuring conversion efficiency. There is also a method (Non-Patent Document 2: Macromolecules, 23, 939-945 (1990)), but this method is to measure with a measuring device after separation by TLC, and after 30 minutes to 1 hour after TLC, Predetermined analysis time with a measuring instrument is required, and analysis requires time and man-hours. In addition, in TLC, it is difficult to separate a polymer having a molecular weight of 100,000 or more.
このように、従来の測定技術では、分子鎖末端が変性された変性共重合体と、分子鎖末端が変性されていない非変性共重合体との混合物中の、変性共重合体と非変性共重合体との比を測定することは、煩雑な工程が必要であり、かつ分析時間も長時間となることから、迅速かつ正確な測定を必要とする場合、例えば、製造現場における工程管理や、製品試験に十分な方法とは言えず、この測定を短時間かつ正確に測定する方法が望まれていた。 Thus, in the conventional measurement technique, a modified copolymer and a non-modified copolymer in a mixture of a modified copolymer with a molecular chain terminal modified and a non-modified copolymer with a molecular chain terminal unmodified. Measuring the ratio with the polymer requires a complicated process and also requires a long analysis time, so when quick and accurate measurement is required, for example, process management at the manufacturing site, It is not a sufficient method for product testing, and a method for measuring this measurement in a short time and accurately has been desired.
本発明は、上記事情に鑑みなされたものであり、分子鎖末端が変性された変性共重合体と、分子鎖末端が変性されていない非変性共重合体との混合物中の、変性共重合体と非変性共重合体との比を短時間かつ正確に測定することができる方法を提供することを目的とする。 The present invention has been made in view of the above circumstances, and a modified copolymer in a mixture of a modified copolymer having a molecular chain terminal modified and a non-modified copolymer having a molecular chain terminal unmodified. It is an object of the present invention to provide a method capable of accurately measuring the ratio of a non-modified copolymer in a short time.
本発明者は、上記目的を達成するため鋭意検討を重ねた結果、分子鎖末端が下記一般式（１）
又は下記一般式（２）
で表されるアミノ基で封鎖された変性共重合体と、
上記共役ジエンモノマーと上記ビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が上記アミノ基で封鎖されていない非変性共重合体
とを含む高分子材料中の上記変性共重合体と上記非変性共重合体とを、表面シラノール基が非修飾のシリカゲル又は表面シラノール基の一部若しくは全部がアミノプロピル基で修飾されたシリカゲルを固定相、極性溶媒と非極性溶媒との混合溶媒を移動相とする液体クロマトグラフィーにて分離することが可能であり、これにより、検量線を作成することなく、分子量が５，０００程度の低分子量のものから１，０００，０００の高分子量のものまで、特に、従来、測定が困難であった分子量が１００，０００以上のものであっても変性共重合体と非変性共重合体との混合物中の変性共重合体と非変性共重合体との比を直接的に短時間かつ正確に測定できることを見出し、本発明をなすに至った。
As a result of intensive studies to achieve the above object, the present inventor has a molecular chain terminal represented by the following general formula (1).
Or the following general formula (2)
A modified copolymer blocked with an amino group represented by:
The modified copolymer in a polymer material comprising a copolymer of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer, the molecular chain terminal of which is not blocked with the amino group. Mix the mixture and the above-mentioned non-modified copolymer with silica gel whose surface silanol groups are unmodified or silica gel whose surface silanol groups are partially or entirely modified with aminopropyl groups, and a mixture of a polar solvent and a nonpolar solvent. Separation by liquid chromatography using a solvent as a mobile phase is possible, and thus, a low molecular weight molecular weight of about 5,000 to 1,000,000 high molecular weight can be obtained without preparing a calibration curve. In particular, a modified copolymer in a mixture of a modified copolymer and a non-modified copolymer, even if the molecular weight is conventionally 100,000 or more, which has been difficult to measure. It found that the ratio of the non-modified copolymer can be directly quickly and accurately measured, and they were therefore able to complete the present invention.
