JPS6359462B2 - - Google Patents
Info
- Publication number
- JPS6359462B2 JPS6359462B2 JP56072049A JP7204981A JPS6359462B2 JP S6359462 B2 JPS6359462 B2 JP S6359462B2 JP 56072049 A JP56072049 A JP 56072049A JP 7204981 A JP7204981 A JP 7204981A JP S6359462 B2 JPS6359462 B2 JP S6359462B2
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- monomer
- liquid chromatography
- solubility parameter
- packing material
- 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.)
- Expired
Links
- 239000000178 monomer Substances 0.000 claims description 44
- 229920001577 copolymer Polymers 0.000 claims description 39
- 238000012856 packing Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 16
- 238000004811 liquid chromatography Methods 0.000 claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 230000002209 hydrophobic effect Effects 0.000 claims description 11
- 239000007900 aqueous suspension Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- BRXKVEIJEXJBFF-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol Chemical compound OCC(C)C(CO)(CO)CO BRXKVEIJEXJBFF-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- MSJGUMNGNXUWKB-UHFFFAOYSA-N C(C(=C)C)(=O)OC(COC(C(=C)C)=O)CCCCCCCCCC Chemical compound C(C(=C)C)(=O)OC(COC(C(=C)C)=O)CCCCCCCCCC MSJGUMNGNXUWKB-UHFFFAOYSA-N 0.000 claims 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 14
- 239000003480 eluent Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 9
- 238000010557 suspension polymerization reaction Methods 0.000 description 9
- UCTWMZQNUQWSLP-UHFFFAOYSA-N adrenaline Chemical compound CNCC(O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-UHFFFAOYSA-N 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 150000003943 catecholamines Chemical class 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SFLSHLFXELFNJZ-QMMMGPOBSA-N (-)-norepinephrine Chemical compound NC[C@H](O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-QMMMGPOBSA-N 0.000 description 4
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-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
- ALLHBGFTFKPCDX-UHFFFAOYSA-N C(C(=C)C)(=O)OC(COC(C(=C)C)=O)CCCCCCCCCCCCCC Chemical compound C(C(=C)C)(=O)OC(COC(C(=C)C)=O)CCCCCCCCCCCCCC ALLHBGFTFKPCDX-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229960002748 norepinephrine Drugs 0.000 description 4
- SFLSHLFXELFNJZ-UHFFFAOYSA-N norepinephrine Natural products NCC(O)C1=CC=C(O)C(O)=C1 SFLSHLFXELFNJZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- -1 dobamine Chemical class 0.000 description 3
- 238000005259 measurement Methods 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
- 238000005192 partition Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 3
- 238000003756 stirring Methods 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000012472 biological sample Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 239000010419 fine particle 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
- 230000003993 interaction Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- IAKGBURUJDUUNN-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-3-methylbutane-1,4-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(C)C(CO)(CO)CO IAKGBURUJDUUNN-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- KITXMWBTZKEAEO-UHFFFAOYSA-N C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(C(CO)(CO)CO)C Chemical compound C(C=C)(=O)O.C(C=C)(=O)O.C(O)C(C(CO)(CO)CO)C KITXMWBTZKEAEO-UHFFFAOYSA-N 0.000 description 1
- 101001052506 Homo sapiens Microtubule-associated proteins 1A/1B light chain 3A Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 102100024178 Microtubule-associated proteins 1A/1B light chain 3A Human genes 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- IZMILXUBYXMQBP-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(C)C(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(C)C(CO)(CO)CO IZMILXUBYXMQBP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 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
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 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
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 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
