JPH0450765A - Packing material for liquid chromatograph - Google Patents
Packing material for liquid chromatographInfo
- Publication number
- JPH0450765A JPH0450765A JP2160751A JP16075190A JPH0450765A JP H0450765 A JPH0450765 A JP H0450765A JP 2160751 A JP2160751 A JP 2160751A JP 16075190 A JP16075190 A JP 16075190A JP H0450765 A JPH0450765 A JP H0450765A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- packing material
- mixture
- hydroxyethyl methacrylate
- saccharified
- 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.)
- Pending
Links
- 238000012856 packing Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 title abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims abstract description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims abstract description 10
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 11
- 239000007900 aqueous suspension Substances 0.000 claims description 10
- 238000004811 liquid chromatography Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000725 suspension Substances 0.000 abstract 2
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 230000004304 visual acuity Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 16
- 239000000945 filler Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 229920005654 Sephadex Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000001042 affinity chromatography Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000005373 porous glass Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- QBUKAFSEUHGMMX-MTJSOVHGSA-N (5z)-5-[[3-(1-hydroxyethyl)thiophen-2-yl]methylidene]-10-methoxy-2,2,4-trimethyl-1h-chromeno[3,4-f]quinolin-9-ol Chemical compound C1=CC=2NC(C)(C)C=C(C)C=2C2=C1C=1C(OC)=C(O)C=CC=1O\C2=C/C=1SC=CC=1C(C)O QBUKAFSEUHGMMX-MTJSOVHGSA-N 0.000 description 1
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- 206010029719 Nonspecific reaction Diseases 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000011543 agarose gel Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- -1 glycosyl ethyl methacrylate Chemical compound 0.000 description 1
- 125000003147 glycosyl group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、液体クロマトグラフ用充填剤に関し、より特
定的には、ゲルパーミェーションクロマトグラフ（以下
、ＧＰＣと略す）及びアフィニティークロマトグラフに
用いるのに適した充填剤に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a packing material for liquid chromatography, and more specifically, gel permeation chromatograph (hereinafter abbreviated as GPC) and affinity chromatograph. The present invention relates to a filler suitable for use in.
従来より、天然高分子や合成高分子の分子量及び分子量
分布を迅速に測定する方法として、液体り凸マドグラフ
の一種であるＧＰＣが広く利用されている。ＧＰＣでは
、使用するカラム充填剤によって試料に対して用いられ
る溶媒の種類が制限され、従って測定の対象となる高分
子の種類も制約を受けざるを得なかった。BACKGROUND ART Conventionally, GPC, which is a type of liquid polygon graph, has been widely used as a method for rapidly measuring the molecular weight and molecular weight distribution of natural polymers and synthetic polymers. In GPC, the type of solvent that can be used for a sample is limited depending on the column packing material used, and therefore the type of polymer to be measured is also restricted.
現在、ＧＰＣ用充填剤としては、ポリスチレンゲルが最
もよく使用されている。ポリスチレンゲルは、スチレン
とジビニルベンゼンとの共重合体であり、優れた分解能
及び広い分子量分布に対する優れた分割能並びに大きな
機械的強度等の長所を有するがミこの共重合体は非極性
高分子であり疎水性である。従って、はとんどすべての
有機溶媒により溶解した試料液を用いることができるが
、水溶液系の試料液に適用して分子量を一測定すること
はできなかった。Currently, polystyrene gel is most commonly used as a packing material for GPC. Polystyrene gel is a copolymer of styrene and divinylbenzene, and has advantages such as excellent resolution, excellent resolution for a wide molecular weight distribution, and large mechanical strength. However, this copolymer is a nonpolar polymer. Yes, it is hydrophobic. Therefore, although it is possible to use a sample solution dissolved in almost any organic solvent, it has not been possible to measure the molecular weight by applying this method to an aqueous sample solution.
そこで、水溶液系試料を適用し得る充填剤として、上記
スチレンゲルに代えて、多孔性シリカ、多孔性ガラスま
たは架橋デキストランゲル等が使用されてきた。Therefore, instead of the above-mentioned styrene gel, porous silica, porous glass, crosslinked dextran gel, etc. have been used as fillers to which aqueous samples can be applied.
