CN1133076C - Ether-type bond fixed phase and its preparing process - Google Patents
Ether-type bond fixed phase and its preparing process Download PDFInfo
- Publication number
- CN1133076C CN1133076C CN 01109965 CN01109965A CN1133076C CN 1133076 C CN1133076 C CN 1133076C CN 01109965 CN01109965 CN 01109965 CN 01109965 A CN01109965 A CN 01109965A CN 1133076 C CN1133076 C CN 1133076C
- Authority
- CN
- China
- Prior art keywords
- ether
- stationary phase
- type bond
- preparation
- epoxycyclohexyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention discloses a preparing method of an ether type bonded stationary phase. A silicon coupling agent containing beta-(3, 4-epoxy cyclohexyl) radicals firstly reacts with alkyl alcohol and then is covalently bonded with a particulate carrier containing hydroxy. Since epoxy rings in the beta-(3, 4-epoxy cyclohexyl) radicals are more active than that of common gamma-epoxypropyl oxopropyl radicals, the bonding process of the present invention dose not need a catalyst. Additionally, the reaction process is simple. The stationary phase prepared by the method can be effectively used for the separation of liquid phase chromatographs, particularly the separation of alkaline organic compounds, and separation efficiency is high.
Description
Technical field
The invention belongs to a kind of liquid-phase chromatographic analysis ether-type bond stationary phase and preparation method.
Background technology
Reversed-phase high-performance liquid chromatography now has been widely used in numerous areas such as biology, chemistry, pharmacy, according to statistics, has 80% separation to carry out under rp mode approximately.
About 600 kinds of commercial now reversed-phase high-performance liquid chromatography post, wherein most alkyl chain is from C
2-C
18This can realize the analysis separation requirement to most material.In numerous inverse bonded fillers, having is to be bonded to earlier on the silica gel matrix by middle coupling reagent (as amino, epoxy radicals, thiazolinyl etc.) in a large number, obtains with the acyl chlorides that contains alkyl chain, alcohol or acid reaction again.
The still residual a considerable amount of silanol bases in silica gel surface after modification, this make some polar compound particularly the interaction of alkaline organic compound and residual silicon alcohol radical usually cause the chromatographic peak profile hangover, the peak broadens, even produces irreversible adsorption.In order to address this problem, often to adopt damping fluid be moving phase or separate under higher pH value.But adopt " embedded " polar functional group sometimes or contain the bonding phase of three-dimensional blocking group, the separation that can under better simply moving phase condition, be satisfied with polar compound.
Summary of the invention
The purpose of this invention is to provide a kind of ether-type bond stationary phase and preparation method, this preparation method's process is simple, and material is easy to get, and does not need the para-linkage stationary phase to carry out sealing.
To achieve these goals, after the present invention adopts the silicone couplet contain β-(3, the 4-epoxycyclohexyl) group to react with alkylol again with the particulate carrier covalent bonding of hydroxyl, and obtain the ether-type bond stationary phase, this stationary phase can be represented with following structural formula:
Wherein R is that carbon number is from the individual alkyl of 1-20.
Said fixing mutually in, better composition is that R is a carbon number from 4-18 alkyl.
Above-mentioned its synthetic route of ether-type bond stationary phase provided by the invention is:
Wherein R is a carbon number from 1 to 20 alkyl;
Particulate is the porous that has hydroxyl, withstand voltage, particle that epigranular distributes, can be silica gel, hydroxyapatite or the polymkeric substance of unformed or ball-type;
Used coupling agent is to contain β-(3, the 4-epoxycyclohexyl) single, double or trifunctional compound, can be β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl chlorodimethyl silane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane;
Carbon number in the used alkylol is from 4 to 18;
Organic solvent is benzene,toluene,xylene or dioxane.