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 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
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
- B01J20/287—Non-polar phases; Reversed phases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
- B01J20/285—Porous sorbents based on polymers
Description
【発明の詳細な説明】
本発明は液体クロマトグラフイー用充填剤に関
するものであり、特に逆相分配型高速液体クロマ
トグラフイーに用いて好適な充填剤に関する。従
来の液体クロマトグラフイー用充填剤、特に逆相
分配型液体クロマトグラフイー用充填剤として
は、多孔性シリカの表面にオクタデシル基を導入
したODSタイプのものと、ポリスチレンゲルタ
イプのものがよく利用されている。しかしながら
近時、臨床検査技術の発達に伴ない、例えば血
液、尿等の生体試料からカテコールアミン等を高
速でかつ高精度に分離する技術が探究されるに至
つている。カテコールアミンはドーバミン、ノル
アドレナリン、アドレナリン等の骨格を構成する
物質であつて、芳香族系水溶性物質であるが、こ
れをODSタイプのもので分離しようとしても試
料中に存在するフエニル基との相互作用を有する
成分がないために精度よく分離できなかつた。こ
れに対ポリスチレンゲルタイプのものはフエニル
基を有しているために試料成分中のフエニル基と
の相互作用を有する点でODSタイプよりも適し
ている。しかし、ポリスチレンゲルタイプのもの
は有機溶媒中では試料中のフエニル基との相互作
用がすぐれているが、生体試料のように水系溶離
液中ではゲルが濡れず使用できない欠点があつ
た。そこで芳香族系水溶性物質の水系溶離液中
で、該芳香族系水溶性物質の分離を行なうに適し
た液体クロマトグラフイー用充填剤が要望されて
きた。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a packing material for liquid chromatography, and particularly to a packing material suitable for use in reversed phase partition type high performance liquid chromatography. Conventional packing materials for liquid chromatography, especially packing materials for reversed-phase partition liquid chromatography, are commonly used: ODS type, which has octadecyl groups introduced onto the surface of porous silica, and polystyrene gel type. has been done. However, in recent years, with the development of clinical testing techniques, techniques for separating catecholamines and the like from biological samples such as blood and urine at high speed and with high precision have been sought. Catecholamine is a substance that constitutes the skeleton of dobamine, noradrenaline, adrenaline, etc., and is an aromatic water-soluble substance, but even if you try to separate it with an ODS type, it will not interact with the phenyl groups present in the sample. It was not possible to accurately separate the components because there were no components with On the other hand, the polystyrene gel type is more suitable than the ODS type in that it has phenyl groups and thus interacts with the phenyl groups in sample components. However, although polystyrene gel types have excellent interaction with phenyl groups in samples in organic solvents, they have the disadvantage that they cannot be used in aqueous eluents such as biological samples because the gel does not get wet. Therefore, there has been a demand for a packing material for liquid chromatography that is suitable for separating aromatic water-soluble substances in an aqueous eluent.
本発明はこの点に鑑みなされたものであつて、
芳香族系水溶性物質を水系溶離液から分離するこ
とができ、特に逆相分配型高速液体クロマトグラ
フイー用充填剤として使用するに適した、液体ク
ロマトグラフイー用充填剤を提供することを目的
とする。 The present invention has been made in view of this point, and includes:
The purpose of the present invention is to provide a packing material for liquid chromatography that can separate aromatic water-soluble substances from an aqueous eluent and is particularly suitable for use as a packing material for reversed phase partition type high performance liquid chromatography. shall be.
本発明の要旨は、疎水性単量体と親水性単量体
との共重合体であつて、疎水性単量体はフエニル
基を有するビニル系単量体、親水性単量体はテト
ラデシルエチレングリコールジメタアクリレート
およびテトラメチロールプロパン（モノ，ジ，ト
リ，テトラ）アクリレートからなる群から選ばれ
る少くとも１種以上であり、且つ溶解度パラメー
ターが10.0以上の非解離性ビニル系単量体であ
り、前記共重合体の溶解度パラメーターが8.4以
上である、液体クロマトグラフイー用充填剤に存
する。 The gist of the present invention is a copolymer of a hydrophobic monomer and a hydrophilic monomer, wherein the hydrophobic monomer is a vinyl monomer having a phenyl group, and the hydrophilic monomer is a tetradecyl monomer. At least one type selected from the group consisting of ethylene glycol dimethacrylate and tetramethylolpropane (mono, di, tri, tetra) acrylate, and a non-dissociable vinyl monomer with a solubility parameter of 10.0 or more. , the copolymer has a solubility parameter of 8.4 or more, a packing material for liquid chromatography.
次に本発明液体クロマトグラフイー用充填剤に
ついて更に詳細に説明する。 Next, the packing material for liquid chromatography of the present invention will be explained in more detail.