即ち、本発明は、以下の定量方法を提供する。
請求項１：（Ａ）共役ジエンモノマーとビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が下記一般式（１）
又は下記一般式（２）
で表されるアミノ基で封鎖された変性共重合体と、
（Ｂ）上記共役ジエンモノマーと上記ビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が上記アミノ基で封鎖されていない非変性共重合体
とを含む高分子材料中の上記（Ａ）成分と上記（Ｂ）成分との比を定量する方法であって、
上記高分子材料中の上記（Ａ）成分と上記（Ｂ）成分とを、表面シラノール基が非修飾のシリカゲル又は表面シラノール基の一部若しくは全部がアミノプロピル基で修飾されたシリカゲルを固定相、極性溶媒と非極性溶媒との混合溶媒を移動相とする液体クロマトグラフィーにて分離して定量することを特徴とする定量方法。
請求項２：上記共役ジエンモノマーが１，３−ブタジエンであり、上記ビニル芳香族炭化水素モノマーがスチレンであることを特徴とする請求項１記載の定量方法。
請求項３：上記アミノ基がジオクチルアミノ基、ピロリジノ基又はヘキサメチレンイミノ基であることを特徴とする請求項１又は２記載の定量方法。
請求項４：上記高分子材料の数平均分子量が５，０００〜１，０００，０００であることを特徴とする請求項１乃至３のいずれか１項記載の定量方法。
請求項５：上記極性溶媒がクロロホルム、テトラヒドロフラン、メタノール及びエタノールから選ばれる１種又は２種以上であり、かつ上記非極性溶媒がシクロヘキサン、ヘキサン及びヘプタンから選ばれる１種又は２種以上であることを特徴とする請求項１乃至４のいずれか１項記載の定量方法。
That is, the present invention provides the following quantitative method.
Claim 1: (A) A copolymer of a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer, the molecular chain terminal of which is represented by the following general formula (1)
Or the following general formula (2)
A modified copolymer blocked with an amino group represented by:
(B) The above-mentioned polymer in a polymer material comprising a copolymer of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer, wherein the molecular chain terminal is not blocked with the amino group. A method for quantifying the ratio of the component (A) to the component (B),
The stationary phase of the component (A) and the component (B) in the polymer material is a silica gel in which the surface silanol group is unmodified or in which part or all of the surface silanol group is modified with an aminopropyl group, A quantification method comprising separating and quantifying by a liquid chromatography using a mixed solvent of a polar solvent and a nonpolar solvent as a mobile phase.
[2] The method according to [1], wherein the conjugated diene monomer is 1,3-butadiene and the vinyl aromatic hydrocarbon monomer is styrene.
[3] The method according to [1] or [2], wherein the amino group is a dioctylamino group, a pyrrolidino group or a hexamethyleneimino group.
[4] The method according to any one of [1] to [3], wherein the polymer material has a number average molecular weight of 5,000 to 1,000,000.
Claim 5: The polar solvent is one or more selected from chloroform, tetrahydrofuran, methanol and ethanol, and the nonpolar solvent is one or more selected from cyclohexane, hexane and heptane. The quantification method according to any one of claims 1 to 4, wherein:
本発明によれば、分子鎖末端が変性された変性共重合体と、分子鎖末端が変性されていない非変性共重合体との混合物中の、変性共重合体と非変性共重合体との比を短時間かつ正確に測定することができ、特に、従来困難だった１００，０００以上の分子量を有する混合物の測定も可能である。 According to the present invention, a modified copolymer and a non-modified copolymer in a mixture of a modified copolymer with a molecular chain terminal modified and a non-modified copolymer with a molecular chain terminal unmodified. The ratio can be measured accurately in a short time, and in particular, it is possible to measure a mixture having a molecular weight of 100,000 or more, which has been difficult in the past.
以下、本発明につき更に詳述する。
本発明の定量方法は、（Ａ）共役ジエンモノマーとビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が下記一般式（１）
The present invention will be described in further detail below.
The quantitative method of the present invention is a copolymer of (A) a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer, the molecular chain terminal of which is represented by the following general formula (1)
又は下記一般式（２）
Or the following general formula (2)
で表されるアミノ基で封鎖された変性共重合体と、
（Ｂ）上記共役ジエンモノマーと上記ビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が上記アミノ基で封鎖されていない非変性共重合体
とを含む高分子材料中の上記（Ａ）成分と上記（Ｂ）成分との比を定量する方法であり、
上記高分子材料中の上記（Ａ）成分と上記（Ｂ）成分とを、表面シラノール基が非修飾のシリカゲル又は表面シラノール基の一部若しくは全部がアミノプロピル基で修飾されたシリカゲルを固定相、極性溶媒と非極性溶媒との混合溶媒を移動相とする液体クロマトグラフィーにて分離して定量するものである。
A modified copolymer blocked with an amino group represented by:
(B) The above-mentioned polymer in a polymer material comprising a copolymer of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer, wherein the molecular chain terminal is not blocked with the amino group. It is a method for quantifying the ratio of the component (A) to the component (B),
The stationary phase of the component (A) and the component (B) in the polymer material is a silica gel in which the surface silanol group is unmodified or in which part or all of the surface silanol group is modified with an aminopropyl group, It is separated and quantified by liquid chromatography using a mixed solvent of a polar solvent and a nonpolar solvent as a mobile phase.