しかしながら、多孔性シリカや多孔性ガラスのような無
機質系充填剤は、機械的強度は高いものの、分子量分割
能が小さく、分子量分割範囲が狭いという欠点を有する
。However, although inorganic fillers such as porous silica and porous glass have high mechanical strength, they have the drawback of low molecular weight resolution and narrow molecular weight resolution range.
他方、架橋デキストランゲルは分子量分割範囲が狭く機
械的強度が小さいため、比較的高圧の条件下で用いる高
速液体クロマトグラフ用充填剤として使用できないとい
う欠点がある。On the other hand, crosslinked dextran gel has a narrow molecular weight resolution range and low mechanical strength, so it has the disadvantage that it cannot be used as a packing material for high performance liquid chromatography used under relatively high pressure conditions.
さらに、生化学実験に頻用されているアフィニティーク
ロマトグラフでは、上記デキストランゲルや、アガロー
スゲル等が用いられているが、いずれも機械的強度が小
さく、高速で迅速に分離することができなかった。また
、合成高分子に、例えばアミノ基、カルボキシル基また
はカルボニル基等の官能基を導入することにより構成さ
れたアフィニティークロマトグラフ用充填剤も使用され
ているが、非特異的反応を生じたりして、必ずしも満足
の行くものではなかった。Furthermore, affinity chromatographs frequently used in biochemical experiments use the above-mentioned dextran gel, agarose gel, etc., but both have low mechanical strength and cannot perform rapid separation at high speed. In addition, affinity chromatography packing materials constructed by introducing functional groups such as amino groups, carboxyl groups, or carbonyl groups into synthetic polymers are also used, but they may cause nonspecific reactions. , which was not necessarily satisfactory.
本発明は、上述した従来のＧＰＣまたはアフィニティー
クロマトグラフ用充填剤の欠点を解消するものであり、
水溶液系試料液に対して適用することができ、かつ高分
解能及び高理論段数を有する充填剤を提供することを目
的とする。The present invention eliminates the drawbacks of the conventional packing materials for GPC or affinity chromatography described above.
The object of the present invention is to provide a packing material that can be applied to aqueous sample solutions and has high resolution and a high number of theoretical plates.
〔課題を解決するための手段及び作用〕本発明の液体ク
ロマトグラフ用充填剤は、テトラメチロールメタントリ
アクリレートまたはジビニルベンゼン１００重量部と、
糖化ヒドロキシエチルメタクリレート５〜６０重量部と
よりなる混合物を、該混合物は溶解するがその重合体は
溶解しない有機溶媒の存在下において水性懸濁重合する
ことにより得られた多孔性ポリマーよりなることを特徴
とする。[Means and effects for solving the problem] The liquid chromatography packing material of the present invention contains 100 parts by weight of tetramethylolmethane triacrylate or divinylbenzene,
A porous polymer obtained by aqueous suspension polymerization of a mixture consisting of 5 to 60 parts by weight of glycated hydroxyethyl methacrylate in the presence of an organic solvent that dissolves the mixture but does not dissolve the polymer. Features.
以下、本発明の液体クロマトグラフ用充填剤の構成に関
し、作用を併せてより詳細に説明する。Hereinafter, the structure of the packing material for liquid chromatography of the present invention will be explained in more detail together with its effects.
本発明では、充填剤を構成する多孔性ポリマーは、テト
ラメチロールメタントリアクリレートまたはジビニルベ
ンゼン１００重量部に対し、糖化ヒドロキシエチルメタ
クリレートが５〜６０重量部が添加されている。テトラ
メチロールメタントリアクリレートまたはジビニルベン
ゼンを用いるのは、得られた重合体において、これらが
３次元網状架橋し、多孔性ポリマーの機械的強度を高め
るからである。また、糖化ヒドロキシエチルメタクリレ
ートを添加するのは、ヒドロキシ基により親水性が付与
されるからである。In the present invention, in the porous polymer constituting the filler, 5 to 60 parts by weight of saccharified hydroxyethyl methacrylate is added to 100 parts by weight of tetramethylolmethane triacrylate or divinylbenzene. The reason why tetramethylolmethane triacrylate or divinylbenzene is used is that in the resulting polymer, these three-dimensional network crosslinks increase the mechanical strength of the porous polymer. Furthermore, the reason why saccharified hydroxyethyl methacrylate is added is that the hydroxy group imparts hydrophilicity.