本発明液体クロマトグラフイー用充填剤（以下
単に充填剤という）が疎水性単量体と親水性単量
体との共重合体とされるのは、疎水性単量体が共
重合成分とされることによつて、液体クロマトグ
ラフイーにおける芳香族系物質に対する分離能を
付与し、又親水性単量体が共重合成分とされるこ
とによつて水系溶離液からの分離能を付与するた
めである。 The reason why the packing material for liquid chromatography of the present invention (hereinafter simply referred to as packing material) is a copolymer of a hydrophobic monomer and a hydrophilic monomer is because the hydrophobic monomer is a copolymer component. In order to provide the ability to separate aromatic substances in liquid chromatography by using a hydrophilic monomer as a copolymer component, and to provide the ability to separate aromatic substances from an aqueous eluent by using a hydrophilic monomer as a copolymer component. It is.
疎水性単量体としてはフエニル基を有するビニ
ル系単量体が使用される。これは、本発明におけ
る充填剤がドーバミン、ノルアドレナリン、アド
レナリン等のカテコールアミン；フエニルアラニ
ン、チロシン等の芳香族アミン酸等の芳香族系水
溶性物質を分離することを主とするものであり、
このためには芳香族系水溶性物質のフエニル基と
の相互作用を有することが好ましいからである。
疎水性単量体としては、例えばスチレン、エチル
スチレン、ジビニルベンゼン、ビニルトルエン、
ビニルナフタレン、Ｎ―ビニルカルバゾール等が
使用される。 As the hydrophobic monomer, a vinyl monomer having a phenyl group is used. This is because the filler in the present invention is mainly used to separate aromatic water-soluble substances such as catecholamines such as dobamine, noradrenaline, and adrenaline; and aromatic amino acids such as phenylalanine and tyrosine.
For this purpose, it is preferable to have an interaction with the phenyl group of the aromatic water-soluble substance.
Examples of hydrophobic monomers include styrene, ethylstyrene, divinylbenzene, vinyltoluene,
Vinylnaphthalene, N-vinylcarbazole, etc. are used.
親水性単量体としては、溶解度パラメーター10
以上の非解離性ビニル系単量体が使用される。充
填剤が芳香族系水溶性物質を水系溶離液から分離
するのに適したものとするには、共重合体が水系
溶離液に濡れる程度の親水性が必要であるが、疎
水性単量体の共重合成分による分離能を妨げない
程度に制限されなければならない。このため親水
性単量体としては、かなり親水性の高いものを少
量含有する共重合体が好ましいので、親水性単量
体は溶解度パラメーターが10.0以上であつて、共
重合体の溶解度パラメーターが8.4以上のものが
使用されるのである。溶解度パラメーター（SP
値）は、親水性の程度を表わす数値であつて、密
度（ρ）、分子量（Ｍ）、凝集エネルギー定数(G)か
ら次の式によつて求められる。 As a hydrophilic monomer, the solubility parameter is 10
The above non-dissociable vinyl monomers are used. For a filler to be suitable for separating aromatic water-soluble substances from an aqueous eluent, the copolymer must be hydrophilic enough to be wetted by the aqueous eluent; must be limited to an extent that does not interfere with the separation ability of the copolymerized components. Therefore, as a hydrophilic monomer, it is preferable to use a copolymer containing a small amount of something highly hydrophilic, so the hydrophilic monomer should have a solubility parameter of 10.0 or more, and the solubility parameter of the copolymer should be 8.4. The above are used. Solubility parameter (SP
The value) is a numerical value representing the degree of hydrophilicity, and is determined from the density (ρ), molecular weight (M), and cohesive energy constant (G) using the following formula.
SP＝ρΣG／Ｍ
親水性単量体の溶解度パラメーターが10.0より
も小さい場合には親水性の程度が低い共重合体し
か得られないので、共重合体は水系溶離液からの
芳香族水溶性物質の分離に適さないものとなる。
そして共重合体の親水性を高めようとすれば親水
性単量体の共重合成分割合を増やす必要があり、
疎水性単量体の共重合成分割合を減らすことにな
るので、分離能を低下させることになる。 SP=ρΣG/M If the solubility parameter of the hydrophilic monomer is less than 10.0, only a copolymer with a low degree of hydrophilicity can be obtained, so that the copolymer is free from aromatic water-soluble substances from the aqueous eluent. It becomes unsuitable for separation.
In order to increase the hydrophilicity of the copolymer, it is necessary to increase the proportion of the copolymerized hydrophilic monomer.
