CN1847250A - Silane reagent with high reaction activity and its prepn process - Google Patents
Silane reagent with high reaction activity and its prepn process Download PDFInfo
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- CN1847250A CN1847250A CN 200510046255 CN200510046255A CN1847250A CN 1847250 A CN1847250 A CN 1847250A CN 200510046255 CN200510046255 CN 200510046255 CN 200510046255 A CN200510046255 A CN 200510046255A CN 1847250 A CN1847250 A CN 1847250A
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Abstract
The present invention is silane reagent with high reaction activity and its preparation process. The silane reagent has the molecular structure of RMe2SiOSO2CF3, where, R=alkyl(C1,C2,C4,C6,C8 & C18),perfluoroalkyl, & and aryl. It is prepared with trifluoromethyl sulfonic acid and silane chloride or aryl silane as material and through reaction in liquid phase system and under protection of inert gas. The present invention has the features of mild reaction condition, easy control of the reaction process inside liquid phase, high efficiency, fast conversion, less side reactions and easy separation of the product.
Description
Technical field:
The present invention relates to the silica gel chemical modification technique, a kind of silane reagent, its preparation method of high reaction activity are provided especially, and utilize the silane reagent preparation of this high reaction activity to have the technology of the silica gel of high efficiency separation performance.Specifically under mild conditions, under protection of inert gas, in liquid-phase system, adopting trifluoromethane sulfonic acid and chlorinated silane or aryl-silane is raw material, synthesizes the silane reagent of high reaction activity.Under protection of inert gas, under the effect of organic bases, in liquid-phase system, utilize the fluorinated silane reagent of high reaction activity again, synthesize silica gel material fast with high efficiency separation performance.This silica gel material with high efficiency separation performance of institute's synthetic can be used for fine separation fields such as high performance liquid chromatography stationary phase, industrial chromatography.
Background technology:
The silica gel material of chemical modification is widely used in the liquid chromatography isolation technique, and these silica gel materials are commerical prod normally.Yet the development of silica gel chemical modification technique is subjected to the restriction of the material modified reactive behavior of bonding, and current only have several silane reagents with reactive behavior to use, as chlorinated silane and organoalkoxysilane.In silica gel bonded modifying process, when using chlorinated silane and organoalkoxysilane as silane reagent, usually need be than higher temperature of reaction (solvent needs to reflux) and long reaction times (being generally 24h or longer time).
Trimethyl silicone hydride trifluoromethyl sulfonic acid (Trimethylsilyl triflate) is a good silylating reagent, extensive application in Silanization reaction.Compare with the chloro methyl-monosilane that contains same structure and replacement, silicon fluoride alkanisation reagent has higher reactive behavior.Current, these silicon fluoride alkanisation reagent are counted as has one of the most highly active silane reagent, yet in chromatographic field, they still do not have so far and are employed.
Summary of the invention:
The object of the present invention is to provide a kind of silane reagent that can have high reaction activity at synthetic under the mild conditions, provide simultaneously a kind of can be under mild conditions, utilize the silane reagent of this high reaction activity, synthesize the method for silica gel material fast with high efficiency separation performance.
The present invention specifically provides a kind of silane reagent of high reaction activity, has following molecular structure:
RMe
2SiOSO
2CF
3
R=alkyl (C in the formula
1, C
2, C
4, C
6, C
8﹠amp; C
18), perfluoroalkyl ， ﹠amp; Aryl.
The silane reagent of high reaction activity of the present invention is to be raw material with trifluoromethane sulfonic acid and chlorinated silane or aryl-silane, and in liquid-phase system, under the protection of inert gas, reaction obtains.
The present invention also provides the preparation method of the silane reagent of above-mentioned high reaction activity, it is characterized in that: with trifluoromethane sulfonic acid and chlorinated silane or aryl-silane is raw material, in liquid-phase system, reacts under the protection of inert gas.