糖化ヒドロキシエチルメタクリレートは、以下の構造で
表される化合物である。Glycated hydroxyethyl methacrylate is a compound represented by the following structure.
ＣＩ（。CI(.
Ｒ＋ ＯＣＨｘ ＣＨｉ Ｏ−ＣＣ−ＣＨ１（
Ｒ１：ＩＩ数が２以下の糖類から、水酸基１ケが除かれ
た基を表す）
代表的なものとしては、Ｒ，をグルコースから１ケの水
酸基が除かれた基とした次に示すグリコジルエチルメタ
クリレートが好ましい。R+ OCHx CHi O-CC-CH1(
R1: represents a group obtained by removing one hydroxyl group from a saccharide with II number of 2 or less) Typical examples include the following glycosyl group, where R is a group obtained by removing one hydroxyl group from glucose. Ethyl methacrylate is preferred.
糖化しドロキシエチルメタクリレートを上記の割合で添
加するのは、糖化ヒトミキシエチルメタクリレートが５
重量部より少ない場合には目的とする親水性を得ること
ができないからであり、他方、６０重量部を超えて添加
すると架橋度が充分に得られないため、粒子の膨潤度が
大きくなり、液体クロマトグラフ用充填剤として適さな
いからである。Adding saccharified human mixyethyl methacrylate at the above ratio means that saccharified human mixyethyl methacrylate is
This is because if it is less than 60 parts by weight, the desired hydrophilicity cannot be obtained.On the other hand, if it is added in excess of 60 parts by weight, a sufficient degree of crosslinking cannot be obtained, and the degree of swelling of the particles increases, resulting in liquid This is because it is not suitable as a chromatographic packing material.
さらに、本発明では、上記混合物が有機溶媒の存在下で
水性懸濁重合されるのであるが、この有機溶媒としては
、混合物を溶解するがその重合体を溶解しないすべての
有機溶媒を使用することができる０例えば、トルエン、
キシレン、ジエチルベンゼン、もしくはドデシルベンゼ
ン等の芳香族炭化水素類、ヘキサン、ヘプタン、オクタ
ンもしくはデカン等の脂肪族炭化水素類、またはイソア
ミルアルコール、ヘキシルアルコールもしくはオクチル
アルコール等のアルコール類が挙げられる。Furthermore, in the present invention, the above-mentioned mixture is subjected to aqueous suspension polymerization in the presence of an organic solvent, and this organic solvent may be any organic solvent that dissolves the mixture but does not dissolve the polymer. For example, toluene,
Examples include aromatic hydrocarbons such as xylene, diethylbenzene or dodecylbenzene, aliphatic hydrocarbons such as hexane, heptane, octane or decane, or alcohols such as isoamyl alcohol, hexyl alcohol or octyl alcohol.
また、これらの有機溶媒の添加量は何ら限定されるもの
ではないが、上記の割合で得られた混合物に対して、１
５〜２００重量部用いられるのが好ましく、より好まし
くは２０〜１５０重量部である。In addition, the amount of these organic solvents added is not limited in any way, but for the mixture obtained at the above ratio, 1
It is preferable to use 5 to 200 parts by weight, more preferably 20 to 150 parts by weight.
上記混合物は水性懸濁重合されるため、混合物に均一に
溶解されていた有機溶媒は得られた重合体粒子中に分散
して存在する。従って、重合の終了後に、有機溶媒を粒
子中から取り除くことにより、多孔性ポリマーが得られ
る。すなわち、有機溶媒は、多孔性ポリマーにおける細
孔を形成するために用いられている。Since the above mixture is subjected to aqueous suspension polymerization, the organic solvent that was uniformly dissolved in the mixture exists dispersed in the obtained polymer particles. Therefore, by removing the organic solvent from the particles after completion of polymerization, a porous polymer can be obtained. That is, organic solvents are used to form pores in porous polymers.