Since the proportion of copolymerized hydrophobic monomers is reduced, the separation ability is reduced.
又、共重合体の溶解度パラメーターは8.4以上
のものが使用されるが、これは共重合体の水系溶
離液中で濡れをよくするためである。共重合体の
溶解度パラメーターが8.4よりも小さくなると、
共重合体は水に対する濡れが悪くなり、水系溶離
液からの芳香族系水溶性物質の分離に適さないも
のとなる。 Further, the solubility parameter of the copolymer used is 8.4 or more, in order to improve wetting of the copolymer in an aqueous eluent. When the solubility parameter of the copolymer is less than 8.4,
The copolymer has poor wettability with water, making it unsuitable for separating aromatic water-soluble substances from an aqueous eluent.
親水性単量体としては、非解離性ビニル系単量
体が使用される。親水性単量体が、非解離性ビニ
ル系単量体の場合には、イオン交換基を持たない
ので芳香族系水溶性物質との間にイオン交換反応
を起こして結合を生じ離れなくなるようなことが
ないし、又PH値によつて親水性が変つてくるよう
なこともないので分離性能がすぐれたものとな
る。 As the hydrophilic monomer, a non-dissociable vinyl monomer is used. When the hydrophilic monomer is a non-dissociable vinyl monomer, it does not have an ion exchange group, so it causes an ion exchange reaction with the aromatic water-soluble substance to form a bond that does not separate. Furthermore, since the hydrophilicity does not change depending on the pH value, the separation performance is excellent.
非解離性ビニル系単量体としては、テトラデシ
ルエチレングリコールジメタアクリレートおよび
テトラメチロールプロパン（モノ，ジ，トリ，テ
トラ）アクリレートからなる群から選ばれる少く
とも１種であり、且つその選ばれた単量体混合物
（単量体が１種からなるときは、そのもの自体）
の溶解度パラメーターが10.0以上のものが選択さ
れる。 The non-dissociable vinyl monomer is at least one selected from the group consisting of tetradecyl ethylene glycol dimethacrylate and tetramethylolpropane (mono, di, tri, tetra) acrylate; Monomer mixture (when it consists of one type of monomer, the monomer itself)
The solubility parameter of 10.0 or more is selected.
例えば親水性単量体が次式、
で表わされる物質で、ｎ＝14の場合はテトラデシ
ルエチレングリコールジメタクリレートであるが
溶解度パラメーターが16.9であり、疎水性単量体
がジビニルベンゼンの場合は溶解度パラメーター
が8.0であり、共重合体成分としてテトラデシル
エチレングリコールジメタクリレートを5.0重量
％含有する共重合体の溶解度パラメーターが8.4
となり、水に濡れる程度の親水性と芳香族系水溶
性物質の分離に充分なジビニルベンゼンを含有す
るものとなる。しかしながら、ｎ＝２の場合はジ
エチレングリコールジメタクリレートであるが、
溶解度パラメーターが9.7であり、ジビニルベン
ゼンとの共重合体として適度の親水性を付与する
ためには共重合体成分としてジエチレングリコー
ルジメタクリレートを25.0重量％以上含有しなけ
ればならない。 For example, the hydrophilic monomer has the following formula: In the case of n = 14, it is tetradecyl ethylene glycol dimethacrylate, but the solubility parameter is 16.9, and when the hydrophobic monomer is divinylbenzene, the solubility parameter is 8.0, and the copolymer component is The solubility parameter of the copolymer containing 5.0% by weight of tetradecyl ethylene glycol dimethacrylate is 8.4.
Therefore, it is hydrophilic enough to be wetted by water and contains enough divinylbenzene to separate aromatic water-soluble substances. However, when n=2, it is diethylene glycol dimethacrylate,
The solubility parameter is 9.7, and in order to impart appropriate hydrophilicity to the copolymer with divinylbenzene, the copolymer must contain 25.0% by weight or more of diethylene glycol dimethacrylate.
しかし上記の場合、共重合体の溶解度パラメー
ターは8.4とすることができるが、共重合体成分
のジビニルベンゼンの割合が少くなるので芳香族
系水溶性物質の分離性能が悪くなる。 However, in the above case, although the solubility parameter of the copolymer can be set to 8.4, the proportion of divinylbenzene in the copolymer component decreases, resulting in poor separation performance for aromatic water-soluble substances.
