KR20030023984A - The manufacturing process of a packing material on HPLC Column - Google Patents
The manufacturing process of a packing material on HPLC Column Download PDFInfo
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- KR20030023984A KR20030023984A KR1020010056760A KR20010056760A KR20030023984A KR 20030023984 A KR20030023984 A KR 20030023984A KR 1020010056760 A KR1020010056760 A KR 1020010056760A KR 20010056760 A KR20010056760 A KR 20010056760A KR 20030023984 A KR20030023984 A KR 20030023984A
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- chlorodimethylsilylmethyl
- silane compound
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- 238000004128 high performance liquid chromatography Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000012856 packing Methods 0.000 title claims description 5
- 239000000463 material Substances 0.000 title description 6
- 230000007717 exclusion Effects 0.000 claims abstract description 14
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- YHMOLPMXYPCHBK-UHFFFAOYSA-N ClC(CCCCCCCCCCCCCCCCCCCCCC)C[SiH](C)C Chemical compound ClC(CCCCCCCCCCCCCCCCCCCCCC)C[SiH](C)C YHMOLPMXYPCHBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- QAHJUMJDFIDRRR-UHFFFAOYSA-N ClC(CCCCCCCCCCCCCCCCCCCCCCCCCC)C[SiH](C)C Chemical compound ClC(CCCCCCCCCCCCCCCCCCCCCCCCCC)C[SiH](C)C QAHJUMJDFIDRRR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000077 silane Inorganic materials 0.000 claims description 25
- -1 silane compound Chemical class 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 11
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 11
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 7
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 7
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 4
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- FDWKPOMSVJQMQS-UHFFFAOYSA-N heptacosane silane Chemical compound [SiH4].CCCCCCCCCCCCCCCCCCCCCCCCCCC FDWKPOMSVJQMQS-UHFFFAOYSA-N 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012454 non-polar solvent Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- GETFKTBXELLOHD-UHFFFAOYSA-N chloro-ethoxy-methylsilane Chemical compound CCO[SiH](C)Cl GETFKTBXELLOHD-UHFFFAOYSA-N 0.000 claims 1
- 230000000295 complement effect Effects 0.000 abstract 1
- 238000001542 size-exclusion chromatography Methods 0.000 abstract 1
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- YTJSFYQNRXLOIC-UHFFFAOYSA-N octadecylsilane Chemical compound CCCCCCCCCCCCCCCCCC[SiH3] YTJSFYQNRXLOIC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- 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
- B01J20/283—Porous sorbents based on silica
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
고성능 액체크로마토그래피 칼럼 제조를 위하여 클로로디메틸실릴메틸 트리코산(Chlorodimethylsilylmethyl tricosane) 및 클로로디메틸실릴메틸 헵타코산 (Chlorodimethylsilylmethyl heptacosane)화합물을 이용하여 역상 칼럼을 제조하므로써 종래의 C18(ODS) 칼럼의 단점을 보완한 우수한 역상 칼럼을 제조하고, 또한 디메틸클로로실란(DMCS)등을 크기배제 크로마토그래피 칼럼에 이용하므로써 고성능의 상온용 및 고온용 겸용 크기배제 칼럼을 제조할 수 있도록 한 발명이다.The disadvantages of conventional C 18 (ODS) columns are prepared by preparing reversed phase columns using chlorodimethylsilylmethyl tricosane and chlorodimethylsilylmethyl heptacosane for the preparation of high performance liquid chromatography columns. It is an invention to prepare a good complementary reversed phase column and dimethylchlorosilane (DMCS) and the like in the size exclusion chromatography column to produce a high performance room temperature and high temperature combined size exclusion column.