また、上記混合物と相溶性の異なる種々の有機溶媒を使
用することにより、多孔性ポリマーの細孔の大きさを任
意に変化させることも可能である。Further, by using various organic solvents having different compatibility with the above mixture, it is also possible to arbitrarily change the size of the pores of the porous polymer.
さらに、水性懸濁重合は公知の任意の方法により行うこ
とができる０例えば上記有ｆｌＡ’Ｒ媒に、上記混合物
及びラジカル発生触媒を熔解し、得られた溶液をポリビ
ニルアルコールまたはリン酸カルシウム等の懸濁重合安
定剤が溶解された水相に添加し、撹拌しつつ５０〜１０
０ ”Ｃに加熱することにより行われる。Furthermore, aqueous suspension polymerization can be carried out by any known method. For example, the above mixture and radical generating catalyst are dissolved in the above-mentioned flA'R medium, and the resulting solution is suspended in polyvinyl alcohol or calcium phosphate. Add to the aqueous phase in which the polymerization stabilizer has been dissolved, and add 50 to 10
This is done by heating to 0''C.
また、上記混合物を、ポリビニルアルコールの存在下で
水性懸濁重合させると、混合物の形態が安定化し、粒径
が比較的均一であり、液体クロマトグラフ用の充填剤と
して好適な多孔性ポリマーを得ることができる。従って
、本発明においては、懸濁重合安定剤として、ポリビニ
ルアルコールを用いることが好ましい。Furthermore, when the above mixture is subjected to aqueous suspension polymerization in the presence of polyvinyl alcohol, the morphology of the mixture is stabilized, the particle size is relatively uniform, and a porous polymer suitable as a filler for liquid chromatography is obtained. be able to. Therefore, in the present invention, it is preferable to use polyvinyl alcohol as the suspension polymerization stabilizer.
上記ラジカル発生触媒は、反応開始剤としてうジカルを
発生する触媒であるが、該触媒としては、例えばベンゾ
イルパーオキサイドもしくはクメンパーオキサイド等の
有機過酸化物、過酸化水素、過硫酸カリウムもしくは過
硫酸アンモニウム等の無機過酸化物、またはアゾビスイ
ソブチロニトリルもしくはアゾビスイソブチロアミド等
のアゾ化合物等の公知のラジカル発生触媒を任意に使用
することができる。The radical generating catalyst described above is a catalyst that generates a radical as a reaction initiator, and examples thereof include organic peroxides such as benzoyl peroxide or cumene peroxide, hydrogen peroxide, potassium persulfate, or ammonium persulfate. Known radical-generating catalysts such as inorganic peroxides such as, or azo compounds such as azobisisobutyronitrile or azobisisobutyramide can be optionally used.
水性懸濁重合により重合されたポリマー粒子は、加熱等
により乾燥され、粒子中の有機溶媒が放出されることに
より多孔性ポリマーとされる。そして、液体クロマトグ
ラフ用充填剤として用いるには、多孔性ポリマーの粒子
が均一であり、かつ粒径が３〜４０μｍの範囲であるこ
とが好ましい。Polymer particles polymerized by aqueous suspension polymerization are dried by heating or the like, and the organic solvent in the particles is released, thereby forming a porous polymer. In order to use the porous polymer as a filler for liquid chromatography, it is preferable that the particles of the porous polymer are uniform and have a particle size in the range of 3 to 40 μm.
また、細孔は粒径により異なるが、一般に粒子の内部に
向かって５０〜２０００人の深さを有することが好まし
い。Although the pores vary depending on the particle size, it is generally preferable that the pores have a depth of 50 to 2000 pores toward the inside of the particle.
本発明によれば、テトラメチロールメタントリアクリレ
ートまたはジビニルベンゼンに対して特爺の割合で糖化
ヒドロキシエチルメタクリレートを混合してなる混合物
を有機溶媒の存在下に水性懸濁重合することにより得ら
れた多孔性ポリマーにより液体クロマトグラフ用充填剤
が構成されるため、その分子中に糖化ヒドロキシエチル
メタクリレート由来の水酸基を有する。従って、親水性
ポリマーに対して良好な分子量分割能を発揮する。According to the present invention, a porous material obtained by aqueous suspension polymerization of a mixture of tetramethylolmethane triacrylate or divinylbenzene in a specific ratio of glycated hydroxyethyl methacrylate in the presence of an organic solvent. Since the packing material for liquid chromatography is composed of a polymer with a hydroxyl content, it has a hydroxyl group derived from glycated hydroxyethyl methacrylate in its molecule. Therefore, it exhibits good molecular weight resolution for hydrophilic polymers.