本発明における前記共重合体を充填剤として使
用しやすい形態にするために、共重合体は水性懸
濁重合によつて得られるのがよく、これによつて
多孔性で球状の形態を有するものが得られる。 In order to make the copolymer in the present invention into a form that is easy to use as a filler, the copolymer is preferably obtained by aqueous suspension polymerization, and thereby has a porous and spherical morphology. is obtained.
水性懸濁重合を行なわせるには、疎水性単量体
であるフエニル基を有するビニル系単量体、親水
性単量体である非解離性ビニル系単量体の混合物
を溶解するが、共重合体を溶解しない有機溶媒の
存在下に共重合反応を行なわせる。上記有機溶媒
としては例えばトルエン、キシレン、ジエチルベ
ンゼン、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、デカン等の
飽和炭化水素類、イソアミルアルコール、ヘキシ
ルアルコール、オクチルアルコール等のアルコー
ル類があげられる。その使用量はなんら限定され
るものではないが前記混合物に対して15〜200重
量％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。なお有機溶媒は前記混合物
に均一に溶解されて、前記混合物が水性懸濁重合
されるので得られた重合体粒子中に分散して存在
しており、重合終了後上記有機溶媒を粒子中から
取除くことにより多孔性で球状の共重合体が得ら
れるのである。 To carry out aqueous suspension polymerization, a mixture of a vinyl monomer having a phenyl group as a hydrophobic monomer and a non-dissociable vinyl monomer as a hydrophilic monomer is dissolved. The copolymerization reaction is carried out in the presence of an organic solvent that does not dissolve the polymer. Examples of the organic solvent include aromatic hydrocarbons such as toluene, xylene, diethylbenzene, and dodecylbenzene, saturated hydrocarbons such as hexane, heptane, octane, and decane, and alcohols such as isoamyl alcohol, hexyl alcohol, and octyl alcohol. It will be done. The amount used is not limited in any way, but it is preferably used in an amount of 15 to 200% by weight, more preferably 20% by weight based on the mixture.
~150 parts by weight. The organic solvent is uniformly dissolved in the mixture, and since the mixture is subjected to aqueous suspension polymerization, it exists dispersed in the resulting polymer particles, and after the polymerization is completed, the organic solvent is removed from the particles. By removing this, a porous and spherical copolymer is obtained.
従つて前記混合体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で球状の共重合
体の細孔の大きさを任意に変化することができ
る。 Therefore, by using various organic solvents having different compatibility with the above-mentioned mixture, the pore size of the porous, spherical copolymer can be arbitrarily changed.
又水性懸濁重合は公知の任意の方法が採用され
ればよく、たとえば前記有機溶媒に、前記混合物
及びラジカル発生触媒を溶解し、得られた溶液を
ポリビニルアルコール、リン酸カルシウム等の懸
濁重合安定剤の分散された水相に添加し撹拌しな
がら50〜100℃に加熱することにより行なわれる。 For aqueous suspension polymerization, any known method may be used; for example, the mixture and radical generating catalyst are dissolved in the organic solvent, and the resulting solution is mixed with a suspension polymerization stabilizer such as polyvinyl alcohol or calcium phosphate. It is carried out by adding it to an aqueous phase in which it is dispersed and heating it to 50 to 100°C while stirring.
上記ラジカル発生触媒は反応開始剤としてラジ
カルを発生する触媒であるが、該触媒としてはた
とえばベンゾイルパーオキサイド、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、過硫酸アンモニウム等の無機過酸化
物、アゾビスイソブチロニトリル、アゾビスイソ
ブチロアミド等のアゾ化合物などの公知の任意の
ラジカル発生触媒が使用される。 The above radical generating catalyst is a catalyst that generates radicals as a reaction initiator, and examples of the catalyst include organic peroxides such as benzoyl peroxide and cumene peroxide, and inorganic peroxides such as hydrogen peroxide, potassium persulfate, and ammonium persulfate. Any known radical-generating catalyst can be used, such as peroxides, azo compounds such as azobisisobutyronitrile, azobisisobutyramide, and the like.