Among the preparation method of the silane reagent of high reaction activity of the present invention, the reaction conditions of described reaction is reaction pressure 0.05～0.5Mpa, 20～125 ℃ of temperature of reaction; Rare gas element is N
2, among He or the Ar one or more; Liquid-phase system is that nonpolar, low-pole is to the middle polarity organic solvent.
Among the preparation method of the silane reagent of high reaction activity of the present invention, described organic solvent is one or more in methylene dichloride, ethylene dichloride, chloroform, benzene,toluene,xylene, normal hexane, Skellysolve A, the hexanaphthene.
Among the preparation method of the silane reagent of high reaction activity of the present invention, described chlorinated silane or aryl-silane structure are as follows:
RMe
2SiCl or RMe
2SiPh
R=alkyl (C in the formula
1, C
2, C
4, C
6, C
8﹠amp; C
18), perfluoroalkyl ， ﹠amp; Aryl.
Typical reaction process is as follows:
X=H in the formula
By separation, purifying, drying process, obtain pure, high reaction activity silicon fluoride alkanisation reagent.
Silane reagent of high reaction activity of the present invention and preparation method thereof has following characteristics:
1. the reaction conditions gentleness is reflected in the liquid phase and carries out, and process is operated control easily.
2. the efficient height transforms soon, just can thoroughly realize in the following short period of time of mild conditions transforming.
3. the reaction process side reaction is few, and resultant is pure, the separate easily purifying.
Utilize the silane reagent of above-mentioned high reaction activity, the present invention provides a kind of preparation method with silica gel of high efficiency separation performance in addition, it is characterized in that: with silica gel in liquid-phase system, protection of inert gas, and under the effect of organic bases, carry out modification with the fluorinated silane reagent of high reaction activity;
The silane reagent of high reaction activity wherein has following molecular structure:
RMe
2SiOSO
2CF
3
R=alkyl (C in the formula
1, C
2, C
4, C
6, C
8﹠amp; C
18), perfluoroalkyl ， ﹠amp; Aryl.
The present invention has among the preparation method of silica gel of high efficiency separation performance, and rare gas element is N
2, among He or the Ar one or more.
The present invention has among the preparation method of silica gel of high efficiency separation performance, and reaction conditions is reaction pressure 0.05～0.5Mpa, 0～125 ℃ of temperature of reaction.
The present invention has among the preparation method of silica gel of high efficiency separation performance, and organic bases is one or more of pyridine, triethylamine, diethylamine, Trimethylamine 99.
The present invention has among the preparation method of silica gel of high efficiency separation performance, and liquid-phase system can be that nonpolar, low-pole is to the middle polarity organic solvent.Organic solvent is preferably one or more in methylene dichloride, ethylene dichloride, chloroform, benzene,toluene,xylene, normal hexane, Skellysolve A, the hexanaphthene.
The present invention has among the preparation method of silica gel of high efficiency separation performance, shown in the formula composed as follows of silica gel:
Silica)-O-SiMe
2R
R=alkyl (C in the formula
1, C
2, C
4, C
6, C
8﹠amp; C
18), perfluoroalkyl, artl or perfluoroaryl.
Typical reaction process is as follows:
By separation, washing, purifying, drying process, obtain silicon ball material pure, the high efficiency separation performance.
The present invention compares with the C18 silica stationary of chlorinated silane preparation with the C18 silica stationary of fluorinated silane preparation and studies show that, under identical preparation process, take out 1h, 2h, 3h, the 24h silicon ball material of preparation down, be filled in the LC post, utilize the LC method to compare research, discovery is in identical preparation process, and the silica gel material of fluorinated silane preparation is purer than the silica gel material of chlorinated silane preparation, separating effect is higher.
The preparation method that the present invention has the silica gel of high efficiency separation performance has following characteristics:
1. the reaction conditions gentleness is reflected in the liquid phase and carries out, and process is operated control easily.
2. the efficient height transforms soon, just can thoroughly realize in the following short period of time of mild conditions transforming.
3. the reaction process side reaction is few, and resultant is pure, the separate easily purifying.