また、テトラメチロールメタントリアクリレート及びジ
ビニルベンゼンは重合されると３次元綱状架橋するため
、多孔性ポリマーの機械的強度は高く、従ってＧＰＣ用
充填剤として特に好適に用いられ得る。Moreover, since tetramethylolmethane triacrylate and divinylbenzene undergo three-dimensional linear crosslinking when polymerized, the mechanical strength of the porous polymer is high, and therefore, it can be particularly suitably used as a filler for GPC.
さらに、本発明の液体クロマトグラフ用充填則は、上記
混合物の重合体を溶解しない有機溶媒の存在下で水性懸
濁重合されて得られるものであるため、有機溶媒を除去
することにより、ポリマーの微粒子内に多くの細孔が形
成され、従って分子量分割能が効果的に高められる。ま
た、上記有機溶媒を変更することにより、任意の大きさ
の細孔を形成することができ、さらに、重合条件を変化
することにより任意の粒子径の粒子を得ることができる
。よって、さまざまな液体クロマトグラフに適切な充填
剤を提供することが可能となる。Furthermore, since the packing rule for liquid chromatography of the present invention is obtained by aqueous suspension polymerization in the presence of an organic solvent that does not dissolve the polymer in the above mixture, removing the organic solvent allows the polymer to be dissolved. Many pores are formed within the microparticles, thus effectively increasing the molecular weight resolution. Further, by changing the organic solvent, pores of any size can be formed, and furthermore, by changing the polymerization conditions, particles of any particle size can be obtained. Therefore, it becomes possible to provide suitable fillers for various liquid chromatographs.
以下、本発明を実施例により詳細に説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
裏旌班上
冷却器、撹拌機、温度針及び演下濾斗が設置された２２
のセパラブルフラスコに、４重量％のボリヒニルアルコ
ール水溶液４００ｄと、グルコシルエメルメタクリレー
ト（日本精化株式会社製）２０ｇ１ジビニルベンゼン８
０ｇ、トルエン１００ｇ及びベンゾイルパーオキサイド
１．５ｇとよりなる混合液を供給した。次に４００ｒｐ
ｍの撹拌速度で撹拌しながら８０°Ｃに昇温し、１０時
間重合反応を行った後冷却した。22 where an upper cooler, a stirrer, a temperature needle, and a lower funnel were installed.
In a separable flask, 400 d of a 4% by weight aqueous solution of borihinyl alcohol, 20 g of glucosyl emer methacrylate (manufactured by Nippon Fine Chemical Co., Ltd.), 8 g of divinylbenzene
A mixed solution consisting of 0g of toluene, 100g of toluene, and 1.5g of benzoyl peroxide was supplied. then 400rp
The temperature was raised to 80° C. while stirring at a stirring speed of m, and the polymerization reaction was carried out for 10 hours, followed by cooling.
冷却後、重合生成物を固液分離した後、熱水及びアセト
ンで洗浄後、乾燥した。得られた粒子径が４〜１３μｍ
の多孔性ポリマーを分級し粒子径５〜７μｍの粒子を集
め液体クロマトグラフ用充ｔｉを得た。この充填剤の３
５１１を３０ｍの蒸留水に分散し、ＣＰＣ用スナステン
レスカラム径７゜９−１長さ５０Ｃ１）に高圧定流量ポ
ンプにより蒸留水を２．、Ｏｄ１分の速度で圧送して充
填した。After cooling, the polymerization product was separated into solid and liquid, washed with hot water and acetone, and then dried. The obtained particle size is 4 to 13 μm
The porous polymer was classified and particles having a particle diameter of 5 to 7 μm were collected to obtain a liquid chromatography solution. 3 of this filler
511 was dispersed in 30 m of distilled water, and 2.5 m of distilled water was added to a Suna stainless steel column for CPC (diameter 7°9-1 length 50C1) using a high-pressure constant flow pump. , Od1 minute.