上記水性懸濁重合によつて重合体された共重合
体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つて多孔性で球状の共重合
体となされ、液体クロマトグラフイー用充填剤と
なされるのである。そして液体クロマトグラフイ
ー用充填剤となされるには多孔性で球状の共重合
体の粒子径は均一であり且３〜40μmの範囲であ
るのが好ましく又細孔は粒子径により異なるが一
般に粒子の内部に向つて50〜2000オングストロー
ムあるのが好ましい。 The copolymer particles polymerized by the above-mentioned aqueous suspension polymerization are dried by heating, etc., and the organic solvent in the particles is released, resulting in a porous and spherical copolymer. It is used as a filler. In order to be used as a packing material for liquid chromatography, the particle size of the porous, spherical copolymer is preferably uniform and in the range of 3 to 40 μm, and the pore size varies depending on the particle size, but in general, the particle size is uniform. 50 to 2000 angstroms toward the interior of the surface is preferred.
本発明液体クロマトグラフイー用充填剤は、カ
テコールアミン、芳香族アミノ酸等の芳香族系水
溶性物質、水系溶離液から分離性能がすぐれてお
り、例えば血液、尿等の生体試料中の芳香族系水
溶性物質の高速液体クロマトグラフイーによる分
析に利用して有用である。 The packing material for liquid chromatography of the present invention has excellent separation performance from aromatic water-soluble substances such as catecholamines and aromatic amino acids, and from aqueous eluents. It is useful for analyzing chemical substances by high performance liquid chromatography.
次に本発明の実施例を記す。 Next, examples of the present invention will be described.
実施例 １
冷却器、撹拌機、温度計および滴下ロートの設
置された２セパラブルフラスコに４重量％のポ
リビニルアルコール水溶液400mlとテトラデシル
エチレングリコールジメタアクリレート（SP値
16.9）５ｇ、ジビニルベンゼン95ｇ、トルエン
100ｇおよびベンゾイルパーオキサイド1.5ｇより
なる混合液を供給した。次に400r.p.mの撹拌速度
で撹拌しながら80℃に昇温し10時間重合反応を行
つて冷却した。冷却後重合生成物を母液分離した
後、熱水及びアセトンで洗浄して粒子径が５〜
14μmの多孔性で球状の共重合体（SP値8.4）を得
た。得られた多孔性で球状の共重合体のうち微粒
子及び粗粒子を取除いて得られた粒子径６〜9μm
の充填剤５mlを30mlの水―メタノール（１／１）
混合溶媒に分散し、ステンレスカラム（直径4.0
mm、長さ25cm）に高圧定流量ポンプにより水―メ
タノール（１／１）の混合溶媒を2.0ml／分の速
度で圧送して充填した。Example 1 In a two-separable flask equipped with a condenser, stirrer, thermometer, and dropping funnel, 400 ml of a 4% by weight polyvinyl alcohol aqueous solution and tetradecyl ethylene glycol dimethacrylate (SP value
16.9) 5g, divinylbenzene 95g, toluene
A mixture of 100 g and 1.5 g of benzoyl peroxide was fed. Next, the temperature was raised to 80° C. while stirring at a stirring speed of 400 rpm, a polymerization reaction was carried out for 10 hours, and the mixture was cooled. After cooling, the polymerization product is separated from the mother liquor, and then washed with hot water and acetone to reduce the particle size to 5-5.
A spherical copolymer with a porosity of 14 μm (SP value 8.4) was obtained. A particle size of 6 to 9 μm obtained by removing fine particles and coarse particles from the porous and spherical copolymer obtained.
5ml of filler and 30ml of water-methanol (1/1)
Disperse in a mixed solvent and use a stainless steel column (diameter 4.0
mm, length 25 cm) was filled with a mixed solvent of water and methanol (1/1) at a rate of 2.0 ml/min using a high-pressure constant flow pump.
得られたカラムを高速液体クロマトグラフイー
（島津製作所製、商品名LC3A型）に接続し、標
準カテコールアミン３種を試料とし、0.1Mリン
酸１カリ（PH3.6）を溶離液として測定したとこ
ろ第１図に示す如く、各ピークは完全に分離し、
正常な対称形であつた。 The obtained column was connected to high performance liquid chromatography (manufactured by Shimadzu Corporation, product name LC3A type), and measurements were performed using three standard catecholamines as samples and 0.1M monopotassium phosphate (PH3.6) as the eluent. As shown in Figure 1, each peak is completely separated,
It had a normal symmetrical shape.
