CN101293962B - Aryl hybridisation silica gel and uses thereof - Google Patents

Aryl hybridisation silica gel and uses thereof Download PDF

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CN101293962B
CN101293962B CN2008100390948A CN200810039094A CN101293962B CN 101293962 B CN101293962 B CN 101293962B CN 2008100390948 A CN2008100390948 A CN 2008100390948A CN 200810039094 A CN200810039094 A CN 200810039094A CN 101293962 B CN101293962 B CN 101293962B
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silica gel
aryl
formula
phenyl
hybridization
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CN101293962A (en
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梁鑫淼
张永平
柯燕雄
金郁
余丹华
俞晖
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East China University of Science and Technology
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Abstract

The invention relates to an aromatic hybrid silica gel and the application thereof. The aromatic hybrid silica gel is polymerized from aromatic silicane, silicate ester, template agents and alkali by the sol-gel process. The aromatic hybrid silica gel can be used as a matrix material for stationary phase of liquid chromatography after pore-enlarging treatment and has good resistance to pressure and acids or alkalis, etc.

Description

Aryl hybridisation silica gel and uses thereof
Technical field
The present invention relates to a kind of aryl hybridisation silica gel and uses thereof.
Background technology
Mostly existing commonly used liquid chromatography silica filler is the high-purity silica gel that tetraethoxysilane or silicate are polymerized, and has the problem of moving phase pH value range of application little (the pH value is 2～8) and chemically unstable in chromatographic applications with this class silica gel chromatographic stationary that is matrix more.Use this class stationary phase and some special compounds such as alkalescence or acidic cpd are being carried out liquid-phase chromatographic analysis when separating, if the pH value of moving phase is not regulated, the chromatographic peak of these compounds has conditions of streaking more, but the pH value is too small or spend the life-span that metropolitan influences liquid-phase chromatographic column, and therefore how to address these problems is emphasis and the difficult point that chromatographic stationary is studied mutually always.
The development of hybridisation silica gel and application are from having solved this problem to a great extent.Hybridisation silica gel is meant in the silica gel forming process, has two kinds or two or more silane monomers to participate in the silica gel spheroidal particle that polyreaction forms.
Document (Vivian Rebbin, Rainer Schmidt, and Michael Froba.Angew.Chem.Int.Ed.2006,45,5210-5214) reported a kind of phenyl hybridization silica gel and the application aspect liquid chromatography stuffing thereof.Though the existing phenyl hybridization silica gel that is used for liquid chromatography stuffing has good performance, and room for improvement is still arranged.
Summary of the invention
The objective of the invention is to, a kind of novel aryl hybridisation silica gel and uses thereof is provided.
The said aryl hybridisation silica gel of the present invention, it is mainly made through the sol-gel method polymerization by aryl-silane, silicon ester, template and alkali, it is characterized in that, and wherein said aryl-silane is a compound shown in the formula I:
Figure S2008100390948D00011
Among the formula I: Ar is C 5～C 10Aromatic ring yl, R 1And R 2Independently be selected from methyl or the ethyl respectively a kind of, and (R 2O) 3Si-and-Si (OR 1) 3Position or contraposition each other;
Said silicon ester has structure shown in the formula II:
Figure S2008100390948D00012
Among the formula II: R 3And R 4Independently be selected from methyl or the ethyl a kind of respectively;
Said template is: C 12～C 20Quaternary ammonium salt shown in Armeen or the formula III, or they the two mixture;
Figure S2008100390948D00021
In the formula III: R 5, R 6, R 7And R 8Independently be selected from C respectively 1～C 20A kind of in the alkyl, and R 5, R 6, R 7And R 8In have one at least for C 12～C 20Alkyl; X is halogen (F, Cl, Br or I);
Said alkali is ammoniacal liquor or sodium hydroxide.
In optimal technical scheme of the present invention, Ar is C 5～C 7Aromatic ring yl; Preferred Ar is a group shown in formula IV or the formula V
Figure S2008100390948D00022
The substituent replacement of curve representation among formula IV and formula V position.
In another optimal technical scheme of the present invention, R 1And R 2Identical.
In another optimal technical scheme of the present invention, used silicon ester is methyl silicate or tetraethyl silicate.
Above-mentioned aryl hybridisation silica gel can be used as liquid chromatography stationary phase substrate material after reaming is handled.
Description of drawings
Fig. 1 is scanning electron microscope (SEM) figure by embodiment 1,5,6 and 7 obtained hybridisation silica gels;
Wherein A-embodiment 1, B-embodiment 5, C-embodiment 6, D-embodiment 7;