得られた充填カラムを高速液体クロマトグラフ（島津製
作所製、商品名；島津高速液体りロマトグラフＬＣ−５
型）に接続し、分子量の異なる標準デキストラン及びポ
リエチレングリコールを試料とし、蒸留水を溶離液とし
て分子量を測定したところ、分子量３５万以下において
良好な分子量分割能を有しており、各ピークは正常な対
称形であった。The obtained packed column was packed in a high-performance liquid chromatograph (manufactured by Shimadzu Corporation, product name: Shimadzu High-Performance Liquid Chromatograph LC-5).
When the molecular weight was measured using standard dextran and polyethylene glycol with different molecular weights as samples and using distilled water as the eluent, it had good molecular weight resolution at molecular weights of 350,000 or less, and each peak was normal. It had a symmetrical shape.
またグルコースを用いて測定したカラム１本当たりの理
論段数は５０００段１０．５ｍであった。Further, the number of theoretical plates per column measured using glucose was 5000 plates and 10.5 m.
亥崖班呈
グリコジルエチルメタクリレート３０ｇ１テトラメチロ
ールメタントリアクリレート７０ｇ、トルエン１００ｇ
及びベンゾイルパーオキサイド１゜５ｇよりなる混合液
を使用した以外は実施例１で行ったのと同様にして水性
懸濁重合、固液分動、熱水及びアセトン洗浄、次いで乾
燥を行い、粒子径５〜１５μｍの多孔性ポリマーを得た
。30g of glycosyl ethyl methacrylate, 70g of tetramethylolmethane triacrylate, 100g of toluene
Aqueous suspension polymerization, solid-liquid partitioning, washing with hot water and acetone, and then drying were carried out in the same manner as in Example 1, except that a mixed solution consisting of 1.5 g of benzoyl peroxide and 1.5 g of benzoyl peroxide was used. A porous polymer of 5-15 μm was obtained.
得られた多孔性ポリマーのうち粗粒子を取り除いて得ら
れた粒子径８〜ｌＯμｍの液体クロマトグラフ用充填剤
３５ｍを８０ｍの蒸留水に分散し、ＧＰＣ用スナステン
レスカラム径７．９閣、長さ５０３）に高圧定流量ポン
プにより蒸留水を１゜６ａｅ／分の速度で圧送して充填
した。35 m of a liquid chromatography packing material with a particle size of 8 to 10 μm obtained by removing coarse particles from the porous polymer obtained was dispersed in 80 m of distilled water, and a Suna stainless steel column for GPC with a diameter of 7.9 mm and a length of 503) was filled with distilled water by force-feeding it at a rate of 1°6 ae/min using a high-pressure constant flow pump.
得られた充填カラムを実施例１で使用した高速液体クロ
マトグラフに接続し、分子量の異なる標準デキストラン
及びポリエチレングリコールを試料とし、蒸留水を溶離
液として分子量を測定したところ、分子量４０万以下に
おいて良好な分子量分割能を有しており、各ピークは正
常な対称形であった。The obtained packed column was connected to the high performance liquid chromatograph used in Example 1, and the molecular weight was measured using standard dextran and polyethylene glycol with different molecular weights as samples and distilled water as the eluent. As a result, a molecular weight of 400,000 or less was good. It had excellent molecular weight resolution, and each peak had a normal symmetrical shape.
またエチレングリコールを用いて測定したカラム１本当
たりの理論段数は６０００段１０．５ｍであった。The number of theoretical plates per column measured using ethylene glycol was 6000 plates and 10.5 m.