Embodiment:
Concrete reaction process is as follows: 0.1mol chlorinated silane or aryl-silane and 30mL organic solvent are added respectively in the three-necked bottle, feed exsiccant N
20.1mol trifluoromethane sulfonic acid and 15mL organic solvent are mixed and add in the constant pressure funnel, dropwise be added drop-wise under magnetic agitation in the reaction flask, control reaction temperature is 10～50 ℃, reacts 1h under normal pressure.Reactant detects by NMR and additive method.Final product obtains pure three at last and fluoridizes silane reagent through washing, purifying, vacuum separation, drying.
With 0.01mol silica gel 160 ℃ the time more than the dry 8h, until reaching constant weight.It is added the ground three-necked bottle, it is evenly spread in the organic solvent, feed the exsiccant protection of inert gas, in reaction flask, add exsiccant organic bases (0.01mol) and 50mL anhydrous organic solvent then.0.01mol fluorinated silane reagent and 10mL organic solvent are mixed and adds in the constant pressure funnel, under agitation dropwise be added drop-wise in the reaction flask, control reaction temperature is 0～60 ℃, but reaction 3h complete reaction.Then, the reactant hydrolysis, be cooled to room temperature,, obtain pure anti-phase silicon ball stationary phase at last through washing, drying.
Elaborate the present invention below by example, but this invention not merely is confined to following example.
Embodiment 1:
34.71mL (0.1mole) octadecyl dimethylchlorosilane and 30mL methylene dichloride are added respectively in the three-necked bottle, feed exsiccant N
28.85mL trifluoromethane sulfonic acid (0.1mole) and 15mL toluene are mixed and add in the constant pressure funnel, dropwise be added drop-wise under magnetic agitation in the reaction flask, control reaction temperature is 25 ℃, reacts 1h under normal pressure.Reactant detects by NMR and additive method.Final product obtains pure octadecyl dimethyl trifluoromethane sulfonic acid base silane reagent at last through vacuum separation, drying.
Embodiment 2:
26.05mL (0.1mole) octyl dimethylchlorosilane and 30mL dimethylbenzene are added respectively in the three-necked bottle, feed exsiccant He.10.15mL trifluoromethane sulfonic acid (0.1mole) and 15mL normal hexane are mixed and add in the constant pressure funnel, dropwise be added drop-wise under magnetic agitation in the reaction flask, control reaction temperature is 20 ℃, reacts 1h under 0.2Mpa.Reactant detects by NMR and additive method.Final product obtains pure octyl dimethyl trifluoromethane sulfonic acid base silane reagent at last through purifying, vacuum separation, drying.
Embodiment 3:
17.23mL normal-butyl dimethylchlorosilane (0.1mole) and 30mL ethylene dichloride are added respectively in the three-necked bottle, feed exsiccant N
29.73mL trifluoromethane sulfonic acid (0.1mole) and 15mL chloroform are mixed and add in the constant pressure funnel, dropwise be added drop-wise under magnetic agitation in the reaction flask, control reaction temperature is 40 ℃, reacts 1h under 0.08Mpa.Reactant detects by NMR and additive method.Final product obtains pure normal-butyl dimethyl trifluoromethane sulfonic acid base silane reagent at last through purifying, vacuum separation, drying.
Embodiment 4:
21.2mL dimethyl diphenyl silane (0.1mole) and 30mL methylene dichloride are added respectively in the three-necked bottle, feed exsiccant N
28.85mL trifluoromethane sulfonic acid (0.1mole) and 15mL methylene dichloride are mixed and add in the constant pressure funnel, dropwise be added drop-wise under magnetic agitation in the reaction flask, control reaction temperature is 30 ℃, reacts 1h under normal pressure.Reactant detects by NMR and additive method.Final product obtains pure phenyl dimethyl trifluoromethane sulfonic acid base silane reagent at last through purifying, vacuum separation, drying.