Fig. 2 is to use embodiment 1 prepared phenyl hybridization spherical silica gel that benzene, naphthalene, luxuriant and rich with fragrance chromatogram are kept design sketch;
Fig. 3 is to use embodiment 6 prepared phenyl hybridization spherical silica gels that benzene, naphthalene, luxuriant and rich with fragrance chromatogram are kept design sketch.
Embodiment
With Ar is that phenylene (suc as formula the group shown in IV or the formula V) is example, and the key step for preparing aryl hybridisation silica gel of the present invention is:
In methyl alcohol or aqueous ethanolic solution [alcohol is 1 with the volume ratio of water: (0.2～5)], add template, alkali, phenyl silane and silicon ester, under 15 ℃～65 ℃ conditions, reacted 1～24 hour, filter, solids gets target compound after washing with alcohol and vacuum-drying.
Wherein: the concentration range of the total amount of aryl-silane monomer and silicon ester in solvent is (0.5～5.0mmol/mL); The mol ratio of aryl-silane monomer, silicon ester, alkali and template is: 1: (0.01～100): (0.0001～0.005): (0.1～0.5).
Is 1 with the above-mentioned phenyl hybridization silica gel that makes, water and expanding agent by mass ratio: (5～50): mix (0.2～2), thermal response more than 100 ℃ 72 hours, filter, the gained solids is 1 with 1% methanol hydrochloride solution by mass ratio: mix (5～50), refluxed about 24 hours, must be through the phenyl hybridization silica gel of reaming processing, it can be used as liquid chromatography stationary phase substrate material.
Wherein said expanding agent is N, N-dimethyl amino dodecane, N, N-dimethyl ten amine, N, N-dimethyl tetradecy lamine, N, N-dimethyl cetylamine or N, existing expanding agent such as Dymanthine.
The present invention has following advantage:
1, has very high stability.The chromatography matrix parting material that obtains has very high withstand voltage and anti-pH performance, both can directly be used for hydrophilic post as chromatograph packing material, also can be used for key function molecular matrix material.
2, the spheroidal particle particle diameter is even.The spheroidal particle particle diameter that utilizes aforesaid method to obtain is very even, need not carry out particle screen selecting more substantially and just can directly utilize.
3, having of aryl is beneficial to the separation performance that strengthens the reverse-phase chromatography stationary phase.Owing in silica gel, there is a lot of aromatic rings, strengthened hydrophobic interaction power and π-π reactive force like this, will improve a lot to separation performance like this as the reverse-phase chromatography stationary phase.
4, preparation process is simple, can obtain the spheroidal particle of different-grain diameter by the ratio that changes silane reagent, helps realizing commercialization.Present method obtains the phenyl hybridization silica gel spheroidal particle of different-grain diameter size easily, so just can satisfy the requirement of different chromatographic grade stationary phase, also is beneficial to and satisfies commercial needs.
The invention will be further described below in conjunction with embodiment, and its purpose only is better to understand content of the present invention.Should be appreciated that the cited case does not limit protection scope of the present invention.
Embodiment 1
(1) in the 2000mL there-necked flask, adds 500mL dehydrated alcohol and 500mL distilled water, add 8.0g tetradecy lamine and 1.0g cetyl trimethylammonium bromide in the whipping process, add ammoniacal liquor 2.0mL again, add (0.01mol, 4.0g) 1 then, two (ethyl-silicone) benzene (BTEB) of 4-and (0.08mol, 20.8g) ethyl silicate, 40 ℃ of reaction 3h filter, use washing with alcohol, vacuum-drying.
(2) solid and the 8g N that 10g is obtained by step (1), N-dimethyl amino dodecane, 200mL distilled water join in the 1L reactor, 130 ℃ of reaction 96h, with the solid transfer after filtering in the 200mL1% ethanol solution hydrochloride, backflow 24h, filter, use the 500mL washing with alcohol, vacuum-drying 12 hours.Utilize scanning electron microscope analysis (the results are shown in Figure 1A), recording size is 1.5 μ m.
Embodiment 2
In embodiment 1 step (1), adopt 1, two (ethyl-silicone) benzene of 3-replace 1 among the embodiment 1, two (ethyl-silicone) benzene of 4-, other step of press embodiment 1 is operated, can with the different spheroidal particle of structure among the embodiment 1.
Embodiment 3
In embodiment 1 step (1), adopt 1, two (methoxyl group the is silica-based) benzene of 4-replace 1 among the embodiment 1, two (ethyl-silicone) benzene of 4-, other step of press embodiment 1 is operated, can with the different spheroidal particle of structure among the embodiment 1.
Embodiment 4
In embodiment 1 step (1), adopt methyl silicate to replace tetraethyl silicate among the embodiment 1, other step of press embodiment 1 is operated, can with the identical spheroidal particle of structure among the embodiment 1.
Embodiment 5
