JPH0458153A - Production of crosslinked copolymer particle for reversed-phase liquid chromatography and column for reversed-phase liquid chromatography - Google Patents
Production of crosslinked copolymer particle for reversed-phase liquid chromatography and column for reversed-phase liquid chromatographyInfo
- Publication number
- JPH0458153A JPH0458153A JP2168742A JP16874290A JPH0458153A JP H0458153 A JPH0458153 A JP H0458153A JP 2168742 A JP2168742 A JP 2168742A JP 16874290 A JP16874290 A JP 16874290A JP H0458153 A JPH0458153 A JP H0458153A
- Authority
- JP
- Japan
- Prior art keywords
- reversed
- crosslinked copolymer
- liquid chromatography
- copolymer particles
- phase liquid
- 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
- 239000002245 particle Substances 0.000 title claims abstract description 29
- 229920001577 copolymer Polymers 0.000 title claims abstract description 20
- 238000004366 reverse phase liquid chromatography Methods 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 15
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims description 5
- 239000007900 aqueous suspension Substances 0.000 claims description 4
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 238000012856 packing Methods 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 4
- 238000004811 liquid chromatography Methods 0.000 abstract description 3
- 238000005192 partition Methods 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 2
- 150000007513 acids Chemical class 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Hexyl benzoate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 8
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 8
- DDRJAANPRJIHGJ-UHFFFAOYSA-N creatinine Chemical compound CN1CC(=O)NC1=N DDRJAANPRJIHGJ-UHFFFAOYSA-N 0.000 description 8
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 8
- 239000007863 gel particle Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- -1 aliphatic alcohols Chemical class 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 239000012736 aqueous medium Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 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 4
- UPTHZKIDNHJFKQ-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.OCC(O)CO UPTHZKIDNHJFKQ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229940109239 creatinine Drugs 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 229940095102 methyl benzoate Drugs 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 230000001681 protective effect Effects 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
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- FAIDIRVMPHBRLT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OCC(O)CO FAIDIRVMPHBRLT-UHFFFAOYSA-N 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 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 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 1
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-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
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- GCNKJQRMNYNDBI-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(2-methylprop-2-enoyloxymethyl)butyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(CC)COC(=O)C(C)=C GCNKJQRMNYNDBI-UHFFFAOYSA-N 0.000 description 1
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000004810 partition chromatography Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 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
- 229940078499 tricalcium phosphate Drugs 0.000 description 1
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 1
- 235000019731 tricalcium phosphate Nutrition 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は逆相液体クロマトグラフィー用架橋共重合体粒
子の製造法及び逆相液体クロマトグラフィー用カラムに
関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing crosslinked copolymer particles for reversed-phase liquid chromatography and a column for reversed-phase liquid chromatography.
従来より液体クロマトグラフィーの一分離様式として、
試料の疎水性の相違による保持の強弱に基づき分離する
逆相分配クロマトグラフィーが知られている。逆相液体
クロマトグラフィーに一般的に用いられるカラム充填剤
としては、下記のものが知られている。Conventionally, as a separation method of liquid chromatography,
Reversed phase partition chromatography is known, which separates samples based on the strength of retention due to differences in hydrophobicity of the sample. The following are known as column packing materials commonly used in reversed phase liquid chromatography.