Claims (1)
ジビニルベンゼン１００重量部と、糖化ヒドロキシエチ
ルメタクリレート５〜６０重量部とよりなる混合物を、
該混合物を溶解するがその重合体は溶解しない有機溶媒
の存在下において水性懸濁重合することにより得られた
多孔性ポリマーよりなることを特徴とする、液体クロマ
トグラフ用充填剤。(1) A mixture consisting of 100 parts by weight of tetramethylolmethane triacrylate or divinylbenzene and 5 to 60 parts by weight of glycated hydroxyethyl methacrylate,
A packing material for liquid chromatography, comprising a porous polymer obtained by aqueous suspension polymerization in the presence of an organic solvent that dissolves the mixture but does not dissolve the polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160751A JPH0450765A (en) | 1990-06-18 | 1990-06-18 | Packing material for liquid chromatograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2160751A JPH0450765A (en) | 1990-06-18 | 1990-06-18 | Packing material for liquid chromatograph |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0450765A true JPH0450765A (en) | 1992-02-19 |
Family
ID=15721676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2160751A Pending JPH0450765A (en) | 1990-06-18 | 1990-06-18 | Packing material for liquid chromatograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0450765A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010223332A (en) * | 2009-03-24 | 2010-10-07 | Hitachi Plant Technologies Ltd | Shaft-seal device for high-speed rotation apparatus |
| WO2014156994A1 (en) * | 2013-03-29 | 2014-10-02 | 積水化成品工業株式会社 | Porous resin particle, method for producing same, dispersion, and application thereof |
-
1990
- 1990-06-18 JP JP2160751A patent/JPH0450765A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010223332A (en) * | 2009-03-24 | 2010-10-07 | Hitachi Plant Technologies Ltd | Shaft-seal device for high-speed rotation apparatus |
| WO2014156994A1 (en) * | 2013-03-29 | 2014-10-02 | 積水化成品工業株式会社 | Porous resin particle, method for producing same, dispersion, and application thereof |
| CN105246931A (en) * | 2013-03-29 | 2016-01-13 | 积水化成品工业株式会社 | Porous resin particle, method for producing same, dispersion, and application thereof |
| JP6019218B2 (en) * | 2013-03-29 | 2016-11-02 | 積水化成品工業株式会社 | Porous resin particles, production method thereof, dispersion and use thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5902834A (en) | Method of manufacturing particles, and particles that can be produced in accordance with the method | |
| US5292814A (en) | Process for the preparation of monodispersed polymer beads | |
| US6290853B1 (en) | Chromotographic method and device in which a continuous macroporous organic matrix is used | |
| US4140653A (en) | Solid support for liquid chromatography | |
| Hosoya et al. | In situ surface-selective modification of uniform size macroporous polymer particles with temperature-responsive poly-N-isopropylacrylamide | |
| US20120164452A1 (en) | Suspension Homopolymerization of an Isocyanurates | |
| JP3158186B2 (en) | Alkyl group-containing porous resin, production method thereof and use thereof | |
| JP2005510593A (en) | Post-modification of porous support | |
| JPS648304B2 (en) | ||
| JPH0373848A (en) | Packing material for liquid chromatography and production thereof | |
| US4174430A (en) | Process for producing porous polystyrene gel | |
| Bamford et al. | Particulate precipitation polymerization: a convenient procedure for the synthesis of crosslinked polymers useful as polymeric supports | |
| WO2001019885A1 (en) | Single stage seed polymerisation for the production of large polymer particles with a narrow size distribution | |
| JPH0450765A (en) | Packing material for liquid chromatograph | |
| JPS6139619B2 (en) | ||
| JPS6128099B2 (en) | ||
| JPH11189601A (en) | Manufacture of fine polymer particle and manufacture of filler for liquid chromatography | |
| JPH02280833A (en) | Compounding and separating agent and its preparation | |
| Kotha et al. | Beaded reactive polymers, 1. Effect of synthesis variables on pore size and its distribution in beaded glycidyl methacrylate-divinyl benzene copolymers | |
| JPH11193310A (en) | Alkyl-group-containing porous polymer, manufacture thereof and application thereof | |
| JP2002055093A (en) | Method for separating drug in living body specimen, and separation agent used therein | |
| JPH11271294A (en) | Spherical porous cross-linked polymer particle, and preparation thereof | |
| JPS5845658B2 (en) | Packing material for liquid chromatography | |
| JP2559526B2 (en) | Method for producing packing material for liquid chromatography | |
| JPH087198B2 (en) | Quantitative method for glycated hemoglobin |