In embodiment 1 step, adopt (0.018mol, 7.2g) BTEB and (0.072mol, 18.7g) ethyl silicate, other presses the step operation of embodiment 1, and can get size is 2.0 μ m phenyl hybridization silica gel spheroidal particle, utilizes scanning electron microscope analysis (the results are shown in Figure 1B).
Embodiment 6
In embodiment 1 step (1), (0.03mol, 12.0g) BTEB is with (other presses step operation of embodiment 1 for 0.06mol, 15.6g) ethyl silicate, and can get size is 3.0 μ m phenyl hybridization silica gel spheroidal particle in employing.Utilize scanning electron microscope analysis (the results are shown in Figure 1C).
Embodiment 7
In embodiment 1 step (1), (0.045mol, 18.0g) BTEB is with (other presses step operation of embodiment 1 for 0.045mol, 11.7g) ethyl silicate, and can get size is 3.5 μ m phenyl hybridization silica gel spheroidal particle in employing.Utilize scanning electron microscope analysis (the results are shown in Figure 1D).
Embodiment 8
In embodiment 1 step (1), dehydrated alcohol is changed into anhydrous methanol,, other step all by embodiment 1 operation, also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 9
In embodiment 1 step (1), with 500mL dehydrated alcohol and the 500mL distilled water in 167mL dehydrated alcohol and 833mL distilled water or 833mL dehydrated alcohol and 167mL distilled water replacement embodiment 1 step (1), other step all by embodiment 1 operation, also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 10
In embodiment 1 step (1), adopt 8.0g tetradecy lamine and 1.0g cetyl trimethylammonium bromide in 9.0g tetradecy lamine or the 9.0g cetyl trimethylammonium bromide alternative embodiment 1, the step operation that other presses embodiment 1 also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 11
In embodiment 1 step (1), adopt tetradecy lamine in amino dodecane (or cetylamine, stearylamine, the 20 amine etc.) alternative embodiment 1, other step of press embodiment 1 is operated, and also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 12
In embodiment 1 step (1), adopt cetyl trimethylammonium bromide in Trimethyllaurylammonium bromide (or Tetradecyl Trimethyl Ammonium Bromide, octadecyl trimethylammonium bromide, the eicosyl trimethylammonium bromide etc.) alternative embodiment 1, the step operation that other presses embodiment 1 also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 13
In embodiment 1 step (1), adopt N, N-dimethyl amino dodecane, N, N-dimethyl tetradecy lamine, N, N-dimethyl cetylamine, N, tetradecy lamine in the alternative embodiments such as Dymanthine 1, the step operation that other presses embodiment 1 also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 14
In embodiment 1 step (1), (the 1.0mL ammoniacal liquor in the alternative embodiment 1, the step operation that other presses embodiment 1 also can get the phenyl hybridization spherical silica gel among the embodiment 1 to adopt 1.0mL1%NaOH solution.
Embodiment 15
In embodiment 1 step (1), 15 ℃, 35 ℃ or 65 ℃ replace among the embodiment 1 25 ℃ of temperature of reaction, and other step of press embodiment 1 is operated, and also can get the identical spheroidal particle of structure among the embodiment 1.
Embodiment 16
In embodiment 1 step (2), adopt N, N-dimethyl tetradecy lamine (or N, N-dimethyl cetylamine, N, Dymanthine, N, N-dimethyl 20 ammoniums) N in the alternative embodiment 1, N-dimethyl amino dodecane, the step operation that other presses embodiment 1 also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 17
In embodiment 1 step (2), adopt in 80 ℃, 150 ℃, the 200 ℃ alternative embodiments 1 130 ℃, step operation that other presses embodiment 1 also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 18
In embodiment 1 step (2), adopt 96h in 24h, 48h, 120h, the 240h alternative embodiment 1, the step operation that other presses embodiment 1 also can get the phenyl hybridization spherical silica gel among the embodiment 1.
Embodiment 19
Use the prepared phenyl hybridization spherical silica gel of embodiment 2, load 2.1*50mm stainless steel chromatogram post with the homogenate method, under the reverse-phase chromatography pattern with benzene, naphthalene and luxuriant and rich with fragrance biased sample test.As moving phase, the chromatogram of three kinds of compounds keeps (as shown in Figure 2) with acetonitrile/water.
Fig. 2 is the chromatogram reservation design sketch to three kinds of compounds.Used chromatographic condition is: moving phase acetonitrile/water=40: 60, flow velocity: 0.2ml/min; Column temperature: 35 ℃; Detect wavelength: 254nm.
Embodiment 20
Use the prepared phenyl hybridization spherical silica gel of embodiment 5, load 2.1*50mm stainless steel chromatogram post with the homogenate method, under the reverse-phase chromatography pattern with benzene, naphthalene and luxuriant and rich with fragrance biased sample test.As moving phase, the chromatogram of three kinds of compounds keeps (as shown in Figure 3) with acetonitrile/water.
Fig. 3 is the chromatogram reservation design sketch to three kinds of compounds.Used chromatographic condition is: moving phase acetonitrile/water=35: 65, flow velocity: 0.2ml/min; Column temperature: 35 ℃; Detect wavelength: 254nm.

