JPH04239009A - Synthesis of styrene/divinylbenzene copolymer and packing for liquid chromatography - Google Patents
Synthesis of styrene/divinylbenzene copolymer and packing for liquid chromatographyInfo
- Publication number
- JPH04239009A JPH04239009A JP3002753A JP275391A JPH04239009A JP H04239009 A JPH04239009 A JP H04239009A JP 3002753 A JP3002753 A JP 3002753A JP 275391 A JP275391 A JP 275391A JP H04239009 A JPH04239009 A JP H04239009A
- Authority
- JP
- Japan
- Prior art keywords
- divinylbenzene
- styrene
- copolymer
- liquid chromatography
- divinylbenzene copolymer
- 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
- 229920001577 copolymer Polymers 0.000 title claims abstract description 39
- 238000012856 packing Methods 0.000 title claims abstract description 18
- 238000004811 liquid chromatography Methods 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 15
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000000926 separation method Methods 0.000 abstract description 13
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 abstract description 10
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003480 eluent Substances 0.000 abstract description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004458 analytical method Methods 0.000 abstract description 4
- 150000001413 amino acids Chemical class 0.000 description 17
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 15
- 239000003729 cation exchange resin Substances 0.000 description 13
- 239000013060 biological fluid Substances 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はスチレン−ジビニルベン
ゼン共重合体の合成法および液体クロマトグラフィー用
充填剤に関し、さらに詳しくはカラム圧の低いスチレン
−ジビニルベンゼン共重合体の合成法およびこれを用い
た液体クロマトグラフィー用充填剤に関する。[Field of Industrial Application] The present invention relates to a method for synthesizing a styrene-divinylbenzene copolymer and a packing material for liquid chromatography, and more particularly to a method for synthesizing a styrene-divinylbenzene copolymer with low column pressure and its use. This invention relates to a packing material for liquid chromatography.
【０００２】0002
【従来の技術】従来、液体クロマトグラフィーにおける
高分子充填剤には、スチレン−ジビニルベンゼン共重合
体、アクリル系樹脂、ポリ酢酸ビニル、ポリアクリラー
トなどの架橋高分子物質にイオン交換基を付与したイオ
ン交換樹脂が用いられ、このイオン交換樹脂はイオン性
の化合物の分離に利用されている。[Prior Art] Conventionally, polymer fillers used in liquid chromatography include ion exchange groups added to crosslinked polymer materials such as styrene-divinylbenzene copolymer, acrylic resin, polyvinyl acetate, and polyacrylate. Ion exchange resins are used to separate ionic compounds.
【０００３】液体クロマトグラフィー分析の所要時間を
短縮するためには、溶離液を高速で流すことができる耐
圧性の装置と高分子充填剤が必要である。例えば、機械
的強度の小さい高分子充填剤を用いて溶離液を高速で流
すと、充填剤細孔の構造が圧縮され、その結果、カラム
圧が上昇し、装置、特に送液ポンプにかかる負担が大き
くなる。高分子充填剤の機械的強度は、高分子の架橋度
を増加することにより向上させることができるが、架橋
度を変化させると、分離性能、特に多成分アミノ酸の相
互分離性能に大きく影響する。[0003] In order to shorten the time required for liquid chromatography analysis, pressure-resistant equipment and polymeric packing materials that can flow the eluent at high speed are required. For example, when a polymer packing material with low mechanical strength is used and the eluent is flowed at high speed, the pore structure of the packing material is compressed, resulting in an increase in column pressure and a strain on the equipment, especially the liquid pump. becomes larger. The mechanical strength of a polymer filler can be improved by increasing the degree of crosslinking of the polymer, but changing the degree of crosslinking greatly affects the separation performance, especially the ability to separate multicomponent amino acids from each other.