本発明の定量方法においては、上記（Ａ）成分である変性共重合体と、上記（Ｂ）成分である非変性共重合体とは、主鎖の構造が同じであるから、両者の分子量が同じであれば、示差屈折率検出器、紫外吸収検出器等の検出器により得られる変性共重合体及び非変性共重合体のピークを、変性共重合体及び非変性共重合体各々の量に対応する値として、面積比によって、直接変性共重合体と非変性共重合体との比を、予め検量線を作成することなく算出することができる。また、変性共重合体と非変性共重合体との分子量が異なる場合であっても、分子量による検出強度の差を予め測定しておけばよく、この結果から分子量差による強度差を換算するのみで、面積比によって、直接変性共重合体と非変性共重合体との比を算出することができる。 In the quantification method of the present invention, the modified copolymer as the component (A) and the non-modified copolymer as the component (B) have the same main chain structure. If they are the same, the peak of the modified copolymer and the unmodified copolymer obtained by a detector such as a differential refractive index detector or an ultraviolet absorption detector is added to the amount of each of the modified copolymer and the unmodified copolymer. As a corresponding value, the ratio between the directly modified copolymer and the non-modified copolymer can be calculated from the area ratio without preparing a calibration curve in advance. Even if the modified copolymer and the unmodified copolymer have different molecular weights, the difference in the detected intensity due to the molecular weight may be measured in advance, and the intensity difference due to the molecular weight difference is only converted from this result. Thus, the ratio between the directly modified copolymer and the unmodified copolymer can be calculated from the area ratio.
本発明において、分析の対象となる混合物は、（Ａ）成分である共役ジエンモノマーとビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が上記一般式（１）又は（２）で表されるアミノ基で封鎖された変性共重合体と、（Ｂ）共役ジエンモノマーとビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が上記アミノ基、即ち、上記一般式（１）又は（２）で表されるアミノ基で封鎖されていない非変性共重合体とを含むものである。 In the present invention, the mixture to be analyzed is a copolymer of a conjugated diene monomer (A) component and a vinyl aromatic hydrocarbon monomer, and the molecular chain terminal is the above general formula (1) or (2 And (B) a copolymer of a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer, the molecular chain terminal of which is the amino group, that is, the above-mentioned And a non-modified copolymer not blocked with an amino group represented by the general formula (1) or (2).
これら共重合体の骨格を与える共役ジエンモノマーとしては、例えば、１，３−ブタジエン、イソプレン、１，３−ペンタジエン、２，３−ジメチルブタジエン、２−フェニル−１，３−ブタジエン、１，３−ヘキサジエン等が挙げられる。中でも好ましいのは１，３−ブタジエンである。一方、ビニル芳香族炭化水素モノマーとしては、スチレン、α−メチルスチレン、１−ビニルナフタレン、３−ビニルトルエン、エチルビニルベンゼン、ジビニルベンゼン、４−シクロヘキシルスチレン、２，４，６−トリメチルスチレン等を例示することができる。中でも好ましいのは、スチレンである。 Examples of the conjugated diene monomer that gives the skeleton of these copolymers include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 1,3. -Hexadiene and the like. Of these, 1,3-butadiene is preferred. On the other hand, as vinyl aromatic hydrocarbon monomers, styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, etc. It can be illustrated. Of these, styrene is preferred.