Description
본 발명은 고성능 액체크로마토그래피 칼럼 충전제 및 그 제조방법에 관한 것으로서, 특히 클로로디메틸실릴메틸 트리코산(Chlorodimethylsilylmethyl tricosane) 및 클로로디메틸실릴메틸 헵타코산 (Chlorodimethylsilylmethyl heptacosane) 화합물을 이용해 역상 칼럼을 제조함으로써 기존의 C18(ODS) 칼럼의 단점을 보완한 우수한 역상 칼럼을 제조할 수 있고, 또한, 디메틸클로로실란( Dimethylchlorosilane : DMCS)등을 크기배제 크로마토그래피 칼럼에 이용함으로써 고성능의 상온용과 고온용 겸용 크기배제 칼럼을 제조할 수 있도록 한 것이다.The present invention relates to a high performance liquid chromatography column filler and a method for preparing the same, and in particular, to prepare a reverse phase column by using a chlorodimethylsilylmethyl tricosane and a chlorodimethylsilylmethyl heptacosane compound. It is possible to manufacture an excellent reversed phase column that compensates for the shortcomings of the C 18 (ODS) column. It is to be able to manufacture.
액체크로마토그래피 칼럼은 충전제의 종류에 따라 흡착, 분배, 이온교환, 크기배제용으로 나눌 수 있으며, 칼럼에 쓰이는 서포트(support)도 크게 그 재질에 따라 무기충전제와 유기폴리머 충전제로 구분된다. 한편, 흡착 및 분배를 기본원리로 하고 있는 역상 및 순상 고성능 액체크로마토그래피에서는 충전 서포트(support )를 무기충전제의 대표격인 실리카겔을 주로 사용하고 있으며, 이를 이용한 가장 사용범위가 폭넓고, 칼럼효율이 좋으며, 가장 보편적으로 사용되고 있는 HPLC 칼럼이 C18(ODS) 칼럼이다. 이러한 C18(ODS) HPLC 칼럼은 역상 칼럼으로서 수많은 성분들을 쉽게 분석할 수 있고, 선택성이 우수하며, 각종 연구개발 분야 및 관련 분야에서 오래전부터 사용되어 오고 있다.Liquid chromatography columns can be divided into adsorption, distribution, ion exchange, and size exclusion according to the type of filler, and support for the column is largely divided into inorganic filler and organic polymer filler according to their materials. On the other hand, reverse phase and pure phase high performance liquid chromatography based on adsorption and distribution mainly uses silica gel, which is representative of inorganic fillers, and has the widest range of use and good column efficiency. The most commonly used HPLC column is the C 18 (ODS) column. This C 18 (ODS) HPLC column is a reversed phase column that can easily analyze numerous components, has excellent selectivity, and has been used for a long time in various research and development fields and related fields.
그러나 기존의 C18(ODS) 칼럼 역시 치명적인 단점들을 가지고 있다. 그 중 가장 큰 문제점의 하나는 C18(ODS) 칼럼이 물로 대표되는 극성 이동상에서 그 사용이 불가능하다는 점이다. 즉, 물 같은 극성 용매들은 기존 칼럼의 고정상 붕괴를 유도하는 것으로 알려져 있는데, 이에 대한 대표적인 예는 C18(ODS) 칼럼을 이용한 유기산 분석을 들 수 있다. 유기산 분석 및 이의 필요성은 근래에 들어 꾸준히 증가해오고 있으나, 분석에 쓰이는 이동상이 약산성 물질로 완충된 100% 수용액을 쓴다는 점에서 그 문제점이 있다. 즉, C18(ODS) 칼럼을 유기산 분석에 적용시 분석이 반복될수록 그 재현성이 소멸된다. 한편, 상기의 갈수록 증가하고 있는 산도분석(유기산 분석)이나 수성용액 상태에서의 C18(ODS) 칼럼의 이러한 단점은 어떠한 제한 사항도 없는 소수상 역상 칼럼의 개발을 절실히 요구하고 있다.However, existing C 18 (ODS) columns also have fatal drawbacks. One of the biggest problems is that the C 18 (ODS) column is not available for use in the polar mobile phase represented by water. That is, polar solvents such as water are known to induce stationary phase collapse of existing columns. An example of this is organic acid analysis using a C 18 (ODS) column. Organic acid analysis and its necessity have been steadily increasing in recent years, but there is a problem in that the mobile phase used for analysis uses a 100% aqueous solution buffered with a weakly acidic substance. In other words, when the C 18 (ODS) column is applied to the organic acid analysis, the reproducibility disappears as the analysis is repeated. On the other hand, the drawback of the increasing acidity analysis (organic acid analysis) or the C 18 (ODS) column in the aqueous solution state is urgently required to develop a hydrophobic reversed phase column without any limitations.