（Ｉ）シリカゲルの表面をオクタデシル基等の炭化水素
基を有するシランカップリング剤で化学修飾した化学結
合型シリカゲル〔ジェイ・ジェイ・カークランド、ジエ
イ・ジエイ・デステイファノ著、ジャーナル・オブ・ク
ロマトグラフィー・サイエンス（Ｊｏｕｒｎａｌ ｏｆ
Ｃｈｒｏｍａｔｏｇｒａｐｈｙ ５ｃｉｅｎｃｅ）第
８巻、３０９頁、１９７０年〕、
（２）スチレン−ジビニルベンゼン共重合体粒子〔エム
・デイ−・グリーサー、デイ−・ジエイ・ビートザック
著、アナリテイカル・ケミストリー（Ａｎａｌｙｔｉｃ
ａｌ Ｃｈｅｍｉｓｔｒｙ）第４５巻、１３８３頁、１
９７３年〕、
（３）長鎖アルキル鎖を持つメタクリル酸エステル系共
重合体粒子（特開昭６２−９０５３３号公報）。(I) Chemically bonded silica gel in which the surface of silica gel is chemically modified with a silane coupling agent having a hydrocarbon group such as an octadecyl group [written by J.J. Kirkland and G.G. Destifano, Journal of Chromatography Science (Journal of
Chromatography 5science) Vol. 8, p. 309, 1970], (2) Styrene-divinylbenzene copolymer particles [M.D.
al Chemistry) Volume 45, Page 1383, 1
973], (3) Methacrylic acid ester copolymer particles having a long alkyl chain (Japanese Unexamined Patent Publication No. 62-90533).
従来知られている逆相液体クロマトグラフィー用カラム
充填剤のうちシリカゲルは、アルカリに弱（、溶離液の
ｐＨが２〜８の領域に制限されて全てのｐＨ範囲で用い
ることはできないという欠点がある。さらに、シリカ表
面の全てのシラノール基にカップリング剤を化学結合さ
せることは難しく、未反応のシラノール基が残存してい
ることから、塩基性の試料が特異的に吸着されるという
問題もある。Among the conventionally known column packing materials for reversed-phase liquid chromatography, silica gel has the disadvantage that it is weak against alkalis (and cannot be used in all pH ranges because the pH of the eluent is limited to a range of 2 to 8). Furthermore, it is difficult to chemically bond a coupling agent to all the silanol groups on the silica surface, and as unreacted silanol groups remain, there is also the problem that basic samples are specifically adsorbed. be.
また、上記のスチレン−ジビニルベンゼン系及びメタク
リルエステル系の共重合体粒子は、シリカゲルに関する
上述の問題は解決しているものの、各種の溶媒間での膨
潤・収縮が激しいため、溶離液を変えて、クロマトグラ
フィーを行うことが困難であるという問題点がある。In addition, although the above-mentioned styrene-divinylbenzene-based and methacrylic ester-based copolymer particles have solved the above-mentioned problems regarding silica gel, they swell and shrink rapidly between various solvents, so it is necessary to change the eluent. However, there is a problem in that it is difficult to perform chromatography.
本発明は、このような問題点を解決し、耐酸性及び耐ア
ルカリ性を有し、各種溶媒間での膨潤・収縮の差が小さ
く、溶離液の選択幅の広い、逆相分配液体クロマトグラ
フィー用カラム充填剤として有用な架橋共重合体粒子の
効率のよい製造法及び逆相液体クロマトグラフィー用カ
ラムを提供することを目的とする。The present invention solves these problems and provides a solution for reversed-phase partition liquid chromatography that has acid resistance and alkali resistance, has small differences in swelling and shrinkage between various solvents, and has a wide selection of eluents. The object of the present invention is to provide an efficient method for producing crosslinked copolymer particles useful as a column packing material and a column for reversed-phase liquid chromatography.
本発明は、炭素原子数６〜２４の脂肪族アルコールのビ
ニルエステル又はビニルエーテル（Ｉ）と水酸基を持つ
ビニルエステル又はビニルエーテル架橋剤（ＩＩ）とを
、（Ｉ）／（ＩＩ）のモル比が１〜０．０５の範囲とな
るようにして水性懸濁重合させることを特徴とする逆相
液体クロマトグラフィー用架橋共重合体粒子の製造法に
関する。In the present invention, a vinyl ester or vinyl ether of an aliphatic alcohol having 6 to 24 carbon atoms (I) and a vinyl ester or vinyl ether crosslinking agent (II) having a hydroxyl group are used in a molar ratio of (I)/(II) of 1. This invention relates to a method for producing crosslinked copolymer particles for reversed-phase liquid chromatography, which is characterized by carrying out aqueous suspension polymerization so that the particle diameter is in the range of 0.05 to 0.05.