また、（Ａ）成分の共重合体は、その分子鎖の一方又は両方が上記一般式（１）又は（２）で示されるアミノ基で封鎖されたものであるが、この上記一般式（１）で表されるアミノ基としては、ジメチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジ−ｎ−ブチルアミノ基、ジイソブチルアミノ基、ジペンチルアミノ基、ジヘキシルアミノ基、ジヘプチルアミノ基、ジオクチルアミノ基、ジアリルアミノ基、ジシクロヘキシルアミノ基、ブチルイソプロピルアミノ基、ジベンジルアミノ基、メチルベンジルアミノ基、メチルヘキシルアミノ基、エチルヘキシルアミノ基等を例示することができる。中でも、ジオクチルアミノ基が好ましい。 The copolymer of component (A) has one or both of its molecular chains blocked with an amino group represented by the above general formula (1) or (2). The amino group represented by) is dimethylamino group, diethylamino group, dipropylamino group, di-n-butylamino group, diisobutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group. And a diallylamino group, a dicyclohexylamino group, a butylisopropylamino group, a dibenzylamino group, a methylbenzylamino group, a methylhexylamino group, and an ethylhexylamino group. Of these, a dioctylamino group is preferable.
一方、上記一般式（２）で表されるアミノ基としては、トリメチレンイミノ基、ピロリジノ基、ピペリジノ基、２−メチルピペリジノ基、３−メチルピペリジノ基、４−メチルピペリジノ基、３，５−ジメチルピペリジノ基、２−エチルピペリジノ基、ヘキサメチレンイミノ基、ヘプタメチレンイミノ基を例示することができる。中でも、ピロリジノ基又はヘキサメチレンイミノ基が好ましい。 On the other hand, the amino group represented by the general formula (2) includes trimethyleneimino group, pyrrolidino group, piperidino group, 2-methylpiperidino group, 3-methylpiperidino group, 4-methylpiperidino group, 3,5-dimethylpiperidin Group, 2-ethylpiperidino group, hexamethyleneimino group and heptamethyleneimino group. Of these, a pyrrolidino group or a hexamethyleneimino group is preferable.
本発明において、分析の対象となる変性共重合体と非変性共重合体との混合物としては、特に限定されるものではないが、例えば、特開平６−１９９９２１号公報に記載されている方法により得られた共重合体、即ち、炭化水素溶媒中、テトラヒドロフラン等のランダマイザーの存在下又は非存在下で、ｎ−ブチルリチウム等の有機リチウム化合物と、下記一般式（３） In the present invention, the mixture of the modified copolymer and the non-modified copolymer to be analyzed is not particularly limited, but for example, by a method described in JP-A-6-199921. The obtained copolymer, that is, an organic lithium compound such as n-butyllithium in a hydrocarbon solvent in the presence or absence of a randomizer such as tetrahydrofuran, and the following general formula (3)
又は下記一般式（４）
Or the following general formula (4)
で表されるアミン化合物とを接触させて生成する可溶性重合開始剤であるリチウム系重合開始剤により１，３−ペンタジエン等の共役ジエンモノマー及びスチレン等のビニル芳香族炭化水素モノマーの共重合を行う方法により得られた共重合体が挙げられる。この共重合体は、変性共重合体と非変性共重合体との分子量がほぼ同等であることから、本発明を好適に適用し得る混合物である。
A conjugated diene monomer such as 1,3-pentadiene and a vinyl aromatic hydrocarbon monomer such as styrene are copolymerized with a lithium-based polymerization initiator that is a soluble polymerization initiator formed by contacting with an amine compound represented by Examples thereof include a copolymer obtained by the method. This copolymer is a mixture to which the present invention can be suitably applied because the molecular weights of the modified copolymer and the non-modified copolymer are substantially the same.
この場合、上記一般式（３）で表されるアミン化合物としては、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジ−ｎ−ブチルアミン、ジイソブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジヘプチルアミン、ジオクチルアミン、ジアリルアミン、ジシクロヘキシルアミン、ブチルイソプロピルアミン、ジベンジルアミン、メチルベンジルアミン、メチルヘキシルアミン、エチルヘキシルアミン等、上記一般式（４）で表されるアミン化合物としては、トリメチレンイミン、ピロリジン、ピペリジン、２−メチルピペリジン、３−メチルピペリジン、４−メチルピペリジン、３，５−ジメチルピペリジン、２−エチルピペリジン、ヘキサメチレンイミン、ヘプタメチレンイミン等が好ましく挙げられる。 In this case, as the amine compound represented by the general formula (3), dimethylamine, diethylamine, dipropylamine, di-n-butylamine, diisobutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, diallylamine , Dicyclohexylamine, butylisopropylamine, dibenzylamine, methylbenzylamine, methylhexylamine, ethylhexylamine, and the like, amine compounds represented by the above general formula (4) include trimethyleneimine, pyrrolidine, piperidine, 2-methyl Preferred are piperidine, 3-methylpiperidine, 4-methylpiperidine, 3,5-dimethylpiperidine, 2-ethylpiperidine, hexamethyleneimine, heptamethyleneimine and the like.