이어서 크기배제를 기본원리로 하고 있는 LC 칼럼은 주로 유기 폴리머 재질을 가장 보편적으로 사용하고 있는 실정이다. 이러한 크기배제의 원리를 기본으로하고 있는 칼럼 충전물들은 큰 다공성을 지녀야 하며, 입자조성이 균일해야 하며, 물리/화학적으로 안정해야 한다. 한편, 현재 가장 많이 사용되고 있는 폴리머 충전제로서는 그 분리능이 우수하지만 제조비용이 고가이고 공극이 불균일하며, 제한된 용매만을 사용할 수 있다. 또한 폴리머 자체의 열 안정성이 작기 때문에 상온용 크기배제 칼럼과 고온용 크기배제 칼럼을 다르게 제조해서 서로 구분해서 사용해야 하는 큰 단점이 있다.Subsequently, the LC column based on size exclusion is the most commonly used organic polymer material. Column packings based on this principle of size exclusion must have large porosity, uniform particle composition, and be physically and chemically stable. On the other hand, the most commonly used polymer fillers have excellent resolution, but are expensive in manufacturing cost, uneven in voids, and only limited solvents can be used. In addition, since the thermal stability of the polymer itself is small, there is a big disadvantage of using differently preparing the size exclusion column for room temperature and the size exclusion column for high temperature.
한편, 균일한 다공성, 자유로운 용매사용, 고온 및 상온에서 동시 사용 가능 등의 다공성 실리카겔 충전제의 이론적 장점에도 불구하고 현재 크기배제 칼럼으로 많이 사용하지 않는 이유는 실리카겔 자체에 보유하고 있는 실라놀기의 강한 흡착 작용으로 인한 분석시료들이 순수한 크기배제 메카니즘외의 영향을 받기 때문이다.On the other hand, despite the theoretical advantages of porous silica gel fillers such as uniform porosity, free solvent use, simultaneous use at high temperature and room temperature, the reason why it is not widely used as size exclusion column is the strong adsorption of silanol groups in silica gel itself. Analytical samples due to the action are affected outside of the pure size exclusion mechanism.
한편, 이러한 실리카겔에서 실라놀 흡착문제의 단점은 특정한 실란화합물과의 반응에 의해서 완벽하게 해결될 수 있으며, 실리카겔 충전제 자체의 장점으로 인한 기존 폴리머성능 이상의 분리능을 가져올 수 있다.On the other hand, the disadvantage of the silanol adsorption problem in the silica gel can be completely solved by the reaction with a specific silane compound, it can bring the separation ability than the existing polymer performance due to the advantage of the silica gel filler itself.
종래의 가장 보편적인 역상 칼럼인, C18(ODS) 칼럼은 상술한 바와 같이 극성용매를 이동상으로 함에 있어서 치명적인 단점을 가지고 있었다. 그러나, 본 발명은 종래의 옥타데실 실란(Octadecyl silane)을 사용하지 않고, 클로로디메틸실릴메틸 트리코산(Chlorodimethylsilylmethyl tricosane) 및 클로로디메틸실릴메틸 헵타코산(Chlorodimethylsilylmethyl heptacosane)등의 트리코산 실란(silane)과 헵타코산 실란을 이용하여 이러한 단점을 해결했으며, C18(ODS) 칼럼과 비교하여, 그 수명을 크게 향상시킬 수 있다.The C 18 (ODS) column, the most common reversed phase column of the prior art, had a fatal disadvantage in using the polar solvent as the mobile phase as described above. However, the present invention does not use a conventional octadecyl silane, and does not use trichloroic acid silane such as chlorodimethylsilylmethyl tricosane and chlorodimethylsilylmethyl heptacosane. Heptaconic acid silane was used to solve this shortcoming, and compared to the C 18 (ODS) column, the lifetime can be greatly improved.