【０００４】多成分アミノ酸を高い性能で分離する高速
アミノ酸分析計用充填剤としては、スチレン−ジビニル
ベンゼン共重合体にスルホン基を導入したイオン交換樹
脂が用いられている。スチレン−ジビニルベンゼン共重
合体は、スチレンとジビニルベンゼンを水溶液中で懸濁
重合して得られるが、架橋剤モノマーであるジビニルベ
ンゼンには、ｍ−ジビニルベンゼン、ｐ−ジビニルベン
ゼン、エチルビニルベンゼンなどが混在した混合物が用
いられている。例えば特公昭５４−２６３９６号公報で
は、架橋剤モノマーとして純度５５重量％のジビニルベ
ンゼン、４０重量％のエチルビニルベンゼンおよび５重
量％のその他飽和化合物の混合物が用いられている。し
かしながら、近年、特に高速アミノ酸分析計用充填剤と
して、装置に負担をかけないカラム圧の低いスチレン−
ジビニルベンゼン共重合体が要望されている。[0004] As a packing material for a high-speed amino acid analyzer that separates multicomponent amino acids with high performance, an ion exchange resin in which a sulfone group is introduced into a styrene-divinylbenzene copolymer is used. Styrene-divinylbenzene copolymer is obtained by suspension polymerization of styrene and divinylbenzene in an aqueous solution. Divinylbenzene, which is a crosslinking monomer, includes m-divinylbenzene, p-divinylbenzene, ethylvinylbenzene, etc. A mixture of these is used. For example, in Japanese Patent Publication No. 54-26396, a mixture of divinylbenzene with a purity of 55% by weight, ethylvinylbenzene with a purity of 40% by weight and other saturated compounds with a purity of 5% by weight is used as a crosslinking monomer. However, in recent years, styrene, which has low column pressure and does not put a burden on the equipment, has been used as a packing material for high-speed amino acid analyzers.
Divinylbenzene copolymers are desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、前記
従来技術の問題を解決し、機械的強度に優れ、高い分離
性能を有するとともにカラム入口圧を低くすることがで
きるスチレン−ジビニルベンゼン共重合体の合成法およ
びこれを用いた液体クロマトグラフィー用充填剤を提供
することにある。SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art described above, and to provide a styrene-divinylbenzene copolymer which has excellent mechanical strength, high separation performance, and can lower column inlet pressure. An object of the present invention is to provide a method for synthesizing a polymer and a packing material for liquid chromatography using the same.
【０００６】[0006]
【課題を解決するための手段】本発明は、スチレンと、
実質的に異性体が混在しないジビニルベンゼンとを反応
させることを特徴とするスチレン−ジビニルベンゼン共
重合体の合成法およびこれにより得られたスチレン−ジ
ビニルベンゼン共重合体をスルホン化したことを特徴と
する液体クロマトグラフィー用充填剤に関する。[Means for Solving the Problems] The present invention provides styrene and
A method for synthesizing a styrene-divinylbenzene copolymer characterized by reacting it with divinylbenzene in which substantially no isomers are mixed, and the styrene-divinylbenzene copolymer obtained thereby is sulfonated. The present invention relates to a packing material for liquid chromatography.
【０００７】[0007]
【作用】従来のようにスチレンとジビニルベンゼンを共
重合する際に、異性体および多成分が混在するジビニル
ベンゼンを用いると、共重合体中に構造の異なるモノマ
ーが架橋することになり、液体クロマトグラフィー分析
のカラム圧や分離性能に影響を及ぼす充填剤細孔の構造
が不均一となり、充填剤の膨潤度や収縮率等に差が生じ
るため、溶離液を高速で流すとカラム圧が高くなる。し
かし、本発明においては、実質的に異性体が混在しない
ジビニルベンゼンを用いるため、構造のほぼ等しいモノ
マーを架橋することができ、充填剤細孔の構造がほぼ均
一となり、カラム入口圧を低くすることができる。[Function] When copolymerizing styrene and divinylbenzene as in the past, if divinylbenzene, which is a mixture of isomers and multiple components, is used, monomers with different structures will be crosslinked in the copolymer, resulting in liquid chromatography. The structure of the pores of the packing material, which affects the column pressure and separation performance in graphical analysis, becomes non-uniform, resulting in differences in the degree of swelling and shrinkage of the packing material, so the column pressure increases when the eluent is passed at high speed. . However, in the present invention, since divinylbenzene is used that does not substantially contain isomers, monomers with almost the same structure can be crosslinked, and the structure of the packing pores becomes almost uniform, reducing the column inlet pressure. be able to.
【０００８】本発明に用いられるスチレン−ジビニルベ
ンゼン共重合体は、スチレンと、実質的に異性体（ｍ−
ジビニルベンゼンまたはｐ−ジビニルベンゼン）が混在
しないジビニルベンゼンとの共重合により得られる。本
発明において、実質的に異性体が混在しない範囲とは、
異性体の割合が０〜２０体積％、好ましくは０〜１０体
積％をいう。The styrene-divinylbenzene copolymer used in the present invention is substantially an isomer (m-
Divinylbenzene or p-divinylbenzene) is copolymerized with divinylbenzene. In the present invention, the range in which isomers are not substantially mixed is defined as
The proportion of isomers is 0 to 20% by volume, preferably 0 to 10% by volume.