また、本発明は、前記製造法によって製造した架橋共重
合体粒子を充填してなる逆相液体クロマトグラフィー用
カラムに関する。The present invention also relates to a reversed phase liquid chromatography column packed with crosslinked copolymer particles produced by the above production method.
本発明に用いられる脂肪族アルコールの脂肪族鎖は、逆
相分配の分離機能を付与するために必要であり、炭素原
子数が５以下の場合には分離精度が悪（なり、炭素原子
数が２５以上となると、合成が困難となり、実用上適さ
ない。The aliphatic chain of the aliphatic alcohol used in the present invention is necessary to provide the separation function of reversed phase partitioning, and if the number of carbon atoms is 5 or less, the separation accuracy will be poor (and the number of carbon atoms will be poor). When it is 25 or more, synthesis becomes difficult and it is not suitable for practical use.
本発明に用いられる炭素原子数６〜２４の脂肪族アルコ
ールのビニルエステル又はビニルエーテル（Ｉ）として
は、炭素原子数６〜２４の脂肪族アルコールのメタクリ
ル酸エステル、アクリル酸エステル、アリルエーテルな
どが挙げられる。反応性、耐アルカリ性、工業的入手の
容易性を考慮すると、ステアリルメタクリレート及びラ
ウリルメタクリレートが好ましい。Examples of vinyl esters or vinyl ethers (I) of aliphatic alcohols having 6 to 24 carbon atoms used in the present invention include methacrylic esters, acrylic esters, allyl ethers, and the like of aliphatic alcohols having 6 to 24 carbon atoms. It will be done. In consideration of reactivity, alkali resistance, and industrial availability, stearyl methacrylate and lauryl methacrylate are preferred.
本発明に用いられる水酸基を持つビニルエステル又はビ
ニルエーテル架橋剤（ＩＩ）としては、例えば、グリセ
リンのジアクリレート、グリセリンのジメタクリレート
、トリメチロールプロパンのジメタクリレート、トリメ
チロールプロパンのジアクリレート、テトラメチロール
メタンのジ又はトリメタクリレート、テトラメチロール
メタンのジ又はトリアクリレート、グリセリンのジ又は
トリアリルエーテル、トリメチロールプロパンのジアリ
ルエーテル、テトラメチロールメタンのジ又はトリアリ
ルエーテル等が挙げられるが、多価アルコールのポリメ
タクリル酸エステルが好ましい。Examples of the vinyl ester or vinyl ether crosslinking agent (II) having a hydroxyl group used in the present invention include glycerin diacrylate, glycerin dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane diacrylate, and tetramethylolmethane. Examples include di- or tri-methacrylate, di- or tri-acrylate of tetramethylolmethane, di- or triallyl ether of glycerin, diallyl ether of trimethylolpropane, di- or triallyl ether of tetramethylolmethane, etc. Polymethacrylate of polyhydric alcohol Acid esters are preferred.
その中でもグリセリンのジアクリレート、グリセリンの
ジメタクリレートがより好ましい。Among them, glycerin diacrylate and glycerin dimethacrylate are more preferred.
炭素原子数６〜２４の脂肪族アルコールのビニルエステ
ル又はビニルエーテル（Ｉ）と水酸基を持つビニルエス
テル又はビニルエーテル架橋剤（ＩＩ）との比率は、（
Ｉ）が少なすぎると逆相クロマトグラフィー用カラム充
填剤として分離精度が悪（なり、（Ｉｔ）が少なすぎる
と、生成した架橋重合体粒子の耐圧性が下がるか、ある
いは溶媒間での膨潤・収縮の差が太き（なり、（Ｉ）／
（Ｉｎ）のモル比率は１〜０．０５の範囲であることが
好ましい。The ratio of the vinyl ester or vinyl ether (I) of an aliphatic alcohol having 6 to 24 carbon atoms to the vinyl ester or vinyl ether crosslinking agent (II) having a hydroxyl group is (
If I) is too low, the separation accuracy will be poor as a column packing material for reversed phase chromatography, and if (It) is too low, the pressure resistance of the produced crosslinked polymer particles will decrease, or swelling between solvents will occur. The difference in contraction is thick ((I)/
The molar ratio of (In) is preferably in the range of 1 to 0.05.
（Ｉ）及び（ＩＩ）以外のビニル化合物（ＩＩ）を本発
明の目的を阻害しない範囲で必要に応じて併用してもよ
い。ビニル化合物（ＩＩＩ）については、特に制限はな
い。Vinyl compounds (II) other than (I) and (II) may be used in combination as necessary within a range that does not impede the object of the present invention. There are no particular limitations on the vinyl compound (III).
本発明において、炭素原子数６〜２４の脂肪族アルコー
ルのビニルエステル又はビニルエーテル（Ｉ）と水酸基
を持つビニルエステル又はビニルエーテル架橋剤（ＩＩ
）と必要に応じて用いられるビニル化合物（■）〔以下
、（Ｉ）と（ＩＩ）と（ＩＩＩ）を単量体という〕は、
必要に応じて水と相溶しない有機溶媒の存在下に水性懸
濁重合させ、架橋共重合体粒子とされる。In the present invention, a vinyl ester or vinyl ether of an aliphatic alcohol having 6 to 24 carbon atoms (I) and a vinyl ester or vinyl ether crosslinking agent (II) having a hydroxyl group are used.
) and the vinyl compound (■) used as necessary [hereinafter, (I), (II) and (III) are referred to as monomers],
If necessary, aqueous suspension polymerization is carried out in the presence of an organic solvent that is incompatible with water to obtain crosslinked copolymer particles.
水性懸濁重合は、水性媒体中で懸濁重合を行うものであ
るが、この水性媒体としては、水は必須であり、また、
懸濁系の安定性を阻害しない範囲で水溶性有機溶媒を溶
解した水を使用してもよい。In aqueous suspension polymerization, suspension polymerization is carried out in an aqueous medium, and water is essential as the aqueous medium, and
Water in which a water-soluble organic solvent is dissolved may be used within a range that does not impair the stability of the suspension system.
重合は、重合開始剤の存在下で行う。重合開始剤として
は、過酸化ベンゾイル、過酸化ジクロルベンゾイル、過
酸化ジクミル、過酸化ジー第三ブチル、２，５−ジ（ペ
ルオキシベンゾエート）ヘキシン−３，１，３−ビス（
第三ブチルペルオキシイソプロビル）ベンゼン、過酸化
ラウロイル、過酢酸第三ブチル、２，５−ジメチル−２
，５−ジ（第三ブチルペルオキシ）ヘキシン−３，２゜
５−ジメチル−２，５−ジ（第三ブチルペルオキシ）ヘ
キサン及び過安息香酸第三ブチル、メチルエチルケトン
ペルオキシド、メチルシクロヘキサノンペルオキシド等
の有機過酸化物、アゾビスイソブチロニトリル及びジメ
チルアゾジイソブチレート等のアゾ系化合物が挙げられ
る。これらを１種又は２種以上使用することができる。Polymerization is carried out in the presence of a polymerization initiator. As a polymerization initiator, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-di(peroxybenzoate)hexyne-3,1,3-bis(
tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2
, 5-di(tert-butylperoxy)hexane-3,2゜5-dimethyl-2,5-di(tert-butylperoxy)hexane and organic peroxides such as tert-butyl perbenzoate, methyl ethyl ketone peroxide, and methyl cyclohexanone peroxide. Examples include azo compounds such as oxides, azobisisobutyronitrile, and dimethylazodiisobutyrate. One or more types of these can be used.
この使用量は単量体の種類などにより適宜法められるも
のであるが、好ましくは単量体の総量に対して０．１〜
４．０重量％使用される。The amount to be used is determined as appropriate depending on the type of monomer, but it is preferably 0.1 to 100% based on the total amount of monomers.
4.0% by weight is used.
また、本発明において、分散剤として難溶性リン酸塩、
水溶性高分子保護コロイドなどを重合系に添加すること
ができる。難溶性リン酸塩としては、リン酸三カルシウ
ム、リン酸マグネシウム等がある。高分子保護コロイド
としては、ポリビニルアルコール、アルキルセルロース
、ヒドロキシアルキルセルロース、カルボキシアルキル
セルロース等の水溶性セルロース誘導体、ポリアクリル
酸ナトリウム等がある。難溶性リン酸塩は重合系に存在
する物質全量に対して０．０１重量％以上、水溶性高分
子保護コロイドは１〜０．００１重量％の範囲で使用さ
れるのが好ましい。In addition, in the present invention, a poorly soluble phosphate as a dispersant,
Water-soluble polymeric protective colloids and the like can be added to the polymerization system. Examples of sparingly soluble phosphates include tricalcium phosphate and magnesium phosphate. Examples of the polymeric protective colloid include polyvinyl alcohol, water-soluble cellulose derivatives such as alkylcellulose, hydroxyalkylcellulose, and carboxyalkylcellulose, and sodium polyacrylate. It is preferable that the sparingly soluble phosphate is used in an amount of 0.01% by weight or more, and the water-soluble polymer protective colloid is used in an amount of 1 to 0.001% by weight based on the total amount of substances present in the polymerization system.
その他、粒径調節等のために分散助剤として陰イオン系
界面活性剤を重合系に添加したり、単量体や水と相溶し
ない有機溶媒が水へ移行する溶解性を低下させる等のた
めに水溶性無機塩を重合系に添加することができる。In addition, anionic surfactants may be added to the polymerization system as dispersion aids to control particle size, etc., or organic solvents that are incompatible with monomers and water may reduce the solubility of the monomers or organic solvents that migrate into water. Water-soluble inorganic salts can be added to the polymerization system for this purpose.
単量体、分散剤、重合開始剤及び必要に応じて用いられ
る分散助剤、必要に応じて用いられる水と相溶しない有
機溶媒等は、これらを予め混合して又は各々を水性媒体
に添加して分散させる。この場合、よく分散させるため
に、ホモミキサー等により高速攪拌するのが好ましく、
この高速攪拌は、重合初期まで続けることができる。こ
れ以降の重合は、プロペラ攪拌機等を用いて通常の攪拌
下で行う。なお、水性媒体は、単量体及び前記の水と相
溶しない有機溶媒の総量に対して１〜５０重量倍使用す
るのが好ましい。この場合、水性媒体としては、水が使
用されるが、懸濁系の安定性を阻害しない範囲で水溶性
有機溶媒を溶解して含む水を使用してもよい。Monomers, dispersants, polymerization initiators, dispersion aids used as necessary, organic solvents that are incompatible with water used as necessary, etc. may be mixed in advance or each added to the aqueous medium. and disperse. In this case, in order to disperse well, it is preferable to stir at high speed using a homomixer etc.
This high-speed stirring can be continued until the initial stage of polymerization. The subsequent polymerization is carried out under normal stirring using a propeller stirrer or the like. The aqueous medium is preferably used in an amount of 1 to 50 times the total amount of the monomer and the water-incompatible organic solvent. In this case, water is used as the aqueous medium, but water containing a water-soluble organic solvent dissolved therein may also be used as long as it does not impede the stability of the suspension system.
また、重合時に水と相溶しない有機溶媒を添加すること
により生成する架橋共重合体粒子を多孔性にすることが
できる。Further, by adding an organic solvent that is incompatible with water during polymerization, the resulting crosslinked copolymer particles can be made porous.
本発明で用いられる水と相溶しない有機溶媒とは、２５
℃で水１００ｇに対しての溶解量が１５ｇ以下のもので
あり、例えば、トルエン、ジエチルベンゼン、ドデカン
、イソアミルアルコール、クロロベンゼン、酢酸エチル
、酢酸プロピル、酢酸ブチル、セロソルブアセテート等
がある。これらの溶媒は、単独で用いてもよいし、２種
以上を混合して用いても良い。これらの使用量は、単量
体総量に対して０〜３００重量％使用されるのが好まし
い。水と相溶しない有機溶媒が少ないと、得られる粒子
を多孔性にし難（なり、多すぎると、得られる粒子の空
隙率が大きくなりすぎて、耐圧性が乏しくなる傾向があ
る。The organic solvent that is incompatible with water used in the present invention is 25
The amount dissolved in 100 g of water at °C is 15 g or less, such as toluene, diethylbenzene, dodecane, isoamyl alcohol, chlorobenzene, ethyl acetate, propyl acetate, butyl acetate, cellosolve acetate, and the like. These solvents may be used alone or in combination of two or more. The amount of these used is preferably 0 to 300% by weight based on the total amount of monomers. If the amount of the organic solvent that is incompatible with water is small, it will be difficult to make the obtained particles porous (if it is too large, the porosity of the obtained particles will become too large and the pressure resistance will tend to be poor).
重合反応は、通常、７０〜９０℃の温度範囲で６〜１０
時間行なう。The polymerization reaction is usually carried out at a temperature range of 70 to 90°C for 6 to 10 minutes.
Do time.
以上のようにして得られた架橋共重合体粒子である粒径
１〜２００μｍ１好ましくは１〜１５μｍの球状粒子は
、必要に応じて分級し、逆相クロマトグラフィー用カラ
ム充填剤として使用できる。The crosslinked copolymer particles obtained as described above, spherical particles having a particle size of 1 to 200 μm, preferably 1 to 15 μm, can be classified as necessary and used as a column packing material for reversed phase chromatography.
充填は公知の方法に準じて行なうことができる。Filling can be performed according to a known method.
次に、本発明を実施例によりさらに詳しく説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１
ステアリルメタクリレート５３．６ｇ、グリセリンジメ
タクリレー）１４６．４ｇ、セロソルブアセテ−）２０
０ｇ及びアゾビスイソブチロニトリル１．０ｇの混合物
を０．１重量％のメチルセルロース水溶液２．２１中に
懸濁させ、ホモミキサーを使用して高速攪拌下、室温で
約ＩＯ分間混合し、その後普通のプロペラ攪拌装置に移
して８０℃で６時間反応させて、水及び有機溶媒に不溶
なオクタデシル基量２０重量％の架橋共重合体粒子（ゲ
ル粒子）を得た。このゲル粒子を５濾過して集め、水２
ノ、次いでメタノール２Ｉ！で洗浄後、風乾した。Example 1 Stearyl methacrylate 53.6g, glycerin dimethacrylate) 146.4g, cellosolve acetate) 20
A mixture of 0 g and 1.0 g of azobisisobutyronitrile was suspended in 0.1% by weight aqueous methylcellulose solution 2.21 and mixed for about 10 minutes at room temperature under high speed stirring using a homomixer, and then The mixture was transferred to a common propeller stirring device and reacted at 80° C. for 6 hours to obtain crosslinked copolymer particles (gel particles) having an octadecyl group content of 20% by weight and insoluble in water and organic solvents. The gel particles are collected by 5 filtration, and water 2
No, then methanol 2I! After washing, it was air-dried.
風乾したゲル粒子を篩い分けして、８〜２５μｍの粒度
とし、直径６．０ ｍｍ Ｘ長さ１５０ｍｍのステンレ
スカラムに充填し、逆相ＧＰＣカラムを作製した。この
逆相ＧＰＣカラムでクレアチニン、安息香酸メチル、安
息香酸ブチル及び安息香酸ヘキシルを分離したクロマト
グラムを第１図として示した。第１図において、１．２
．３及び４の符号は、それぞれクレアチニン、安息香酸
メチル、安息香酸ブチル及び安息香酸ヘキシルの溶出容
量のピークを示すものである。移動相（溶離液）として
アセトニトリル：水（７０：３０（容積比）〕を用い、
流量は１．０ｍｔ’／分、圧力は２０ｋｇｆ／ｃＸｌと
し、検出はＵＶ２５４ｎｍで行った。なお、水１００％
、メタノール１００％を通液した場合でも、充填したゲ
ル粒子間に空隙は形成されないことを確認した。The air-dried gel particles were sieved to a particle size of 8 to 25 μm, and packed into a stainless steel column with a diameter of 6.0 mm and a length of 150 mm to prepare a reversed phase GPC column. FIG. 1 shows a chromatogram in which creatinine, methyl benzoate, butyl benzoate, and hexyl benzoate were separated using this reversed-phase GPC column. In Figure 1, 1.2
．． The numbers 3 and 4 indicate the elution volume peaks of creatinine, methyl benzoate, butyl benzoate, and hexyl benzoate, respectively. Using acetonitrile:water (70:30 (volume ratio)) as the mobile phase (eluent),
The flow rate was 1.0 mt'/min, the pressure was 20 kgf/cXl, and detection was performed at UV 254 nm. In addition, 100% water
It was confirmed that even when 100% methanol was passed through, no voids were formed between the filled gel particles.
実施例２
耐アルカリ性試験として、実施例１で得た逆相ＧＰＣカ
ラムに１０ｍＭ Ｎａ２ＣＯ＊ ＨＣｆ （ｐＨ＝１
１）緩衝液を流速１．０−／ ｍｉ ｎで２５０時間連
続通液した後、実施例１と同様にしてクレアチニン他３
種の化合物を分離した。そのときのクロマトグラムを第
２図として示した。第２図のパターンは、第１図のパタ
ーンとほとんど変わっておらず、良好な分離能を示して
おり、これからゲル粒子は耐アルカリ性が優れているこ
とがわかった。Example 2 As an alkali resistance test, 10mM Na2CO*HCf (pH=1
1) After continuously passing the buffer solution at a flow rate of 1.0/min for 250 hours, creatinine and other 3
The species compounds were separated. The chromatogram at that time is shown in FIG. The pattern in FIG. 2 is almost the same as the pattern in FIG. 1 and shows good separation ability, which indicates that the gel particles have excellent alkali resistance.
実施例３
単量体としてステアリルメタクリレ−） ４０．６ｇ及
びグリセリンジメタクリレート１５９．６ ｇを使用し
た以外は、実施例１と同様にして風乾したゲル粒子を得
た。Example 3 Air-dried gel particles were obtained in the same manner as in Example 1, except that 40.6 g of stearyl methacrylate and 159.6 g of glycerin dimethacrylate were used as monomers.
このゲル粒子を実施例１と同様に篩い分け、カラム充填
し、実施例１と同一条件で分析を行い、クレアチニン、
安息香酸メチル、安息香酸ブチル及び安息香酸ヘキシル
を分離した。このときのクロマトグラムを第３図として
示した。The gel particles were sieved and packed in a column in the same manner as in Example 1, and analyzed under the same conditions as in Example 1.
Methyl benzoate, butyl benzoate and hexyl benzoate were separated. The chromatogram at this time is shown in FIG.
本発明によって製造した架橋共重合体粒子は、耐酸性及
び耐アルカリ性に優れ、各種の溶媒間での膨潤・収縮の
差が小さ（、これを用いた逆相分配クロマトグラフィー
用カラムは、優れた特性を有する。The crosslinked copolymer particles produced according to the present invention have excellent acid resistance and alkali resistance, and have small differences in swelling and shrinkage between various solvents. have characteristics.