本発明の定量方法は、上述したような（Ａ）成分の変性共重合体と、（Ｂ）成分の非変性共重合体との混合物である高分子材料中の、（Ａ）成分と（Ｂ）成分とを液体クロマトグラフィー、特に高速液体クロマトグラフィー（ＨＰＬＣ）で分離するものであるが、この場合の固定相として、表面シラノール基が非修飾のシリカゲル又は表面シラノール基の一部若しくは全部がアミノプロピル基で修飾されたシリカゲルを用いる。このようなものとしては、市販品を用い得、例えば、Ｍｅｒｃｋ社製 ＬｉＣｈｒｏｓｏｒｂ Ｓｉ６０等が挙げられる。 The quantification method of the present invention comprises the components (A) and (B) in the polymer material which is a mixture of the modified copolymer (A) and the non-modified copolymer (B) as described above. ) Components are separated from each other by liquid chromatography, particularly high performance liquid chromatography (HPLC). In this case, as the stationary phase, silica gel whose surface silanol groups are unmodified or part or all of the surface silanol groups are amino. Silica gel modified with propyl groups is used. As such a thing, a commercial item can be used, For example, Merck Corporation LiChrosorb Si60 etc. are mentioned.
一方、移動相（溶離液）としては、極性溶媒と非極性溶媒との混合溶媒を用いる。この場合、極性溶媒としては、上述した高分子材料を溶解可能であり、かつ吸着クロマトグラフィーにおける溶媒能力が高いものが用いられ、例えば、クロロホルム、テトラヒドロフラン、メタノール及びエタノールから選ばれる１種又は２種以上を用いることが好適である。この場合、クロロホルム及び／又はテトラヒドロフランと、メタノール及び／又はエタノールとを容量比で９９．９／０．１〜９５／５で混合したものを極性溶媒として用いることが特に好ましい。 On the other hand, a mixed solvent of a polar solvent and a nonpolar solvent is used as the mobile phase (eluent). In this case, as the polar solvent, those capable of dissolving the above-described polymer material and having a high solvent ability in adsorption chromatography are used. For example, one or two kinds selected from chloroform, tetrahydrofuran, methanol and ethanol are used. It is preferable to use the above. In this case, it is particularly preferable to use as a polar solvent a mixture of chloroform and / or tetrahydrofuran and methanol and / or ethanol at a volume ratio of 99.9 / 0.1 to 95/5.
また、非極性溶媒としては、上述した高分子材料を溶解可能であり、かつ吸着クロマトグラフィーにおける溶媒能力が低いものが用いられ、例えば、シクロヘキサン、ヘキサン及びヘプタンから選ばれる１種又は２種以上を用いることが好適である。 In addition, as the nonpolar solvent, those capable of dissolving the above-described polymer material and having a low solvent ability in adsorption chromatography are used. For example, one or more selected from cyclohexane, hexane and heptane are used. It is preferable to use it.
極性溶媒と非極性溶媒との混合比は、特に限定されるものではないが、極性溶媒／非極性溶媒＝１／９〜５／５（容量比）とすることが好ましい。 The mixing ratio of the polar solvent and the nonpolar solvent is not particularly limited, but is preferably polar solvent / nonpolar solvent = 1/9 to 5/5 (volume ratio).
（Ａ）成分及び（Ｂ）成分の定量に用いる検出器としては、示差屈折率検出器（ＲＩ）、紫外吸収検出器（ＵＶ）等を用い得るが、検出感度及び汎用性に優れ、精度よく定量できる観点からエバポレイト光散乱検出器を用いることも好適である。なお、液体クロマトグラフィーによる分離及び検出における他の条件は、従来公知の一般的な液体クロマトグラフィー条件を適用し得る。 As a detector used for quantification of the component (A) and the component (B), a differential refractive index detector (RI), an ultraviolet absorption detector (UV), etc. can be used, but it has excellent detection sensitivity and versatility, and has high accuracy. From the viewpoint of quantification, it is also preferable to use an evaporator light scattering detector. In addition, conventionally well-known general liquid chromatography conditions can be applied to other conditions in separation and detection by liquid chromatography.