尚P1はノルアドレナリン、P2はアドレナリン、
P3はドーバミンの吸光度ピークを示する。 Note that P 1 is noradrenaline, P 2 is adrenaline,
P3 indicates the absorbance peak of dobamine.
実施例 ２
テトラメチロールプロパンジアクリレート（５
％）、テトラメチロールプロパントリアクリレー
ト（55％）およびテトラメチロールプロパンテト
ラアクリレート（40％）からなる親水性ビニルモ
ノマー（混合物SP値11.9）30ｇ、ジビニルベン
ゼン70ｇおよ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で行つ
たと同様にして水性懸濁重合を行い、粒径４〜
15μmの多孔性で球状の共重合体（SP値9.2）を得
た。Example 2 Tetramethylolpropane diacrylate (5
%), 30 g of hydrophilic vinyl monomer (mixture SP value 11.9) consisting of tetramethylolpropane triacrylate (55%) and tetramethylolpropane tetraacrylate (40%), 70 g of divinylbenzene and 1.5 g of benzoyl peroxide.
Aqueous suspension polymerization was carried out in the same manner as in Example 1 except that a mixed solution consisting of
A spherical copolymer with a porosity of 15 μm (SP value 9.2) was obtained.
得られた多孔性ポリマーのうち微粒子および粗
粒子を取除いて得られた粒子径10〜12μmの充填
剤５mlを水―メタノール（１／１）混合溶媒30に
分散させ、ステンレスカラム（直径４mm、長さ25
cm）に高圧定流量ポンプにより、水―メタノール
（１／１）混合溶媒を2.0ml／分の速度で圧送して
充填した。 5 ml of a filler with a particle size of 10 to 12 μm obtained by removing fine particles and coarse particles from the porous polymer obtained was dispersed in a mixed solvent of water and methanol (1/1), and then placed in a stainless steel column (diameter 4 mm, length 25
cm) was filled with water-methanol (1/1) mixed solvent at a rate of 2.0 ml/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イーおよび試料を用い、
0.1Mリン酸１カリ（PH3.6）を溶離液として測定
した結果、各成分の分離は良好であつた。 Using the obtained packed column in high performance liquid chromatography and the sample used in Example 1,
As a result of measurement using 0.1M monopotassium phosphoric acid (PH3.6) as an eluent, the separation of each component was good.
比較例 １
モノエチレングリコールジメタアクリレート
（SP値9.17）30ｇ、ジビニルベンゼン70（SP値
8.0）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と同様に水性
懸濁重合を行ない、SP値8.4の共重合体を得た。
これを実施例１と同様に分球及びカラム充填を行
ない、更に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イー及び試料を用い
0.1Mリン酸緩衝液（PH3.6）を溶離液として測定
した結果第２図に示すような結果を得た。P1は
ノルアドレナリン、P2はアドレナリン、P3はド
ーパミンの吸光度ピークを示すが、夫々が重なり
合つており、分離が完全には行なわれなかつた。Comparative example 1 Monoethylene glycol dimethacrylate (SP value 9.17) 30g, divinylbenzene 70 (SP value
Aqueous suspension polymerization was carried out in the same manner as in Example 1, except that a mixed solution consisting of 8.0) and 1.5 g of benzoyl peroxide was used to obtain a copolymer with an SP value of 8.4.
This was divided into spheres and packed into a column in the same manner as in Example 1, and the resulting packed column was subjected to high performance liquid chromatography and the sample used in Example 1.
As a result of measurement using 0.1M phosphate buffer (PH3.6) as an eluent, the results shown in FIG. 2 were obtained. P 1 shows the absorbance peaks of noradrenaline, P 2 shows the absorbance peaks of adrenaline, and P 3 shows the absorbance peaks of dopamine, but these peaks overlapped with each other, so they could not be completely separated.
比較例 ２
ベータハイドロキシエチルメタアクリレート
（SP値10.69）10ｇ、ジビニルベンゼン90（SP値
8.0）及びアゾイソブチロニトリル1.0ｇよりなる
混合物を使用した以外は実施例１と同様に水性懸
濁重合を行ないSP値8.27の共重合体を得た。Comparative example 2 Beta hydroxyethyl methacrylate (SP value 10.69) 10g, divinylbenzene 90 (SP value
8.0) and azoisobutyronitrile (1.0 g) was used, but aqueous suspension polymerization was carried out in the same manner as in Example 1 to obtain a copolymer with an SP value of 8.27.