Embodiment 5:
With the ball-type silicon materials of 0.01mol 5um 160 ℃ the time more than the dry 8h, until reaching constant weight.It is added the ground three-necked bottle, it is evenly spread in the 50mL methylene dichloride, feed exsiccant N
2Protection adds exsiccant 1.29mL triethylamine then in reaction flask.The octadecyl dimethyl three of 0.01mol embodiment 1 preparation is fluoridized in sulfonic acid silane reagent and mixing of 10mL methylene dichloride and the adding constant pressure funnel, under agitation dropwise be added drop-wise in the reaction flask, control reaction temperature is 25 ℃, complete reaction behind the reaction 3h under normal pressure.Then, the reactant hydrolysis, be cooled to room temperature,, obtain the anti-phase silicon ball of pure C18 stationary phase at last, fill it in the LC post and estimate through washing, drying.Synthetic materials performance evaluation sees Table 1.
Table 1
| Performance index | Fractions tested | Numerical value |
| Symmetry of peak | Uridylic | 1.89 |
| Oil of mirbane | 1.59 | |
| Naphthalene | 1.35 | |
| Fluorenes | 1.27 | |
| Every meter stage number | Uridylic | 44754 |
| Oil of mirbane | 68025 | |
| Naphthalene | 78899 | |
| Fluorenes | 76619 |
Chromatographic condition: post specification: 5 μ m, 4.6mm * 150mm
Moving phase: methyl alcohol: water=85: 15,0.9mL/min
Detect: UV254nm
Embodiment 6:
With the amorphous silicon material of 0.01mol 5um 160 ℃ the time more than the dry 8h, until reaching constant weight.It is added the ground three-necked bottle, it is evenly spread in the 50mL toluene, feed exsiccant He protection, in reaction flask, add exsiccant 0.7mL Trimethylamine 99 then.The octyl dimethyl three of 0.01mol embodiment 2 preparations is fluoridized in sulfonic acid silane reagent and mixing of 10mL ethylene dichloride and the adding constant pressure funnel, under agitation dropwise be added drop-wise in the reaction flask, control reaction temperature is 20, complete reaction behind the reaction 3h under 0.3Mpa.Then, the reactant hydrolysis, be cooled to room temperature,, obtain the anti-phase silicon ball of pure C8 stationary phase at last, fill it in the LC post and estimate through washing, drying.Synthetic materials performance evaluation sees Table 2.
Table 2
| Performance index | Fractions tested | Numerical value |
| Symmetry of peak | Uridylic | 1.58 |
| Oil of mirbane | 1.30 | |
| Naphthalene | 1.20 | |
| Fluorenes | 1.12 | |
| Every meter stage number | Uridylic | 62376 |
| Oil of mirbane | 94153 | |
| Naphthalene | 93956 | |
| Fluorenes | 91663 |
Chromatographic condition: post specification: 5 μ m, 4.6mm * 150mm
Moving phase: methyl alcohol: water=85: 15,0.9mL/min
Detect: UV254nm
Embodiment 7:
With the ball-type silicon materials of 0.01mol 5um 160 ℃ the time more than the dry 8h, until reaching constant weight.It is added the ground three-necked bottle, it is evenly spread in the 50mL methylene dichloride, feed exsiccant Ar protection, in reaction flask, add exsiccant 1.29mL diethylamine then.The phenyl dimethyl three of 0.01mol embodiment 4 preparations is fluoridized in sulfonic acid silane reagent and mixing of 10mL dimethylbenzene and the adding constant pressure funnel, under agitation dropwise be added drop-wise in the reaction flask, control reaction temperature is 35 ℃, complete reaction behind the reaction 3h under 0.08Mpa.Then, the reactant hydrolysis, be cooled to room temperature,, obtain the anti-phase silicon ball of phenyl stationary phase at last, fill it in the LC post and estimate through washing, drying.Synthetic materials performance evaluation sees Table 3.