Claims (4)

1. aryl hybridisation silica gel, it is mainly made through the sol-gel method polymerization by aryl-silane, silicon ester, template and alkali, it is characterized in that, and wherein said aryl-silane is a compound shown in the formula I; Said silicon ester has structure shown in the formula II; Said template is: C 12～C 20Quaternary ammonium salt shown in Armeen or the formula III, or they the two mixture; Said alkali is ammoniacal liquor or sodium hydroxide;
Figure FSB00000318698800011
Wherein: Ar is a group shown in formula IV or the formula V, R 1And R 2Independently be selected from methyl or the ethyl respectively a kind of, and (R 2O) 3Si-and-Si (OR 1) 3Position or contraposition each other; R 3And R 4Independently be selected from methyl or the ethyl a kind of respectively; R 5, R 6, R 7And R 8Independently be selected from C respectively 1～C 20A kind of in the alkyl, and R 5, R 6, R 7And R 8In have one at least for C 12～C 20Alkyl; X is a halogen;
The substituent replacement of curve representation among formula IV and formula V position.
2. aryl hybridisation silica gel as claimed in claim 1 is characterized in that, wherein R 1And R 2Identical.
3. aryl hybridisation silica gel as claimed in claim 2 is characterized in that, wherein used silicon ester is methyl silicate or tetraethyl silicate.
4. as the application of any described aryl hybridisation silica gel in preparative liquid chromatography stationary phase substrate material in the claim 1～3.
CN2008100390948A 2008-06-18 2008-06-18 Aryl hybridisation silica gel and uses thereof Expired - Fee Related CN101293962B (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6417236B1 (en) * 2000-06-02 2002-07-09 The United States Of America As Represented By The Secretary Of The Army Active topical skin protectants using hybrid organic polysilsesquioxane materials
US6559070B1 (en) * 2000-04-11 2003-05-06 Applied Materials, Inc. Mesoporous silica films with mobile ion gettering and accelerated processing
WO2003055452A1 (en) * 2001-03-30 2003-07-10 University Of California Hybrid organic-inorganic adsorbents
CN1532201A (en) * 2003-03-18 2004-09-29 中国科学院大连化学物理研究所 Process for preparing high specific surface area hetero phenyl silica-gel
WO2005087369A1 (en) * 2004-03-16 2005-09-22 The Governing Council Of The University Of Toronto Hybrid porous organic-metal oxide materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6559070B1 (en) * 2000-04-11 2003-05-06 Applied Materials, Inc. Mesoporous silica films with mobile ion gettering and accelerated processing
US6417236B1 (en) * 2000-06-02 2002-07-09 The United States Of America As Represented By The Secretary Of The Army Active topical skin protectants using hybrid organic polysilsesquioxane materials
WO2003055452A1 (en) * 2001-03-30 2003-07-10 University Of California Hybrid organic-inorganic adsorbents
CN1532201A (en) * 2003-03-18 2004-09-29 中国科学院大连化学物理研究所 Process for preparing high specific surface area hetero phenyl silica-gel
WO2005087369A1 (en) * 2004-03-16 2005-09-22 The Governing Council Of The University Of Toronto Hybrid porous organic-metal oxide materials

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