これを用い実施例１と同様に分球及びカラム充
填を行ない、更に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イー及び試料
を用い0.1Mリン酸カリ（PH3.2）を溶離液として
送液したところ、高圧（100Kg／cm2）にしても、
わずかしか溶出せず、分離パターンは得られなか
つた。 Using this, sphere separation and column packing were performed in the same manner as in Example 1, and the obtained packed column was further used in Example 1.
When 0.1M potassium phosphate (PH3.2) was sent as the eluent using the high-performance liquid chromatography and sample used in , even at high pressure (100Kg/cm 2 ),
Only a small amount was eluted and no separation pattern was obtained.
第１図は実施例１におけるクロマトグラム、第
２図は比較例１におけるクロマトグラムである。
FIG. 1 is a chromatogram in Example 1, and FIG. 2 is a chromatogram in Comparative Example 1.
Claims (1)
あつて、疎水性単量体はフエニル基を有するビニ
ル系単量体、親水性単量体はテトラデシルエチレ
ングリコールジメタアクリレートおよびテトラメ
チロールプロパン（モノ、ジ、トリ、テトラ）ア
クリレートからなる群から選ばれる少くとも１種
以上であり、且つ溶解度パラメーターが10.0以上
の非解離性ビニル系単量体であり、前記共重合体
の溶解度パラメーターが8.4以上である液体クロ
マトグラフイー用充填剤。 ２ 共重合体が、水性懸濁共重合体である、特許
請求の範囲第１項記載の液体クロマトグラフイー
用充填剤。 ３ 共重合体が、多孔性で球状の形態を有する、
特許請求の範囲第１項又は第２項記載の液体クロ
マトグラフイー用充填剤。[Scope of Claims] 1. A copolymer of a hydrophobic monomer and a hydrophilic monomer, where the hydrophobic monomer is a vinyl monomer having a phenyl group, and the hydrophilic monomer is a tetrahydrophilic monomer. A non-dissociable vinyl monomer that is at least one member selected from the group consisting of decylethylene glycol dimethacrylate and tetramethylolpropane (mono, di, tri, tetra) acrylate and has a solubility parameter of 10.0 or more. A packing material for liquid chromatography, wherein the copolymer has a solubility parameter of 8.4 or more. 2. The packing material for liquid chromatography according to claim 1, wherein the copolymer is an aqueous suspension copolymer. 3. The copolymer has a porous and spherical morphology.
A packing material for liquid chromatography according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56072049A JPS57186167A (en) | 1981-05-12 | 1981-05-12 | Packing agent for liquid chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56072049A JPS57186167A (en) | 1981-05-12 | 1981-05-12 | Packing agent for liquid chromatography |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57186167A JPS57186167A (en) | 1982-11-16 |
| JPS6359462B2 true JPS6359462B2 (en) | 1988-11-18 |
Family
ID=13478134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56072049A Granted JPS57186167A (en) | 1981-05-12 | 1981-05-12 | Packing agent for liquid chromatography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57186167A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2559525B2 (en) * | 1989-09-29 | 1996-12-04 | 積水化学工業株式会社 | Method for producing packing material for liquid chromatography |
| US6482867B1 (en) * | 1998-08-28 | 2002-11-19 | Shiseido Co., Ltd. | Polymer packing material for liquid chromatography and a producing method thereof |
| US20130048853A1 (en) * | 2010-04-28 | 2013-02-28 | Hitachi High-Technologies Corporation | Adsorbent and Method for Producing Same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4962194A (en) * | 1972-05-10 | 1974-06-17 | ||
| JPS564051A (en) * | 1979-06-22 | 1981-01-16 | Sekisui Chem Co Ltd | Filler for high speed liquid chromatography |
-
1981
- 1981-05-12 JP JP56072049A patent/JPS57186167A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4962194A (en) * | 1972-05-10 | 1974-06-17 | ||
| JPS564051A (en) * | 1979-06-22 | 1981-01-16 | Sekisui Chem Co Ltd | Filler for high speed liquid chromatography |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57186167A (en) | 1982-11-16 |
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