또한, 이미 언급했듯이 종래에는 크기배제 칼럼으로서 주로 폴리머 재질을 사용하였으며, 이는 비싼 조제단가, 불균일한 공극, 제한된 사용 용매같은 단점뿐만 아니라, 열적으로 불안정하기 때문에 상온용과 고온용 칼럼으로 따로 구분되어야 한다는 단점이 있다. 따라서, 본 발명은 서포트(support)로 다공성 실리카겔을 사용하고, 알맞는 실란화합물 커플링하고, 이로 인해 실리카겔이 가지고 있는 실라놀기의 흡착작용을 제거하므로써, 제조단가가 저렴해지고, 분리능이 우수하며, 고온 및 상온에서 겸용할 수 있는 크기배제 칼럼을 생산할 수 있도록 한 방법을 제공하는데 그 목적이 있다.In addition, as already mentioned, conventionally, polymer materials are mainly used as size exclusion columns, which are not only disadvantages such as expensive preparation units, uneven pores, and limited use solvents, but are also thermally unstable. There are disadvantages. Therefore, the present invention uses a porous silica gel as a support, and coupling a suitable silane compound, thereby eliminating the adsorption action of the silanol groups possessed by the silica gel, resulting in low manufacturing cost and excellent separation performance. It is an object of the present invention to provide a method for producing a size exclusion column that can be used both at high temperature and at room temperature.
도 1 은 상온에서의 실시예 2 에 의해 제조된 GPC 칼럼과 종래 상업용 GPC 칼럼의 샘플 테스트 결과를 나타낸 그래프이다.1 is a graph showing sample test results of a GPC column prepared by Example 2 and a conventional commercial GPC column at room temperature.
도 2 는 고온에서의 실시예 2 에 의해 제조된 GPC 칼럼과 종래 상업용 GPC 칼럼의 샘플 테스트 결과를 나타낸 그래프이다.2 is a graph showing sample test results of a GPC column prepared by Example 2 at a high temperature and a conventional commercial GPC column.
본 발명은 상술한 바와 같이 종래기술상의 문제점을 해결하기 위하여 전혀 새로운 방법을 창안한 것으로 그 구성을 이하에 설명한다. 즉,The present invention has been devised a completely new method to solve the problems in the prior art as described above, the configuration will be described below. In other words,
본 발명은 기본적으로 고성능 액체크로마토그래피 칼럼 충전제 제조를 위해 클로로디메틸실릴메틸 트리코산(Chlorodimethylsilylmethyl tricosane), 클로로디메틸실릴메틸 헵타코산(Chlorodimethylsilylmethyl heptacosane)등의 트리코산 실란(tricosane silane)과 헵타코산 실란(heptacosane silane) 및 작용기가 클로로(chloro)대신 메톡시(methoxy), 에톡시(ethoxy)로 구성된 실란화합물로 결합된 충전제 제조단계를 가진다.Basically, the present invention is intended to prepare chlorodimethylsilylmethyl tricosane, chlorodimethylsilylmethyl heptacosane, tricosane silane and heptaconic acid silane for the preparation of high performance liquid chromatography column fillers. (heptacosane silane) and a functional group has a filler manufacturing step combined with a silane compound consisting of methoxy (ethoxy) instead of chloro (chloro).