第１図は実施例１におけるクロマトグラム、第２図は実
施例２におけるクロマトグラム及び第３図は実施例３に
おけるクロマトグラムである。
符号の説明
１・・・クレアチニンのピーク
２・・・安息香酸メチルのピーク
３・・・安息香酸ブチルのピーク
４・・・安息香酸ヘキシルのピーク
溶出時間（分）
第
図
溶出時間（分）
第
図FIG. 1 is a chromatogram in Example 1, FIG. 2 is a chromatogram in Example 2, and FIG. 3 is a chromatogram in Example 3. Explanation of symbols 1...Creatinine peak 2...Methyl benzoate peak 3...Butyl benzoate peak 4...Hexyl benzoate peak elution time (minutes) Fig. Elution time (minutes) figure
Claims (1)
ステル又はビニルエーテル（ I ）と水酸基を持つビニ
ルエステル又はビニルエーテル架橋剤（II）とを、（
I ）／（II）のモル比が１〜０．０５の範囲となるよう
にして水性懸濁重合させることを特徴とする逆相液体ク
ロマトグラフィー用架橋共重合体粒子の製造法。 ２、炭素原子数６〜２４の脂肪族アルコールのビニルエ
ステル（ I ）がラウリルメタクリレート又はステアリ
ルメタクリレートである請求項１記載の逆相液体クロマ
トグラフィー用架橋共重合体粒子の製造法。 ３、水酸基を持つビニルエステル架橋剤（II）が多価ア
ルコールのポリメタクリル酸エステルである請求項１又
は２記載の逆相液体クロマトグラフィー用架橋共重合体
粒子の製造法。 ４、請求項１、２又は３記載の製造法によって製造した
架橋共重合体粒子を充填してなる逆相液体クロマトグラ
フィー用カラム。[Claims] 1. A vinyl ester or vinyl ether of an aliphatic alcohol having 6 to 24 carbon atoms (I) and a vinyl ester or vinyl ether crosslinking agent (II) having a hydroxyl group, (
A method for producing crosslinked copolymer particles for reversed-phase liquid chromatography, characterized by carrying out aqueous suspension polymerization such that the molar ratio of I)/(II) is in the range of 1 to 0.05. 2. The method for producing crosslinked copolymer particles for reversed-phase liquid chromatography according to claim 1, wherein the vinyl ester (I) of an aliphatic alcohol having 6 to 24 carbon atoms is lauryl methacrylate or stearyl methacrylate. 3. The method for producing crosslinked copolymer particles for reversed-phase liquid chromatography according to claim 1 or 2, wherein the vinyl ester crosslinking agent (II) having a hydroxyl group is a polymethacrylate ester of a polyhydric alcohol. 4. A reversed phase liquid chromatography column packed with crosslinked copolymer particles produced by the production method according to claim 1, 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2168742A JPH0458153A (en) | 1990-06-27 | 1990-06-27 | Production of crosslinked copolymer particle for reversed-phase liquid chromatography and column for reversed-phase liquid chromatography |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2168742A JPH0458153A (en) | 1990-06-27 | 1990-06-27 | Production of crosslinked copolymer particle for reversed-phase liquid chromatography and column for reversed-phase liquid chromatography |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0458153A true JPH0458153A (en) | 1992-02-25 |
Family
ID=15873576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2168742A Pending JPH0458153A (en) | 1990-06-27 | 1990-06-27 | Production of crosslinked copolymer particle for reversed-phase liquid chromatography and column for reversed-phase liquid chromatography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0458153A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003104294A1 (en) * | 2002-06-05 | 2003-12-18 | Imperial College Innovations Limited | Polyvinyl ethers |
| US7491779B2 (en) | 2002-06-05 | 2009-02-17 | Imperial College Of Science, Technology And Medicine | Polyvinyl ethers |
-
1990
- 1990-06-27 JP JP2168742A patent/JPH0458153A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003104294A1 (en) * | 2002-06-05 | 2003-12-18 | Imperial College Innovations Limited | Polyvinyl ethers |
| US7491779B2 (en) | 2002-06-05 | 2009-02-17 | Imperial College Of Science, Technology And Medicine | Polyvinyl ethers |
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