本発明は、数平均分子量が５，０００〜１，０００，０００、特に、従来の方法では短時間、かつ高精度の分析が極めて困難であった数平均分子量が１００，０００以上の高分子材料の定量において威力を発揮し、例えば、５〜１０分程度という極めて短時間で高精度の分析が可能である。 The present invention relates to a polymer material having a number average molecular weight of 5,000 to 1,000,000, in particular, a polymer material having a number average molecular weight of 100,000 or more, which was extremely difficult to analyze with high accuracy in a short time by the conventional method. Power is demonstrated in the quantitative determination of, and for example, highly accurate analysis is possible in an extremely short time of about 5 to 10 minutes.
以下、実施例を挙げて本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。なお、合成例で用いた全ての原料は脱水精製したものを用いた。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to the following Example. All raw materials used in the synthesis examples were dehydrated and purified.
［合成例１〜７］
乾燥し、窒素置換された８００ｍｌの耐圧ガラス容器に、表１の処方に従って、シクロヘキサン、１，３−ブタジエンモノマー、スチレンモノマー、テトラヒドロフラン（ＴＨＦ）、ヘキサメチレンイミン（ＨＭＩ）、ピロリジン、ジオクチルアミンを注入し、これにｎ−ブチルリチウム（ＢｕＬｉ）を加えた後、５０℃で２時間重合を行った。重合系は重合開始から終了まで、全く沈澱は見られず均一に透明であった。重合転化率はほぼ１００％であった。重合溶液の一部をサンプリングし、イソプロピルアルコールを加え、固形物を乾燥し、ゴム状共重合体を得た。この共重合体の分子量分布を測定した結果を表１に併記する。
[Synthesis Examples 1 to 7]
According to the formulation shown in Table 1, cyclohexane, 1,3-butadiene monomer, styrene monomer, tetrahydrofuran (THF), hexamethyleneimine (HMI), pyrrolidine, and dioctylamine are injected into an 800 ml pressure-resistant glass container that has been dried and purged with nitrogen. Then, n-butyllithium (BuLi) was added thereto, followed by polymerization at 50 ° C. for 2 hours. From the start to the end of the polymerization, the polymerization system was uniformly transparent without any precipitation. The polymerization conversion was almost 100%. A part of the polymerization solution was sampled, isopropyl alcohol was added, and the solid was dried to obtain a rubbery copolymer. The results of measuring the molecular weight distribution of this copolymer are also shown in Table 1.
なお、共重合体の数平均分子量（Ｍｎ）の測定は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ：東ソー製 ＨＬＣ−８０２０、カラム：東ソー製 ＧＭＨ−ＸＬ（２本直列））により、示差屈折率検出器（ＲＩ）を用いて行い、単分散ポリスチレンを標準とするポリスチレン換算値とした。 The number average molecular weight (Mn) of the copolymer was measured by gel permeation chromatography (GPC: Tosoh HLC-8020, column: Tosoh GMH-XL (two in series)). This was carried out using a vessel (RI), and the value was converted to polystyrene using monodisperse polystyrene as a standard.
［実施例１〜６］
合成例１〜６で得られた各々の共重合体中の変性共重合体と非変性共重合体とを下記の液体クロマトグラフィーにより分析し、変性共重合体と非変性共重合体との比を求めた。結果を表２に示す。
[Examples 1 to 6]
The modified copolymer and the unmodified copolymer in each of the copolymers obtained in Synthesis Examples 1 to 6 were analyzed by the following liquid chromatography, and the ratio of the modified copolymer to the unmodified copolymer was determined. Asked. The results are shown in Table 2.
分析試料調製
各合成例において得られたゴム状共重合体を下記溶離液に１ｍｇ／ｍｌの濃度で溶解させたものを分析試料溶液とした。
液体クロマトグラフィー（ＨＰＬＣ）
カラム：Ｍｅｒｃｋ社製 ＬｉＣｈｒｏｓｏｒｂ Ｓｉ６０（径４ｍｍ、長さ２５０ｍｍ）
溶離液：（１ｖｏｌ％エタノール−９９ｖｏｌ％クロロホルム液）／シクロヘキサン＝３／７
検出器：ＵＶ（２５４ｎｍ）
温度：４０℃
流速：１ｍｌ／ｍｉｎ
試料注入量：２０μｌ
クロマトグラムの描画及びピーク面積の計数は電位差積算型データ処理機（インテグレータ）による。
Analytical sample preparation The rubbery copolymer obtained in each synthesis example was dissolved in the following eluent at a concentration of 1 mg / ml to obtain an analytical sample solution.