【０００９】共重合は、例えば、粒径調整剤としてポリ
ビニルアルコール等の水溶性高分子を、粒径付着防止剤
としてドデシル硫酸ナトリウム等の界面活性剤を溶解し
た水溶液中に、スチレン、ジビニルベンゼンおよび重合
開始剤を仕込み、懸濁重合法によって行われる。分離性
能に優れた微粒子状の共重合体を得るためには、モノマ
ー濃度を水１リットルに対して１００ｇ以下、水溶性高
分子の濃度を５．０×１０−２ｇ／ｍｌ以上、攪拌速度
を毎分１，５００回転以上、重合温度を５０〜１００℃
の範囲とするのが好ましい。Copolymerization is carried out by, for example, adding styrene, divinylbenzene, and A polymerization initiator is charged and suspension polymerization is carried out. In order to obtain a fine particulate copolymer with excellent separation performance, the monomer concentration should be 100 g or less per liter of water, the water-soluble polymer concentration should be 5.0 x 10-2 g/ml or more, and the stirring speed should be adjusted. 1,500 revolutions per minute or more, polymerization temperature 50-100℃
It is preferable to set it as the range of.
【００１０】重合開始剤としては、過酸化ベンゾイル、
過酸化ｔｅｒｔ−ブチル等の過酸化物、アゾビスイソブ
チルニトリル、アゾビスシクロヘキサンニトリル等のア
ゾ化合物が用いられ、通常、モノマーに対して１重量％
以上添加される。As a polymerization initiator, benzoyl peroxide,
Peroxides such as tert-butyl peroxide, azo compounds such as azobisisobutylnitrile and azobiscyclohexanenitrile are used, and usually 1% by weight based on the monomer.
or more is added.
【００１１】本発明になる液体クロマトグラフィー用充
填剤は、例えば、上記で得られた微粒子状のスチレン−
ジビニルベンゼン共重合体を、テトラクロロエタンで膨
潤させたのち、クロロ硫酸を作用させてスルホン化する
ことにより得られ、この充填剤は、３ｍｅｑ／ｇ以上の
イオン交換容量を有する。The packing material for liquid chromatography according to the present invention is, for example, the fine particulate styrene obtained above.
It is obtained by swelling a divinylbenzene copolymer with tetrachloroethane and then sulfonating it with chlorosulfuric acid, and this filler has an ion exchange capacity of 3 meq/g or more.
【００１２】0012
【実施例】以下、本発明を実施例により詳しく説明する
。[Examples] The present invention will be explained in detail below using examples.
【００１３】実施例１
（１）スチレン−ｐ−ジビニルベンゼン共重合体（ａ）
の合成
内容積５００ｍｌのセパラブル円筒形３つ口フラスコに
、プロペラ形攪拌翼を有する攪拌機、還流冷却器および
窒素導入管を取りつけ、ポリビニルアルコール（重合度
２，０００、ケン化度８０モル％）１２．５ｇおよびド
デシル硫酸ナトリウム０．０１ｇを入れ、２００ｍｌの
蒸留水で溶解した（ポリビニルアルコール濃度：６．２
５×１０−２ｇ／ｍｌ、ドデシル硫酸ナトリウム濃度：
５．０×１０−５ｇ／ｍｌ）。次いで、過酸化ベンゾイ
ル０．３６ｇおよびｐ−ジビニルベンゼン１．１５ｇを
スチレン１８．７ｍｌに溶解して上記水溶液に加え、窒
素ガスを導入しながら毎分３，０００回転で攪拌しつつ
、油浴で反応溶液温度を９０℃に保った。６時間後、反
応器を冷却し、生成物を熱湯トルエンで充分洗浄し、５
０℃以下で乾燥してスチレン−ｐ−ジビニルベンゼン共
重合体（ａ） を得た。この共重合体（ａ） は１〜１
０μｍの球形微粒子であった。またＫＢｒ法により共重
合体（ａ） の赤外吸収スペクトルを測定し、その結果
を図２に示したが、ｐ−ジビニルベンゼンに由来するｐ
−二置換ベンゼン環の吸収が１５１０ｃｍ−１に見られ
た。Example 1 (1) Styrene-p-divinylbenzene copolymer (a)
Synthesis A separable cylindrical three-necked flask with an internal volume of 500 ml was equipped with a stirrer with propeller-shaped stirring blades, a reflux condenser, and a nitrogen introduction tube, and polyvinyl alcohol (degree of polymerization 2,000, degree of saponification 80 mol%) 12 .5g and 0.01g of sodium dodecyl sulfate were added and dissolved in 200ml of distilled water (polyvinyl alcohol concentration: 6.2
5x10-2g/ml, sodium dodecyl sulfate concentration:
5.0 x 10-5 g/ml). Next, 0.36 g of benzoyl peroxide and 1.15 g of p-divinylbenzene were dissolved in 18.7 ml of styrene, added to the above aqueous solution, and stirred at 3,000 rpm while introducing nitrogen gas in an oil bath. The reaction solution temperature was maintained at 90°C. After 6 hours, the reactor was cooled and the product was thoroughly washed with hot water toluene.
It was dried at 0°C or lower to obtain a styrene-p-divinylbenzene copolymer (a). This copolymer (a) is 1 to 1
They were spherical fine particles with a diameter of 0 μm. In addition, the infrared absorption spectrum of copolymer (a) was measured using the KBr method, and the results are shown in Figure 2.
An absorption of the -disubstituted benzene ring was observed at 1510 cm-1.
【００１４】（２）陽イオン交換樹脂（Ａ） の調製テ
トラクロロエタン１５ｍｌが入った三角フラスコに、上
記で得られた共重合体（ａ） ５ｇを加えて６０℃で３
０分間加温し、共重合体を膨潤させ、水冷した後、クロ
ロ硫酸１０ｍｌを加えて攪拌しつつ４時間反応させた。
反応後、氷酢酸により残存クロロ硫酸を分解してスルホ
ニルクロライドが導入された共重合体を、１Ｎ−ＮａＯ
Ｈ溶液中で１時間煮沸し、スルホン基を導入し、球状の
陽イオン交換樹脂（Ａ） を７ｇ得た。得られた陽イオ
ン交換樹脂（Ａ） のイオン交換容量は３．４４ｍｅｇ
／ｇであり、液体クロマトグラフィー用充填剤としては
充分なイオン交換容量を有することがわかった。(2) Preparation of cation exchange resin (A) 5 g of the copolymer (a) obtained above was added to an Erlenmeyer flask containing 15 ml of tetrachloroethane, and the mixture was heated at 60°C for 30 minutes.
After heating for 0 minutes to swell the copolymer and cooling with water, 10 ml of chlorosulfuric acid was added and reacted for 4 hours with stirring. After the reaction, the remaining chlorosulfuric acid was decomposed with glacial acetic acid, and the copolymer into which sulfonyl chloride was introduced was treated with 1N-NaO
The mixture was boiled in H solution for 1 hour to introduce sulfone groups, and 7 g of spherical cation exchange resin (A) was obtained. The ion exchange capacity of the obtained cation exchange resin (A) was 3.44 meg.
/g, indicating that it has a sufficient ion exchange capacity as a packing material for liquid chromatography.
【００１５】（３）生体液アミノ酸の分離得られた陽イ
オン交換樹脂（Ａ） をＮａ型からＬｉ型の樹脂に変え
て内径４．６ｍｍで長さ６０ｍｍの液体クロマトグラフ
ィー用空カラムに充填した。この充填カラムに、リチウ
ム濃度０．０９ＭでｐＨ２．８のクエン酸系緩衝液を、
カラム温度３８℃、流速０．３５ｍｌ／ｍｉｎ で流し
、生体液アミノ酸の分離を行った。このときのカラム圧
は５６ｋｇ／ｃｍ２ であった。(3) Separation of amino acids in biological fluids The obtained cation exchange resin (A) was changed from Na-type to Li-type resin and packed into an empty column for liquid chromatography with an inner diameter of 4.6 mm and a length of 60 mm. . A citric acid buffer solution with a lithium concentration of 0.09M and a pH of 2.8 was added to this packed column.
The column was run at a temperature of 38° C. and a flow rate of 0.35 ml/min to separate amino acids from biological fluids. The column pressure at this time was 56 kg/cm2.
【００１６】（４）標準アミノ酸の分離Ｎａ型の陽イオ
ン交換樹脂（Ａ） を充填した充填カラムに、ナトリウ
ム濃度０．１６ＭでｐＨ３．３のクエン酸系緩衝液を、
カラム温度５７℃で流速０．４０ｍｌ／ｍｉｎ で流し
、標準アミノ酸の分離を行った。このときのカラム圧は
９０ｋｇ／ｃｍ２ であった。(4) Separation of standard amino acids A citric acid buffer solution with a sodium concentration of 0.16M and a pH of 3.3 was added to a packed column filled with Na-type cation exchange resin (A).
Standard amino acids were separated by running the column at a flow rate of 0.40 ml/min at a column temperature of 57°C. The column pressure at this time was 90 kg/cm2.
【００１７】実施例２
（１）スチレン−ｍ−ジビニルベンゼン共重合体（ｂ）
の合成
実施例１（１）において、ｐ−ジビニルベンゼンをｍ−
ジビニルベンゼンに替えた以外は実施例１（１）と同様
の方法で共重合を行い、粒径１〜１０μｍの球形微粒子
のスチレン−ｍ−ジビニルベンゼン共重合体（ｂ） を
得た。この共重合体（ｂ） を実施例１（１）と同様に
赤外吸収スペクトルを測定し、その結果を図３に示した
が、ｍ−ジビニルベンゼンに由来するｍ−二置換ベンゼ
ン環の吸収が７９５ｃｍ−１に見られた。Example 2 (1) Styrene-m-divinylbenzene copolymer (b)
In Synthesis Example 1 (1), p-divinylbenzene was converted to m-
Copolymerization was carried out in the same manner as in Example 1 (1) except that divinylbenzene was used to obtain a styrene-m-divinylbenzene copolymer (b) in the form of spherical fine particles with a particle size of 1 to 10 μm. The infrared absorption spectrum of this copolymer (b) was measured in the same manner as in Example 1 (1), and the results are shown in Figure 3. was observed at 795 cm-1.
【００１８】（２）陽イオン交換樹脂（Ｂ） の調製実
施例１（２）において、上記共重合体（ｂ） を用いた
以外は実施例１（２）と同様にしてスルホン基を導入し
、球状の陽イオン交換樹脂（Ｂ） を７ｇ得た。得られ
た陽イオン交換樹脂（Ｂ） のイオン交換容量は３．０
４ｍｅｑ／ｇであり、液体クロマトグラフィー用充填剤
としては充分なイオン交換容量を有することがわかった
。(2) Preparation of cation exchange resin (B) In Example 1 (2), a sulfone group was introduced in the same manner as in Example 1 (2) except that the above copolymer (b) was used. , 7g of spherical cation exchange resin (B) was obtained. The ion exchange capacity of the obtained cation exchange resin (B) was 3.0.
It was found that the ion exchange capacity was 4 meq/g, which was sufficient as a packing material for liquid chromatography.
【００１９】（３）生体液アミノ酸の分離実施例１（３
）において、上記陽イオン交換樹脂（Ｂ） を用いた以
外は実施例１（３）と同様にして生体液アミノ酸の分離
を行った。このときのカラム圧は６３ｋｇ／ｃｍ２ で
あった。(3) Example 1 of separation of amino acids from biological fluids (3)
), biological fluid amino acids were separated in the same manner as in Example 1 (3) except that the above cation exchange resin (B) was used. The column pressure at this time was 63 kg/cm2.
【００２０】（４）標準アミノ酸の分離実施例１（４）
において、陽イオン交換樹脂（Ｂ） を用いた以外は実
施例１（４）と同様にして標準アミノ酸の分離を行った
。このときのカラム圧は９７ｋｇ／ｃｍ２ であった。(4) Standard amino acid separation Example 1 (4)
Standard amino acids were separated in the same manner as in Example 1 (4) except that cation exchange resin (B) was used. The column pressure at this time was 97 kg/cm2.
【００２１】比較例１
実施例１（１）において、ｐ−ジビニルベンゼンに替え
てｍ−ジビニルベンゼン、ｐ−ジビニルベンゼン、ｍ−
エチルビニルベンゼンおよびｐ−エチルビニルベンゼン
の混合物を用いた以外は実施例１（１）と同様の方法で
共重合を行い、スチレン−ジビニルベンゼン共重合体（
ｃ） を得た。この共重合体（ｃ）の形状は１〜１０μ
ｍの球形微粒子であった。またＫＢｒ法により共重合体
（ｃ） の赤外吸収スペクトルを測定し、その結果を図
４に示したが、ｍ−ジビニルベンゼンとｐ−ジビニルベ
ンゼンに由来するｍ−二置換ベンゼン環およびｐ−二置
換ベンゼン環の吸収が１５１０ｃｍ−１と７９５ｃｍ−
１に見られた。Comparative Example 1 In Example 1 (1), m-divinylbenzene, p-divinylbenzene, m-divinylbenzene was used instead of p-divinylbenzene.
Copolymerization was carried out in the same manner as in Example 1 (1) except that a mixture of ethylvinylbenzene and p-ethylvinylbenzene was used, and styrene-divinylbenzene copolymer (
c) obtained. The shape of this copolymer (c) is 1 to 10μ
They were spherical fine particles of m. In addition, the infrared absorption spectrum of copolymer (c) was measured using the KBr method, and the results are shown in Figure 4. The absorption of disubstituted benzene ring is 1510 cm-1 and 795 cm-1.
Seen in 1.
【００２２】この共重合体（ｃ） を用いて実施例１（
２）と同様にしてスルホン化を行い、イオン交換容量２
．９６ｍｅｑ／ｇの陽イオン交換樹脂（Ｃ） を得た。
この陽イオン交換樹脂（Ｃ） を用いて実施例１（３）
および（４）と同様にして生体液アミノ酸と標準アミノ
酸の分離を行った。このときのカラム圧は生体液アミノ
酸分離時では９２ｋｇ／ｃｍ２ 、標準アミノ酸分離時
では１１５ｋｇ／ｃｍ２ であり、実施例１および２に
比較して高い値を示した。Using this copolymer (c), Example 1 (
Sulfonation is performed in the same manner as in 2), and the ion exchange capacity is 2.
．． A cation exchange resin (C) of 96 meq/g was obtained. Example 1 (3) using this cation exchange resin (C)
And biological fluid amino acids and standard amino acids were separated in the same manner as in (4). The column pressure at this time was 92 kg/cm2 during biological fluid amino acid separation and 115 kg/cm2 during standard amino acid separation, which were higher values compared to Examples 1 and 2.
【００２３】実施例３〜８および比較例２〜６実施例１
（１）において、ｐ−ジビニルベンゼンに１０、１５、
２０、２５、３０、５０、７０、７５、８０、８５およ
び９０体積％のｍ−ジビニルベンゼンを加えた以外は実
施例１（１）と同様にして共重合体を合成し、また実施
例１（２）と同様にしてＮａ型陽イオン交換樹脂を調製
した。さらにこれらを用いて実施例１（３）と同様にし
て生体液アミノ酸の分離を行い、そのときのカラム圧を
測定し、このときの結果を実施例１および２の結果とと
もに図１に示した。図中の○印は実施例１〜８を示し、
△印は比較例２〜６を示す。Examples 3 to 8 and Comparative Examples 2 to 6 Example 1
In (1), p-divinylbenzene has 10, 15,
A copolymer was synthesized in the same manner as in Example 1 (1) except that 20, 25, 30, 50, 70, 75, 80, 85 and 90% by volume of m-divinylbenzene was added, and Example 1 A Na-type cation exchange resin was prepared in the same manner as in (2). Furthermore, using these, biological fluid amino acids were separated in the same manner as in Example 1 (3), and the column pressure at that time was measured. The results are shown in Figure 1 together with the results of Examples 1 and 2. . The ○ marks in the figure indicate Examples 1 to 8,
△ marks indicate Comparative Examples 2 to 6.
【００２４】図１から、２０体積％以下のｍ−ジビニル
ベンゼンを含むｐ−ジビニルベンゼン（実施例１、３〜
５）および２０体積％以下のｐジビニルベンゼンを含む
ｍ−ジビニルベンゼン（実施例２、６〜８）を用いた場
合にはカラム圧が低いことが示される。From FIG. 1, it can be seen that p-divinylbenzene containing 20% by volume or less of m-divinylbenzene (Examples 1 and 3 to
5) and m-divinylbenzene containing 20% by volume or less of p-divinylbenzene (Examples 2, 6-8) show that the column pressure is low.
【００２５】[0025]
【発明の効果】本発明によれば、実質的に異性体の混在
しないジビニルベンゼンを用いて得られたスチレン−ジ
ビニルベンゼン共重合体をイオン交換樹脂化しているた
め、溶離液を高速で流してもカラム入口圧を低くするこ
とができ、液体クロマトグラフィー装置にかかる負担を
減少することができる。また分離性能を低下させずに高
流速で分離を行うことができるため、分析時間を短縮す
ることができる。[Effects of the Invention] According to the present invention, since the styrene-divinylbenzene copolymer obtained using divinylbenzene, which is substantially free of isomers, is made into an ion exchange resin, the eluent can be flowed at high speed. Also, the column inlet pressure can be lowered, and the load placed on the liquid chromatography apparatus can be reduced. Furthermore, since separation can be performed at a high flow rate without reducing separation performance, analysis time can be shortened.
【図１】ｍ−ジビニルベンゼンの使用割合とカラム圧と
の関係を示す図である。FIG. 1 is a diagram showing the relationship between the usage ratio of m-divinylbenzene and column pressure.
【図２】実施例１で得られたスチレン−ｐ−ジビニルベ
ンゼン共重合体（ａ）の赤外吸収スペクトル図である。FIG. 2 is an infrared absorption spectrum diagram of the styrene-p-divinylbenzene copolymer (a) obtained in Example 1.
【図３】実施例２で得られたスチレン−ｍ−ジビニルベ
ンゼン共重合体（ｂ）の赤外吸収スペクトル図である。FIG. 3 is an infrared absorption spectrum diagram of the styrene-m-divinylbenzene copolymer (b) obtained in Example 2.
【図４】比較例１で得られたスチレン−ジビニルベンゼ
ン共重合体（ｃ） の赤外吸収スペクトル図である。FIG. 4 is an infrared absorption spectrum diagram of the styrene-divinylbenzene copolymer (c) obtained in Comparative Example 1.
Claims (3)
ないジビニルベンゼンとを反応させることを特徴とする
スチレン−ジビニルベンゼン共重合体の合成法。1. A method for synthesizing a styrene-divinylbenzene copolymer, which comprises reacting styrene with divinylbenzene in which substantially no isomers are present.
ビニルベンゼンを用いることを特徴とする請求項１記載
のスチレン−ジビニルベンゼン共重合体の合成法。2. The method for synthesizing a styrene-divinylbenzene copolymer according to claim 1, wherein divinylbenzene containing 20% by volume or less of isomers is used.
ビニルベンゼン共重合体をスルホン化したことを特徴と
する液体クロマトグラフィー用充填剤。3. A packing material for liquid chromatography, characterized in that the styrene-divinylbenzene copolymer according to claim 1 or 2 is sulfonated.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3002753A JPH04239009A (en) | 1991-01-14 | 1991-01-14 | Synthesis of styrene/divinylbenzene copolymer and packing for liquid chromatography |
| EP19920300266 EP0496513A3 (en) | 1991-01-14 | 1992-01-13 | Process for producing ionexchange resins and use of the resins for separating amino acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3002753A JPH04239009A (en) | 1991-01-14 | 1991-01-14 | Synthesis of styrene/divinylbenzene copolymer and packing for liquid chromatography |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04239009A true JPH04239009A (en) | 1992-08-26 |
Family
ID=11538108
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3002753A Pending JPH04239009A (en) | 1991-01-14 | 1991-01-14 | Synthesis of styrene/divinylbenzene copolymer and packing for liquid chromatography |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04239009A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181842A1 (en) * | 2017-03-30 | 2018-10-04 | 新日鉄住金化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer, method for producing same, curable resin composition and cured product thereof |
-
1991
- 1991-01-14 JP JP3002753A patent/JPH04239009A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018181842A1 (en) * | 2017-03-30 | 2018-10-04 | 新日鉄住金化学株式会社 | Soluble polyfunctional vinyl aromatic copolymer, method for producing same, curable resin composition and cured product thereof |
| JPWO2018181842A1 (en) * | 2017-03-30 | 2020-02-20 | 日鉄ケミカル＆マテリアル株式会社 | Soluble polyfunctional vinyl aromatic copolymer, method for producing the same, curable resin composition and cured product thereof |
| US11130861B2 (en) | 2017-03-30 | 2021-09-28 | Nippon Steel Chemical & Material Co., Ltd. | Soluble polyfunctional vinyl aromatic copolymer, method for producing same, curable resin composition and cured product thereof |
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