Synthesis step is as follows:
1) pre-service of particulate carrier: add hydrochloric acid or salpeter solution in the ratio that adds 20%5ml in the 1g particulate carrier, after the ultrasonic dispersing, backflow 2-8 hour, be dipped to neutrality with double distilled water, in 100～150 ℃ of dryings, obtain the particulate that the surface has even distribution hydroxyl;
2) contain β-(3, the 4-epoxycyclohexyl) silicone couplet of group and alkylol reaction: contain β-(3 by 1ml, the 4-epoxycyclohexyl) ratio of the silicone couplet of group adding 20ml organic solvent places flask, add the organic solution that contains alkylol while stirring, 60-90 ℃ was reacted 4-8 hour under the nitrogen protection, and the cooling of reaction back is standby;
3) preparation of ether-type bond stationary phase: the acid-treated hydroxyl particulate of learning from else's experience; 120-160 ℃ vacuum drying 4-6 hour; under driving, vacuum adds product and the organic solvent that second step made; nitrogen protection; 90-120 ℃ stirring reaction 8-24 hour, filter, use toluene and methanol wash for several times respectively; vacuum drying 6-12 hour, obtain the ether-type bond stationary phase.
Because the space multistory protective effect of cyclohexyl suppresses the interaction of alkaline matter and silicon hydroxyl in the resulting stationary phase of the present invention; the liquid chromatography that therefore can be used for organic compound is effectively separated; particularly to the separation of alkaline organic compound, the ratio of methyl alcohol and water just can satisfy the compartment analysis requirement of sample in the common only need adjusting moving phase.Simultaneously, because the epoxide ring in β-(3, the 4-epoxycyclohexyl) group is more active than the epoxide ring of common γ-glycidyl oxygen propyl group, so bonding process of the present invention does not need catalyzer and course of reaction simple.Compare with traditional inverse bonded stationary phase preparation process, preparation process of the present invention does not need the para-linkage stationary phase to carry out sealing, and end product just can be realized the separation to most materials, its separating effect height under the condition of simple flow phase as methyl alcohol and water.
Description of drawings
Below in conjunction with drawings and Examples the present invention is done further to describe:
Fig. 1 is the chromatogram of embodiment 5;
Fig. 2 is the chromatogram of embodiment 6;
Fig. 3 is the chromatogram of embodiment 7;
Fig. 4 is the chromatogram of embodiment 8.
Embodiment
Embodiment 1: get 3,4 epoxycyclohexyl ethyl trimethoxy silane 3.3ml, toluene 50ml stirs in three-neck flask, logical nitrogen protection.Slowly drip the mixed solution of octanol 4.5ml and toluene 20ml then, 90 ℃ of stirring and refluxing 8 hours, cool drying is preserved stand-by.Get 5g through acid-treated 5 microns silicon balls in reactor, 150 ℃ of vacuum drying 6 hours add above-mentioned intermediate product under vacuum drives; under the nitrogen protection, 120 ℃ of stirring and refluxing 12 hours are filtered; after solids was used toluene and methanol wash, vacuum drying 12 hours got end product.
Embodiment 2: get 3,4 epoxycyclohexyl ethyl chlorodimethyl silane 3.2ml, 40ml dimethylbenzene, the potpourri of 18 pure 5.6ml and 20ml dimethylbenzene, after dripping, 90 ℃ of stirring reactions 4 hours, add the 6.0g hydroxyapatite again, 100 ℃ of vacuum drying 6 hours, 100 ℃ of stirring and refluxing 8 hours, vacuum drying 6 hours.All the other conditions are with embodiment 1.
Embodiment 3: get 4.5ml3,4 epoxycyclohexyl ethyl-methyl dimethoxy silane and 70ml benzene, the mixed solution of Dropwise 5 .6ml butanols and 20ml benzene then, 75 ℃ of stirring and refluxing 6 hours, add the 8g titanium dioxide microballoon sphere again, 120 ℃ of vacuum drying 6 hours, 90 ℃ of stirring and refluxing 24 hours, vacuum drying 8 hours.All the other conditions are with embodiment 1.