Table 3
| Performance index | Fractions tested | Numerical value |
| Symmetry of peak | Uridylic | 1.05 |
| Oil of mirbane | 1.04 | |
| Naphthalene | 0.97 | |
| Fluorenes | 1.03 | |
| Every meter stage number | Uridylic | 86760 |
| Oil of mirbane | 90569 | |
| Naphthalene | 93247 | |
| Fluorenes | 86777 |
Chromatographic condition: post specification: 5 μ m, 4.6mm * 150mm
Moving phase: methyl alcohol: water=85: 15,0.9mL/min
Detect: UV254nm
Claims (6)
1, a kind of silane reagent of high reaction activity has following molecular structure:
RMe
2SiOSO
2CF
3
R=alkyl (C in the formula
1, C
2, C
4, C
6, C
8﹠amp; C
18), perfluoroalkyl ， ﹠amp; Aryl.
2, according to the silane reagent of the described high reaction activity of claim 1, it is characterized in that: described silane reagent is to be raw material with trifluoromethane sulfonic acid and chlorinated silane or aryl-silane, and in liquid-phase system, under the protection of inert gas, reaction obtains.
3, the preparation method of the silane reagent of the described high reaction activity of a kind of claim 1 is characterized in that: with trifluoromethane sulfonic acid and chlorinated silane or aryl-silane is raw material, in liquid-phase system, reacts under the protection of inert gas.
4, according to the preparation method of the silane reagent of the described high reaction activity of claim 3, it is characterized in that: the reaction conditions of described reaction is reaction pressure 0.05～0.5Mpa, 20～125 ℃ of temperature of reaction; Rare gas element is N
2, among He or the Ar one or more; Liquid-phase system is that nonpolar, low-pole is to the middle polarity organic solvent.
5, according to the preparation method of the silane reagent of the described high reaction activity of claim 4, it is characterized in that: described organic solvent is one or more in methylene dichloride, ethylene dichloride, chloroform, benzene,toluene,xylene, normal hexane, Skellysolve A, the hexanaphthene.
6, according to the preparation method of the silane reagent of the described high reaction activity of claim 5, it is characterized in that: described chlorinated silane or aryl-silane structure are as follows:
RMe
2SiCl or RMe
2SiPh
R=alkyl (C in the formula
1, C
2, C
4, C
6, C
8﹠amp; C
18), perfluoroalkyl ， ﹠amp; Aryl.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911196A (en) * | 2012-11-19 | 2013-02-06 | 江西国化实业有限公司 | Preparation method of trifluoromethanesulfonic acid trimethylsilyl ester |
| CN103588803A (en) * | 2013-10-14 | 2014-02-19 | 青岛文创科技有限公司 | Preparation method of trimethylsilyl trifluoromethanesulfonate |
| EP2876110A1 (en) * | 2013-11-22 | 2015-05-27 | Samsung SDI Co., Ltd. | Silane compound, method for preparing the same and polycarbonate resin composition comprising the same |
| CN108373481A (en) * | 2017-11-30 | 2018-08-07 | 江西国化实业有限公司 | A kind of preparation method of Trimethylsilyl trifluoromethanesulfonate |
-
2005
- 2005-04-15 CN CN 200510046255 patent/CN1847250A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911196A (en) * | 2012-11-19 | 2013-02-06 | 江西国化实业有限公司 | Preparation method of trifluoromethanesulfonic acid trimethylsilyl ester |
| CN103588803A (en) * | 2013-10-14 | 2014-02-19 | 青岛文创科技有限公司 | Preparation method of trimethylsilyl trifluoromethanesulfonate |
| EP2876110A1 (en) * | 2013-11-22 | 2015-05-27 | Samsung SDI Co., Ltd. | Silane compound, method for preparing the same and polycarbonate resin composition comprising the same |
| CN104650131A (en) * | 2013-11-22 | 2015-05-27 | 三星Sdi株式会社 | Silane compound, method for preparing the same and polycarbonate resin composition comprising the same |
| CN104650131B (en) * | 2013-11-22 | 2018-05-18 | 乐天尖端材料株式会社 | Silane compound, its preparation method and include its poly carbonate resin composition |
| CN108373481A (en) * | 2017-11-30 | 2018-08-07 | 江西国化实业有限公司 | A kind of preparation method of Trimethylsilyl trifluoromethanesulfonate |
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