상기 화합물의 기본재료로는 50Å∼300Å 의 실리카겔을 정제하여 사용한다. 그 후, 정제된 실리카겔 일정량을 클로로디메틸실릴메틸 트리코산 또는 클로로디메틸실릴메틸 헵타코산등의 트리코산 실란과 헵타코산 실란 및 작용기가 클로로 (chloro)대신 메톡시, 에톡시로 구성된 실란화합물과 톨루엔등의 비극성 유기용매하에서 일정시간 반응시킨다. 반응온도는 각 실란화합물의 비등점보다 높은 온도로 한다.As a base material of the compound, silica gel of 50 kV to 300 kV is purified and used. Subsequently, a predetermined amount of the purified silica gel was mixed with a trico silane such as chlorodimethylsilylmethyl trichoic acid or chlorodimethylsilylmethyl heptacoic acid, a silane compound consisting of heptaconic silane and a functional group of methoxy and ethoxy instead of chloro. It is made to react for some time in nonpolar organic solvents, such as toluene. The reaction temperature is higher than the boiling point of each silane compound.
이상과 같이 하여 표면개질된 실리카겔은 적당한 유기용매의 세척과정이 거치는데, 그 순서는 극성 용매에서 비극성 용매로의 극성감소 순서로 하며, 그 후 약 100℃ 에서 진공건조시킨다. 그 후 엔드캐핑(endcapping)과정을 거치면, 최종적인 트리코산 실란과 헵타코산 실란 칼럼 충전물이 제조완성된다.As described above, the surface-modified silica gel is subjected to a washing process of an appropriate organic solvent, and the order thereof is in the order of decreasing the polarity from the polar solvent to the non-polar solvent, followed by vacuum drying at about 100 ° C. After the endcapping process, the final trichoic acid silane and heptaconic acid silane column packing are completed.
본 발명상의 상기 제조단계에 따른 실시예를 들어 보다 구체적으로 이하의 실시예로 상세히 설명한다.For example according to the manufacturing step of the present invention will be described in detail in the following examples.
(실시예 1)(Example 1)
500mL 삼구 플라스크 및 질소 통기 장치를 준비한 후 5g 의 정제된 실리카겔을 삼구 플라스크에 넣는다. 그 후 질소 기류하의 삼구 플라스크에 톨루엔 200mL 를 첨가하고 질소로 가득 채운다. 이 상태에서 약 20 분간 교반시키고 나서 클로로디메틸실릴메틸 헵타코산(Chlorodimethylsilylmethyl heptacosane)을 30mL 를 가하고 150℃ 에서 약 24 시간 반응시킨다. 반응이 마감되면 반응물을 여과하고 세척과정을 거친다. 세척과정을 거친 고형물들은 진공 건조기에서 24 시간 동안 건조시키며 건조된 생성물은 위와 동일한 방법으로 엔드캡핑(endcapping)용 실란을 이용해엔드캡핑(endcapping)하며 최종적인 충전물을 완성한다. 실시예 1 의 방법으로 제조된 고성능 액체크로마토그래피 칼럼의 유기산 물질의 체류시간 재현성으로 종래의 칼럼과의 체류시간 재현성과 대비한 결과를 표 1 에 기재하였다.After preparing a 500 mL three-necked flask and a nitrogen venting device, 5 g of purified silica gel is placed in a three-necked flask. Thereafter, 200 mL of toluene is added to the three-necked flask under nitrogen stream and filled with nitrogen. After stirring for 20 minutes in this state, 30 mL of chlorodimethylsilylmethyl heptacosane is added and reacted at 150 ° C for about 24 hours. At the end of the reaction, the reactants are filtered and washed. The washed solids are dried in a vacuum dryer for 24 hours, and the dried product is endcapped using the endcapping silane in the same manner as above to complete the final filling. Table 1 shows the results of the retention time reproducibility of the organic acid material of the high performance liquid chromatography column prepared by the method of Example 1 in comparison with the retention time reproducibility with the conventional column.
표 1. 실시예 1 방법에 의해 제조된 고성능 액체크로마토그래피 칼럼과 기존 ODS 칼럼과의 유기산 물질의 체류시간 재현성 비교(Eluent : 100% H2O, 0.1% H3PO4)Table 1.Comparison of residence time reproducibility of organic acid materials between high performance liquid chromatography column prepared by the method of Example 1 and conventional ODS column (Eluent: 100% H 2 O, 0.1% H 3 PO 4 )
본 발명은 또한, 크기배제 칼럼 제조를 위한 디메틸클로로실란 (Dimethylchlorosilane : DMCS) 및 클로로(chloro)기 대신 메톡시나 에톡시로 된 실란화합물이나 메틸클로로실란(MCS), 메틸트리클로로실란(Methyltrichlorosilane : MTCS)을 이용한 표면개질 단계를 가진다.The present invention also provides a silane compound of methoxy or ethoxy instead of dimethylchlorosilane (DMCS) and a chloro group, methylchlorosilane (MCS), methyltrichlorosilane (Methyltrichlorosilane: MTCS) has a surface modification step.
기본 재료로는 100Å∼600Å 의 실리카겔을 정제하여 사용한다. 그 후 정제된 실리카겔 일정량을 상기 디메틸클로로실란이나 메틸클로로실란 및 클로로기 대신 메톡시나 에톡시로 된 실란화합물과 톨루엔의 비극성 유기용매 하에서 일정시간 반응시키면, 반응온도는 각 실란화합물 끓는점보다 높은 온도로 한다. 이상과 같이 표면개질된 실리카겔은 적당한 유기용매의 세척과정을 거치는데 즉, 그 순서는 극성에서 비극성으로 극성이 감소하는 시약순서대로 하며, 그 후 약 100℃ 에서 진공건조시킨다.As a basic material, silica gel of 100 Pa to 600 Pa is purified and used. Then, when a predetermined amount of purified silica gel is reacted with a silane compound of methoxy or ethoxy and a nonpolar organic solvent of toluene instead of dimethylchlorosilane, methylchlorosilane, or chloro group for a certain time, the reaction temperature is higher than the boiling point of each silane compound. Shall be. As described above, the surface-modified silica gel undergoes a washing process of an appropriate organic solvent, that is, the sequence is in the order of reagents decreasing in polarity from polarity to nonpolarity, and then vacuum dried at about 100 ° C.
한편, 메틸트리클로로실란(MTCS)을 이용할 경우는 실리카겔과 반응시 상온에서 진행되며 나머지는 동일하다. 그 후 엔드캡팅(endcapping)공정을 거치면 최종적인 크기배제 칼럼 충전물이 완성 제조된다.Meanwhile, when methyltrichlorosilane (MTCS) is used, the reaction proceeds at room temperature when reacted with silica gel and the rest is the same. The endcapping process then completes the final size exclusion column fill.
상기 원리에 의한 칼럼 충전제 제조시의 실시예를 들면 다음과 같다.Examples of the column filler preparation according to the above principle are as follows.
(실시예 2)(Example 2)
500mL 삼구 플라스크 및 질소 통기 장치를 준비한 후 5g 의 정제된 실리카겔을 삼구 플라스크에 넣는다. 그 후 질소 기류하의 삼구 플라스크에 톨루엔 200mL 를 첨가하고 질소로 가득 채운다. 이 상태에서 약 20 분간 교반시키고 나서 디메틸클로로실란(DMCS)을 30mL 를 가하고 150℃ 에서 약 24 시간 반응시킨다. 반응이 마감되면 반응물을 여과하고 세척과정을 거친다. 이상의 단계를 거친 고형물들은 진공 건조기에서 24 시간 동안 건조시키며 건조된 생성물은 위와 동일한 방법으로 엔드캡핑(endcapping)용 실란을 이용해 엔드캡핑하며 최종적인 충전물을 완성한다.After preparing a 500 mL three-necked flask and a nitrogen venting device, 5 g of purified silica gel is placed in a three-necked flask. Thereafter, 200 mL of toluene is added to the three-necked flask under nitrogen stream and filled with nitrogen. After stirring for about 20 minutes in this state, 30 mL of dimethylchlorosilane (DMCS) is added and reacted at 150 degreeC for about 24 hours. At the end of the reaction, the reactants are filtered and washed. The solids passed through the above steps are dried in a vacuum dryer for 24 hours, and the dried product is end capped using the silane for endcapping in the same manner as above to complete the final filling.