Embodiment 4: get 3.3ml3,4 epoxycyclohexyl ethyl trimethoxy silanes and 30ml dioxane, the mixed solution of Dropwise 5 ml tetradecyl alchohol and 20ml dioxane then, 60 ℃ of stirring reactions 4 hours, add the unformed silica gel of 5g again, 160 ℃ of vacuum drying 4 hours, 110 ℃ were refluxed vacuum drying 10 hours 12 hours.The remaining reaction condition is with embodiment 1.
Embodiment 5, the stationary phase of using embodiment 1 to prepare, the filling of homogenate method is in 150mm, and in the stainless steel column of internal diameter 4.6mm, the gained chromatographic column is used for the sample separation potpourri.Fig. 1 is for estimating C
8The normal aromatic hydrocarbons mixture that adopts of stationary phase, the i.e. chromatogram of 1 uracil, 2 nitrobenzene, 3 naphthalenes, 4 acenaphthenes.Chromatographic condition is as follows: mobile phase methanol is 65 to 35 with the volume ratio of water, flow velocity 0.8ml/min, and 25 ℃ of column temperatures detect wavelength 254nm.
Embodiment 6, the chromatographic column of using embodiment 5 to prepare have been separated 1 benzene, 2 naphthalenes, 3 biphenyl, 4 luxuriant and rich with fragrance potpourris, and Fig. 2 is its chromatogram, and its chromatographic condition is with embodiment 5.
Embodiment 7, with the chromatographic column of embodiment 5 preparation, separated several alkaline mixts, i.e. 1 aminophylline, 2 pyridine procaines, 3 N, N-diethylaniline, 4 papaverines, chromatogram result such as Fig. 3, its chromatographic condition is with embodiment 5.
Embodiment 8, the chromatographic column of using embodiment 5 to prepare, separated neutral, acid and alkaline organic mixture, i.e. 1 aminophylline, 2 phenol, 3 para-totuidine, 4 toluene, 5 ethylbenzene, Fig. 4 is its chromatogram, mobile phase methanol is 55 to 45 with the volume ratio of water, and all the other conditions are with embodiment 5.
Preparation process of the present invention is simple, need not sealing, and raw material is easy to get, and end product is good reproducibility in batches, and stability is higher, and resulting stationary phase can be used for the liquid chromatography of organic compound effectively and separate, and wherein alkali compounds is had separating effect preferably.
Claims (9)
1, a kind of ether-type bond stationary phase is characterized in that, closes with the particulate carrier covalency of hydroxyl after adopting the silicone couplet contain β-(3, the 4-epoxycyclohexyl) group to react with alkylol to obtain again, and structure is:
Wherein R is a carbon number from 1 to 20 alkyl.
2, a kind of ether-type bond stationary phase according to claim 1 is characterized in that R is that carbon number is from the individual alkyl of 4-18.
3, a kind of preparation method of ether-type bond stationary phase, synthesis step is as follows:
1) pre-service of particulate carrier: add hydrochloric acid and salpeter solution in the ratio that adds 20%5ml in the 1g particulate carrier, after the ultrasonic dispersing, backflow 2-8 hour, be dipped to neutrality with double distilled water, in 100-150 ℃ of drying, obtain the particulate that the surface has even distribution hydroxyl;
2) contain β-(3, the 4-epoxycyclohexyl) silicone couplet of group and alkylol reaction: contain β-(3 by 1ml, the 4-epoxycyclohexyl) ratio of the silicone couplet of group adding 20ml organic solvent places flask, add the organic solvent that contains alkylol while stirring, 60-90 ℃ was reacted 4-8 hour under the nitrogen protection, and the cooling of reaction back is standby;
3) preparation of ether-type bond stationary phase: the acid-treated hydroxyl particulate of learning from else's experience; 120-160 ℃ vacuum drying 4-6 hour; under driving, vacuum adds product and the organic solvent that second step made; nitrogen protection; 90-120 ℃ stirring reaction 8-24 hour, filter, use toluene and methanol wash for several times respectively; vacuum drying 6-12 hour, obtain the ether-type bond stationary phase.
4, the preparation method of a kind of ether-type bond stationary phase according to claim 3 is characterized in that described particulate is silica gel, the hydroxyapatite of unformed or ball-type or the polymkeric substance that contains hydroxyl.