Liquid chromatography (HPLC)
Column: LiChrosorb Si60 (diameter 4 mm, length 250 mm) manufactured by Merck
Eluent: (1 vol% ethanol-99 vol% chloroform solution) / cyclohexane = 3/7
Detector: UV (254 nm)
Temperature: 40 ° C
Flow rate: 1 ml / min
Sample injection volume: 20 μl
Drawing of the chromatogram and counting of the peak area are performed by a potential difference integration type data processor (integrator).
また、実施例１〜５で得られたクロマトグラムを図１に、実施例１〜５で用いた各共重合体合成時の原料ヘキサメチレンイミンとｎ−ブチルリチウムとの比（ＨＭＩ／ＢｕＬｉ）に対して、対応する共重合体により得られたクロマトグラムの置換共重合体のピーク面積の割合をプロットしたグラフを図２に、実施例６で得られたクロマトグラムを図３に各々示す。 Further, the chromatograms obtained in Examples 1 to 5 are shown in FIG. 1, and the ratio of the raw material hexamethyleneimine and n-butyllithium at the time of synthesizing each copolymer used in Examples 1 to 5 (HMI / BuLi). FIG. 2 is a graph plotting the ratio of the peak area of the substituted copolymer in the chromatogram obtained with the corresponding copolymer, and FIG. 3 is the chromatogram obtained in Example 6.
［実施例７］
合成例７で得られた共重合体中の変性共重合体と非変性共重合体とを、溶離液として（１ｖｏｌ％エタノール−９９ｖｏｌ％クロロホルム液）／シクロヘキサン＝１／９を用いた以外は実施例１と同様の方法で液体クロマトグラフィーにより分析し、変性共重合体と非変性共重合体との比を求めた。結果を表２に示す。また、得られたクロマトグラムを図４に示す。
[Example 7]
The modified copolymer and the unmodified copolymer in the copolymer obtained in Synthesis Example 7 were used except that (1 vol% ethanol-99 vol% chloroform solution) / cyclohexane = 1/9 was used as an eluent. Analysis was performed by liquid chromatography in the same manner as in Example 1 to determine the ratio of the modified copolymer to the unmodified copolymer. The results are shown in Table 2. Moreover, the obtained chromatogram is shown in FIG.
Claims (5)
又は下記一般式（２）
で表されるアミノ基で封鎖された変性共重合体と、
（Ｂ）上記共役ジエンモノマーと上記ビニル芳香族炭化水素モノマーとの共重合体であって、分子鎖末端が上記アミノ基で封鎖されていない非変性共重合体
とを含む高分子材料中の上記（Ａ）成分と上記（Ｂ）成分との比を定量する方法であって、
上記高分子材料中の上記（Ａ）成分と上記（Ｂ）成分とを、表面シラノール基が非修飾のシリカゲル又は表面シラノール基の一部若しくは全部がアミノプロピル基で修飾されたシリカゲルを固定相、極性溶媒と非極性溶媒との混合溶媒を移動相とする液体クロマトグラフィーにて分離して定量することを特徴とする定量方法。 (A) A copolymer of a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer, the molecular chain terminal of which is represented by the following general formula (1)
Or the following general formula (2)
A modified copolymer blocked with an amino group represented by:
(B) The above-mentioned polymer in a polymer material comprising a copolymer of the conjugated diene monomer and the vinyl aromatic hydrocarbon monomer, wherein the molecular chain terminal is not blocked with the amino group. A method for quantifying the ratio of the component (A) to the component (B),
The stationary phase of the component (A) and the component (B) in the polymer material is a silica gel in which the surface silanol group is unmodified or in which part or all of the surface silanol group is modified with an aminopropyl group, A quantification method comprising separating and quantifying by a liquid chromatography using a mixed solvent of a polar solvent and a nonpolar solvent as a mobile phase.
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| KR20180012202A (en) * | 2016-07-26 | 2018-02-05 | 주식회사 엘지화학 | Method for measuring a modified ratio of a polymer |
| KR20190037521A (en) * | 2017-09-29 | 2019-04-08 | 주식회사 엘지화학 | Method for measuring a modified ratio of a polymer |
| WO2019066396A3 (en) * | 2017-09-29 | 2019-05-23 | 주식회사 엘지화학 | Rubber composition |
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| WO2019066396A3 (en) * | 2017-09-29 | 2019-05-23 | 주식회사 엘지화학 | Rubber composition |
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