이 실시예 2 에 의하여 얻어진 충전물, 즉, 상온에서의 실시예 2 에 의하여 제조된 GPC 칼럼과 종래의 상업용 GPC 칼럼의 샘플(PS)과의 비교테스트를 한 결과를 도 1 에 나타내었다. 도 1 에서 종래의 상온용 칼럼에 비해 본 발명으로 제조된상온/고온 겸용 칼럼이 보다 우수한 크로마토그램를 나타냄을 알 수 있다.The result of the comparative test of the packing obtained by Example 2, ie, the sample (PS) of the GPC column manufactured by Example 2 at normal temperature, and the conventional commercial GPC column is shown in FIG. It can be seen from FIG. 1 that the combined normal temperature / high temperature column produced by the present invention shows a better chromatogram compared to the conventional normal temperature column.
또한, 상기 실시예 2 상의 GPC 칼럼과 종래의 GPC 칼럼의 샘플(PE)과의 테스트를 해 본 결과를 도 2 에 나타내었다.In addition, the test results of the GPC column of Example 2 and the sample (PE) of the conventional GPC column is shown in FIG.
도 2 또한 종래의 고온용 칼럼에 비해 본 발명으로 제조된 상온/고온 겸용 칼럼이 보다 우수한 크로마토그램을 나타냄을 알 수 있다.Figure 2 also can be seen that the combination of the normal temperature and high temperature column prepared by the present invention compared to the conventional high temperature column shows a better chromatogram.
이상에서 알 수 있는 바와 같이 본 발명에 의하여 종래의 C18(ODS) 칼럼의 단점을 보완한 신규의 우수한 역상 칼럼을 제조할 수 있을 뿐 아니라, 또한 디메틸클로로실란(DMCS)등을 크기배제 크로마티그래피 칼럼에 이용하므로써 보다 고성능의 상온용 및 고온용을 겸용한 크기배제 칼럼을 제조할 수 있게 되었다.As can be seen from the above, the present invention not only can produce a novel excellent reversed phase column that compensates for the shortcomings of the conventional C 18 (ODS) column, but also dimethylchlorosilane (DMCS) and the like. By using the column, it is possible to manufacture a size exclusion column that combines high performance for room temperature and high temperature.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684630A (en) * | 1979-12-13 | 1981-07-10 | Mitsubishi Chem Ind Ltd | Preparation of filler for liquid gas chromatography |
| JPS6024446A (en) * | 1983-07-20 | 1985-02-07 | Daicel Chem Ind Ltd | Packing agent for separation |
| US5856543A (en) * | 1995-04-15 | 1999-01-05 | Basf Aktiengesellschaft | Silanes comprising branched alkyl chains |
| US5874603A (en) * | 1997-07-15 | 1999-02-23 | Gelest, Inc. | Branched higher alkylsilanes |
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2001
- 2001-09-14 KR KR1020010056760A patent/KR20030023984A/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5684630A (en) * | 1979-12-13 | 1981-07-10 | Mitsubishi Chem Ind Ltd | Preparation of filler for liquid gas chromatography |
| JPS6024446A (en) * | 1983-07-20 | 1985-02-07 | Daicel Chem Ind Ltd | Packing agent for separation |
| US5856543A (en) * | 1995-04-15 | 1999-01-05 | Basf Aktiengesellschaft | Silanes comprising branched alkyl chains |
| US5874603A (en) * | 1997-07-15 | 1999-02-23 | Gelest, Inc. | Branched higher alkylsilanes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030072652A (en) * | 2002-03-06 | 2003-09-19 | 이호재 | Bonding method to induce functional group for ion exchange |
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