5, the preparation method of a kind of ether-type bond stationary phase according to claim 4 is characterized in that described particulate is a silica gel.
6, the preparation method of a kind of ether-type bond stationary phase according to claim 3 is characterized in that described coupling agent is for containing the single, double or trifunctional compound of β-(3, the 4-epoxycyclohexyl).
7, the preparation method of a kind of ether-type bond stationary phase according to claim 6, it is characterized in that described coupling agent is β-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl chlorodimethyl silane or β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane.
8, the preparation method of a kind of ether-type bond stationary phase according to claim 3 is characterized in that described organic solvent is benzene,toluene,xylene or dioxane.
9, the preparation method of a kind of ether-type bond stationary phase according to claim 3 is characterized in that the carbon number in the described used alkylol is 4-18.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01109965 CN1133076C (en) | 2001-03-28 | 2001-03-28 | Ether-type bond fixed phase and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01109965 CN1133076C (en) | 2001-03-28 | 2001-03-28 | Ether-type bond fixed phase and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1376921A CN1376921A (en) | 2002-10-30 |
| CN1133076C true CN1133076C (en) | 2003-12-31 |
Family
ID=4658248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01109965 Expired - Fee Related CN1133076C (en) | 2001-03-28 | 2001-03-28 | Ether-type bond fixed phase and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1133076C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9216403B2 (en) * | 2013-03-15 | 2015-12-22 | Dionex Corporation | Epoxy chemistry derived materials as reversed-phase and hydrophobic interaction chromatography media, method for their synthesis and use |
-
2001
- 2001-03-28 CN CN 01109965 patent/CN1133076C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1376921A (en) | 2002-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kirkland et al. | Synthesis and characterization of highly stable bonded phases for high-performance liquid chromatography column packings | |
| CA1316523C (en) | Liquid chromatography dual zone packing materials and method for making and using same | |
| US7919422B2 (en) | Chiral bisoxazoline catalysts | |
| CN101045201A (en) | Method for preparing liquid phase chromatographic filling of imidazole bond linking silica gel | |
| US20070090052A1 (en) | Chromatographic stationary phase | |
| US20120125843A1 (en) | Methods and materials for performing hydrophobic interaction chromatography | |
| CN102489271A (en) | Preparation method of alkali-resistant silica gel chromatographic column filling material | |
| CN104549183B (en) | Silica gel chromatographic column filling material and preparation method thereof | |
| CN101234337A (en) | Silica matrix chromatogram packing | |
| US9925515B1 (en) | Alkyl functionalized porous silica liquid chromatographic stationary phases and solid phase extraction sorbents | |
| CN1133076C (en) | Ether-type bond fixed phase and its preparing process | |
| CN115178245A (en) | Preparation method and application of organic-inorganic hybrid silica gel particles | |
| US5576453A (en) | Stable, sterically-protected, bonded phase silicas prepared from bifunctional silanes | |
| CN1125337C (en) | Ammonia-type inverse bonded stationary phase and its prepn | |
| CN1152257C (en) | Ester-type reverse bonded fixed phase and its preparing process | |
| US20050187400A1 (en) | Polypodal silanes with embedded hydrophilicity | |
| CN1220055C (en) | Alkyl silica gel bonded chromatographic fixed phase and its prepn process | |
| US7534352B2 (en) | Reversed endcapping and bonding of chromatographic stationary phases using hydrosilanes | |
| EP0186133B1 (en) | Optical resolution of oxycyclopentenone | |
| CN111250069B (en) | Silica gel chromatographic packing and preparation method and application thereof | |
| CN1125336C (en) | Prepn of efficient liquid-phase chromatographic amide bonded stationary phase | |
| CN1110702C (en) | Alkylamine linked chromatographic fixing phase and its preparing process | |
| CN101270187B (en) | Preparation for organotin functionalization periodic mesoporous organosilicon | |
| CN102974329B (en) | Preparation method of sterol-based chromatographic stationary phase | |
| CN1057607C (en) | Double functional chromatographic material and preparing method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |