WO2012055320A1 - 氮氧化硅色谱固定相材料及其制备和应用 - Google Patents

氮氧化硅色谱固定相材料及其制备和应用 Download PDF

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WO2012055320A1
WO2012055320A1 PCT/CN2011/080687 CN2011080687W WO2012055320A1 WO 2012055320 A1 WO2012055320 A1 WO 2012055320A1 CN 2011080687 W CN2011080687 W CN 2011080687W WO 2012055320 A1 WO2012055320 A1 WO 2012055320A1
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silicon oxynitride
stationary phase
group
phase material
alkyl
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French (fr)
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梁鑫淼
万慧慧
薛兴亚
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority claimed from CN201010521325.6A external-priority patent/CN102451667B/zh
Priority claimed from CN201110286467.3A external-priority patent/CN103007904B/zh
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Definitions

  • Silicon oxynitride chromatographic stationary phase material Silicon oxynitride chromatographic stationary phase material and its preparation and application
  • the invention relates to a silicon oxynitride chromatographic stationary phase material and a preparation method and application thereof.
  • the silicon nitride material is nitrided by ammonia gas to prepare a silicon oxynitride material, and a preparation method of a silicon oxynitride chromatographic stationary phase material and its application in separation analysis and solid phase extraction are further provided;
  • the silicon amino group on the surface of the silicon oxide reacts with the surface bonding modifying reagent having different functional groups to provide a method for preparing surface modification bonding of the silicon oxynitride chromatographic stationary phase material and its application in separation analysis, solid phase extraction and the like.
  • HPLC high performance liquid chromatography
  • column packing is essential for chromatographic separation and is the basis for the establishment and development of various HPLC separation modes, and is the key to effective separation.
  • the chromatographic separation performance is closely related to the physicochemical properties of the chromatographic packing. Due to its good mechanical strength, good thermal and chemical stability, and easy to control physical properties (such as pore structure, pore size, specific surface area), the silica gel matrix is a An ideal chromatographic stationary phase material. The most important thing is that the surface of the silica gel is rich in silanol groups, which is easy to be surface chemically modified and is an ideal matrix material for various chemically bonded phases.
  • silica gel fillers have two difficult problems in chromatographic applications [Kirkland, JJ et al. J. Chromatogr. A 1997, 762, 97-1 12.]: (1) Silica gel fillers can be used in chromatography applications.
  • pH > 8 the silica matrix is unstable and easily soluble; when pH ⁇ 2, the surface bonding groups are easily hydrolyzed and lost.
  • pH ⁇ 2 the surface bonding groups are easily hydrolyzed and lost.
  • a certain amount of silanol groups remain on the surface of the alkylated silica gel, which is prone to irreversible adsorption of highly polar substances such as N-containing compounds, resulting in separation of polar analytes in reversed-phase mode. The chromatographic peak is severely tailed off and even the dead adsorption of the analyte.
  • Organic polymer polymers such as organic polymer polymers, graphitized carbon and metal oxides (such as zirconium dioxide, titanium dioxide and aluminum oxide).
  • Organic polymer fillers have good pH chemical stability, but such chromatographic fillers have poor mechanical strength and are easily swelled in organic solvents, making gradient elution difficult, which greatly limits the application range of such materials.
  • Graphitized carbon materials have good mechanical strength and chemical stability. In recent years, they have been used as chromatographic fillers in the separation of highly polar compounds. Because of their difficult surface modification, they are mainly used as a matrix for reversed-phase chromatography mode packing. Moreover, long-term use of the surface may cause heterogeneity, which may lead to non-specific adsorption.
  • Oxygens have attracted widespread attention due to their unique surface properties and good chemical stability.
  • oxides used as chromatographic fillers are mainly zirconium dioxide, titanium dioxide and aluminum oxide.
  • Lewis acid, alkali action sites and anion exchange, cation exchange and ligand exchange centers on the surface of metal oxides Due to the variety of surface forces and complex forces, various modes of action often coexist in the separation process, and the separation mechanism is complicated.
  • the chromatographic behavior of the surface is more difficult to predict than the silica matrix.
  • the silicon oxynitride material is prepared by nitriding silicon oxide with ammonia gas at a high temperature; the prepared silicon oxynitride microparticle material not only has good mechanical strength, porous structure, large specific surface area, and good surface of the silica gel matrix. Chemical stability and thermal stability; and there are abundant Si-NH 2 and Si-NH-Si on the surface of the material, through modification reagents with reactive groups containing epoxy groups, acid chlorides, aldehyde groups, halogens, etc.
  • silylating reagents, etc. can be modified to a hydrophilic or hydrophobic surface.
  • the silicon oxynitride substrate and its surface-modified material can be used as a reverse phase, normal phase, hydrophilic or ion exchange chromatography stationary phase, solid phase. Use of extraction materials or solid phase microextraction materials.
  • Preparation process using silicon oxide particles as raw materials, by using nitriding reaction of ammonia gas with silicon oxide material at high temperature to obtain silicon oxynitride material, using reactive groups containing epoxy groups, acid chlorides, aldehyde groups, halogens, etc.
  • the surface of the silicon oxynitride material is modified by a reagent or a silylation reagent, and a surface modification bonded modified silicon oxynitride chromatographic stationary phase material is further prepared.
  • the preparation process comprises the following steps: (1) passing the silicon oxide material with ammonia gas Nitriding treatment in a high temperature furnace to obtain a silicon oxynitride material;
  • the shape of the silicon oxide stationary phase material particles may be spherical and amorphous.
  • the spherical particle size of the silica stationary phase material is from 0.5 to 200 ⁇ m.
  • the high temperature nitriding treatment gas is ammonia gas.
  • the flow rate of the ammonia gas during the high temperature nitriding treatment in the preparation method of the above nitrogen oxynitride chromatographic stationary phase material is
  • a nitrous oxide chromatographic stationary phase material having a nitrogen content of 0.1-40% by mass can be obtained by controlling the ammonia gas flow rate, the nitriding temperature and the nitriding time.
  • the surface modification bonding modification reagent Z a (R') b Si-R described in the modification reagent may be dC alkyl group, aromatic group or alkyl cyanide.
  • a base an alkylamino group, an alkyl diol group, an alkyl nitro group, an anion/cation exchange group, and an alkyl group or an aromatic group having a polar group.
  • the organic solvent is dichloromethane, methanol, ethanol, toluene, xylene, ethyl acetate or tetrahydrofuran, and the organic solvent contains or not
  • the content of the pyridine and/or triethylamine, pyridine and/or triethylamine in an organic solvent is 0-100%; the amount of the modifying reagent is 1-5 mmol per gram of the silicon oxynitride material, the organic solvent The amount added is 30-60 mL per gram of silicon oxynitride material.
  • the content of nitrogen element in the obtained silicon oxynitride material can be obtained by elemental analysis.
  • the silicon oxynitride microparticle material can be directly used as a chromatographic stationary phase, and can be oxidized by reacting a surface silicon amino group with a modifying reagent containing a reactive group such as an epoxy group, an acid chloride, an aldehyde group or a halogen, or a silylating agent.
  • the surface modification of the silicon material is modified to a hydrophobic, hydrophilic surface, and the modified silicon oxynitride material can be used as a stationary phase for reverse phase, normal phase, hydrophilic or ion exchange chromatography.
  • Applications of silicon oxynitride chromatography stationary phase materials are high performance liquid chromatography stationary phase materials, industrial chromatography stationary phase materials, solid phase extraction materials and solid phase microextraction materials.
  • the preparation process is simple, the industrial production cost is low, and it is beneficial to realize commercial application.
  • the method for preparing a silicon oxynitride chromatographic stationary phase material provided by the invention is simple and convenient, and only needs to be replaced by a simple gas-solid phase nitridation reaction between ammonia gas and a silicon oxide material at a high temperature to obtain a silicon amino group on the surface.
  • a silicon oxynitride chromatographic stationary phase material is simple and convenient, and only needs to be replaced by a simple gas-solid phase nitridation reaction between ammonia gas and a silicon oxide material at a high temperature to obtain a silicon amino group on the surface.
  • Nitriding substitution reaction efficiency is high, and the nitrogen content of the silicon oxynitride chromatographic stationary phase material can be controlled.
  • the nitridation substitution reaction between the ammonia gas and the silicon oxide material is high, and the ammonia gas can not only react with the silanol group to replace the silanol group with the silanol group, but also react with the oxygen in the Si-0-Si bond to form Si- NH-Si bond.
  • a silicon oxynitride chromatographic stationary phase material with a nitrogen content of 0.1-40% can be prepared.
  • the present invention prepares a silicon oxynitride chromatographic stationary phase material by a nitridation substitution reaction between ammonia gas at a high temperature and a hydroxyl group and a Si-0-Si group in a silicon oxide material, which not only maintains the silicon oxide well.
  • the morphology of the material and can maintain the pore structure and surface area of the silica material.
  • the silicon oxynitride prepared by the invention not only has the advantages of good mechanical strength, porous structure, large specific surface area, thermal stability and the like of the silica gel material; but also has abundant silicon amino groups on the surface of the material.
  • the silicon oxynitride material prepared by the invention has abundant silicon amino groups on the surface, and the surface of the material can be further modified into a hydrophilic and hydrophobic surface by reacting a modifying agent with a silicon amino group, and the silicon oxynitride material and Surface-modified materials can be used not only as reverse phase, normal phase, hydrophilic or ion exchange chromatography stationary phases, but also as industrial chromatographic stationary phase materials, solid phase extraction materials and solid phase microextraction materials.
  • the silicon oxynitride matrix and its surface-modified material are used as reverse phase, normal phase, hydrophilic or ion exchange chromatography stationary phases, there is no obvious loss of surface groups, which is easy to be combined with mass spectrometry, which can effectively meet modern life sciences. , environmental science and pharmaceutical, synthetic chemistry requirements.
  • the silicon oxynitride chromatographic stationary phase material prepared by the invention has abundant silicon amino groups on the surface, which effectively reduces and eliminates the existence of silanol groups on the surface of conventional silica gel, and is used for surface modification bonding modified silicon oxychloride chromatography stationary phase materials. When separating strong polar compounds, good separation results can be obtained under mild separation conditions.
  • the silicon oxynitride chromatographic stationary phase material prepared by the invention can well maintain the shape of the silicon oxide material, the pore structure and surface area of the material, and has the advantages of good mechanical strength, porous structure and large specific surface area of the silica gel material.
  • the silicon oxynitride chromatographic stationary phase material prepared by the invention has abundant silicon amino groups on the surface, which effectively reduces and eliminates the existence of silanol groups on the surface of the conventional silica gel, and the surface modified bonded nitrogen oxynitride chromatographic stationary phase material is used for separating the strong poles.
  • a good separation effect can be obtained under mild separation conditions, and it is a beneficial complementary matrix material for a conventional silica gel matrix stationary phase, and has wide application prospects as a chromatographic stationary phase material and a solid phase extraction material.
  • the invention has simple operation, low production cost and is suitable for industrial production.
  • Example 1 is a C8-bonded silicon oxynitride chromatographic stationary phase prepared by reacting an octanoyl chloride reagent in Example 13.
  • Example 2 is a 13 C CP/MAS NMR spectrum of a C18-bonded silicon oxynitride chromatographic stationary phase prepared using the carbon octadimethyldimethylsilane reagent in Example 14.
  • Figures 3 to 4 are chromatograms of chromatographic analysis in Example 16.
  • Example 3 is a porous oxynitride spherical chromatographic stationary phase material prepared in Example 2 of the present invention in acetonitrile/water
  • 1 is thymine
  • 2 is uracil
  • 3 is uridine
  • 4 is adenosine
  • 5 is guanosine
  • 6 is adenine
  • 7 is cytidine
  • 8 is cytosine.
  • 1 is xylose
  • 2 is sorbose
  • 3 is glucose
  • 4 is sucrose
  • 5 is pine disaccharide
  • 6 is maltitol
  • 7 is maltotriose
  • 8 is raffinose.
  • 6 is a chromatogram of a porous oxynitride spherical chromatographic stationary phase material prepared in Example 2 of the present invention in a mobile phase of acetonitrile/20 mM ammonium acetate aqueous solution (aqueous pH adjusted to 9.0) (80/20) mobile phase.
  • Figures 7 to 8 are chromatograms of chromatographic analysis in Examples 17 and 18.
  • 1 is uracil
  • 2 is toluene
  • 3 is ethylbenzene
  • 4 is propylbenzene
  • 5 pentylbenzene.
  • 1 is uracil
  • 2 is propranol
  • 3 is hydroxyphenyl butyl ester
  • 4 is amitriptyline
  • 5 is naphthalene
  • 6 is dipropyl phthalate
  • 7 is hydrazine.
  • the non-porous spherical silica chromatographic stationary phase material having a particle size of 1.5 ⁇ m is subjected to nitriding treatment in a high-temperature furnace having pure and dry ammonia gas, and the flow rate of ammonia gas during high-temperature nitriding treatment is 0.001 L/min.
  • the nitriding temperature was 600 ° C and the nitriding time was 0.1 hour.
  • the obtained silicon oxynitride material was degassed at 30 ° C for 0.1 hour, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen oxide content of the silicon oxynitride stationary phase material was 0.3%.
  • a porous spherical silica chromatographic stationary phase material having a particle size of 5 ⁇ m is subjected to nitriding treatment in a high-temperature furnace equipped with pure dry ammonia gas, and the flow rate of ammonia gas during high-temperature nitriding treatment is 0.2 L/min, nitrogen
  • the crystallization temperature was 850 ° C and the nitriding time was 20 hours.
  • the obtained silicon oxynitride material was degassed at 200 ° C for 20 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen oxide blue chromatography stationary phase material had a nitrogen content of 8.0%.
  • a porous spherical silica chromatographic stationary phase material having a particle size of 0.5 ⁇ m is subjected to nitriding treatment in a high-temperature furnace having pure dry ammonia gas, and a flow rate of ammonia gas at a high temperature nitriding treatment is 50 L/min, nitriding Temperature is At 1200 °C, the nitriding time is 100 hours.
  • the obtained silicon oxynitride material was degassed at 100 ° C for 0.1-20 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen content of the silicon oxynitride stationary phase material was 36.6%.
  • a spherical silica chromatographic stationary phase material having a particle size of 10 ⁇ m is subjected to nitriding treatment in a high-temperature furnace having pure and dry ammonia gas, and a flow rate of ammonia gas at a high temperature nitriding treatment is 0.001 L/min, nitriding
  • the temperature is 600 ° C and the nitriding time is 60 hours.
  • the obtained silicon oxynitride material was degassed at 200 ° C for 5 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen oxide content of the silicon oxynitride stationary phase material was 2.2%.
  • the amorphous silica chromatographic stationary phase material having a particle size of 20-200 ⁇ m is nitrided in a high-temperature furnace with pure dry ammonia gas, and the flow rate of ammonia gas during high-temperature nitriding treatment is 50 L/min.
  • the nitriding temperature is 900 °C and the nitriding time is 300 hours.
  • the obtained silicon oxynitride material was degassed at 60 ° C for 20 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen oxide content of the silicon oxynitride stationary phase material was 20.4%.
  • a porous spherical silica chromatographic stationary phase material having a particle size of 5 ⁇ m is subjected to nitriding treatment in a high-temperature furnace equipped with pure dry ammonia gas, and the flow rate of ammonia gas during high-temperature nitriding treatment is 0.2 L/min, nitrogen
  • the crystallization temperature was 950 ° C and the nitriding time was 36 hours.
  • the obtained silicon oxynitride material was degassed at 200 ° C for 20 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen content of the silicon oxynitride stationary phase material was 10.0%.
  • a porous spherical silica chromatographic stationary phase material having a particle size of 5 ⁇ m is subjected to nitriding treatment in a high-temperature furnace equipped with pure dry ammonia gas, and the flow rate of ammonia gas during high-temperature nitriding treatment is 0.2 L/min, nitrogen
  • the crystallization temperature was 1050 ° C and the nitriding time was 60 hours.
  • the obtained silicon oxynitride material was degassed at 200 ° C for 20 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen oxide content of the silicon oxynitride stationary phase material was 25.0%.
  • a porous spherical silica chromatographic stationary phase material having a particle size of 5 ⁇ m is subjected to nitriding treatment in a high-temperature furnace equipped with pure dry ammonia gas, and the flow rate of ammonia gas during high-temperature nitriding treatment is 0.2 L/min, nitrogen
  • the crystallization temperature was 1050 ° C and the nitriding time was 120 hours.
  • the obtained silicon oxynitride material was degassed at 200 ° C for 20 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen content of the silicon oxynitride stationary phase material was 28.0%.
  • Amorphous silica chromatographic stationary phase material with a particle size of 20 microns in clear pure ammonia The nitriding treatment is carried out in a high-temperature furnace of gas, and the flow rate of ammonia gas at a high-temperature nitriding treatment is 20 L/min, the nitriding temperature is 1100 ° C, and the nitriding time is 100 hours.
  • the obtained silicon oxynitride material was degassed at 100 ° C for 10 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen content of the silicon oxynitride stationary phase material was 32.2%.
  • a porous spherical silica chromatographic stationary phase material having a particle size of 3 ⁇ m is subjected to nitriding treatment in a high-temperature furnace equipped with pure dry ammonia gas, and the flow rate of ammonia gas during high-temperature nitriding treatment is 2 L/min, nitrogen
  • the aging temperature was 800 ° C and the nitriding time was 150 hours.
  • the obtained silicon oxynitride material was degassed at 120 ° C for 5 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen content of the silicon oxynitride stationary phase material was 14.6%.
  • a porous spherical silica chromatographic stationary phase material having a particle size of 1.7 ⁇ m is subjected to nitriding treatment in a high-temperature furnace having pure and dry ammonia gas, and a flow rate of ammonia gas at a high temperature nitriding treatment is 50 L/min, nitrogen
  • the crystallization temperature was 1250 ° C and the nitriding time was 300 hours.
  • the obtained silicon oxynitride material was degassed at 30 ° C for 20 hours, and then washed with water and methanol in that order. Elemental analysis showed that the nitrogen content of the silicon oxynitride stationary phase material was 39.9%.
  • oxynitride spherical stationary phase material prepared in Example 8 10 g of a porous spherical silicon oxynitride material having a particle size of 5 ⁇ m was vacuum dried at 100 ° C for 24 hours. Add 250 mL of toluene or xylene, 30 mmol of reagents 12a-12f in Table 1 to the pretreated silicon oxynitride material, and react at respective temperatures for 3 to 48 hours as shown in Table 1, and filter, and solids in turn.
  • oxynitride spherical stationary phase material prepared in Example 5 5 g of a porous spherical silicon oxynitride material having a particle size of 5 ⁇ m was vacuum dried at 100 ° C for 48 hours. After pretreatment of silicon oxynitride carbon octadimethyl chlorosilane reagent 1.25 mL of pyridine was reacted at 100 °C for 12 hours, filtered, and the solid was washed once with 200 mL of toluene, methanol/water (volume ratio 1/1), methanol, diethyl ether, and dried to give C18 bonded silicon oxynitride.
  • oxynitride spherical stationary phase material prepared in Example 8 10 g of a porous spherical silicon oxynitride material having a particle size of 5 ⁇ m was vacuum dried at 100 ° C for 24 hours. Add 250 mL of toluene or xylene, 40 mmol of silylating reagent 13a-131 in Table 1, and 2 mL of pyridine to the pretreated silicon oxynitride material, and react at the respective temperatures for 3 to 48 hours as shown in Table 1.
  • nucleoside compounds (1 is thymine, 2 is uracil, 3 is uridine, 4 is adenosine, 5 is guanosine, 6 adenine, 7 is cytidine, and 8 is cytosine.
  • the alkylbenzene mixture of toluene, ethylbenzene, propylbenzene, and pentylbenzene exhibited significant reversed-phase chromatographic retention behavior on the column. As the substitution chain increased, the retention time increased and the pentane retention time was the longest.
  • the present invention uses a silicon oxide material as a raw material to prepare a silicon oxynitride chromatographic stationary phase material having a silicon amino group and an imino group on the surface by nitriding an ammonia gas with a silicon oxide material at a high temperature.
  • the nitrogen content of the silicon oxynitride material can be controlled by controlling the flow rate of ammonia gas, the temperature of nitriding, and the nitriding time.
  • the silicon oxynitride material prepared by the invention not only maintains the morphology of the silicon oxide material well, but also maintains the pore structure and specific surface area of the silicon oxide material.
  • the silicon oxynitride material prepared by the invention has good chemical stability and can exist stably in the mobile phase of pH 1-13 without loss, and has wide application prospects as a chromatographic stationary phase material and a solid phase extraction material.
  • the surface of the silicon oxynitride material prepared by the invention contains a large amount of silicon amino groups, and reacts with a modifying reagent containing different functional groups, thereby modifying the surface of the silicon oxynitride material with different polarities and charge properties, and the surface modification bonding can be modified.
  • Sodium oxynitride chromatography stationary phase material is a large amount of silicon amino groups, and reacts with a modifying reagent containing different functional groups, thereby modifying the surface of the silicon oxynitride material with different polarities and charge properties, and the surface modification bonding can be modified.
  • the surface modified bonded modified silicon oxynitride material prepared by the invention contains a large amount of silicon amino groups on the surface, which can effectively reduce and improve the influence of the silanol group in the stationary phase of the silica gel matrix on the separation analysis.
  • a chromatographic stationary phase material solid phase extraction and solid phase microextraction materials have broad application prospects.
  • the invention has simple operation, low production cost and is suitable for industrial production.

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Description

氮氧化硅色谱固定相材料及其制备和应用 技术领域
本发明涉及氮氧化硅色谱固定相材料及其制备方法和应用。具体地说是利用氨气 对氧化硅材料进行氮化处理制备氮氧化硅材料，提供了氮氧化硅色谱固定相材料的制 备方法及其在分离分析、固相萃取等领域的应用； 进一步利用氮氧化硅表面的硅氨基 与具有不同官能团的表面键合改性试剂反应，提供了氮氧化硅色谱固定相材料的表面 修饰键合的制备方法及其在分离分析、 固相萃取等领域的应用。
背景技术
随着以人类健康、 生物工程为核心的生命科学、环境科学及制药、合成化学的迅 猛发展， 高效液相色谱 (HPLCM乍为一种高效、快速、分离条件温和的分离分析技术备 受人们关注， 是目前应用最为广泛的分析分离手段之一。作为 HPLC技术的核心， 色 谱柱填料对于色谱分离至关重要，是各种 HPLC分离模式赖以建立和发展的基础，是 实现有效分离的关键。
色谱分离性能与色谱填料的物化性质密切相关， 由于具有良好的机械强度、较好 的热稳定性和化学稳定性、 易于控制的物理性质 (如孔结构、 孔径、 比表面积)， 硅胶 基质是一种理想的色谱固定相材料。最为重要的是硅胶表面含有丰富的硅羟基， 易于 进行表面化学改性， 是各种化学键合相的理想基质材料。但是， 硅胶填料在色谱应用 中有两个难于解决的问题 [Kirkland, J. J. et al. J. Chromatogr. A 1997, 762, 97-1 12.]： ( 1 ) 硅胶填料在色谱应用中可使用的 pH范围窄，只能在 pH = 2〜8的流动相条件下使用。 pH > 8时， 硅胶基质不稳定， 容易溶解； pH < 2时， 表面键合基团易水解流失。 （2 ) 经过烷基化修饰的硅胶表面仍然残留一定量的硅羟基， 对含 N碱性化合物等较强极 性物质易产生不可逆吸附作用，从而造成反相模式下对极性分析物分离时产生色谱峰 严重脱尾甚至分析物的死吸附。 为了拓宽硅胶基质色谱固定相材料的 pH使用范围， 近来人们推出了有机-无机杂化硅胶 [Neue U.D. et al. Am. Lab. 1999, 31 , 36-39; Wyndham K.D. et al. Anal. Chem. 2003, 75, 6781-6788.] , 将有机基团引入到硅胶骨架 上， 拓宽了其 pH适用范围， 甲基杂化和乙基杂化硅胶的 pH范围为 1-12。 但是骨架 中有机基团的引入也降低了杂化硅胶表面的硅醇基密度，限制了杂化硅胶作为亲水材 料的应用。
人们相继发展了一些其它的色谱基质材料 [Silva C.R. et al. J. Chromatogr. A
2008, 1 191, 90 - 98.] 如有机聚合物高分子、石墨化碳和金属氧化物（如二氧化锆、二 氧化钛和氧化铝）等。 有机聚合物填料 pH化学稳定性好， 但是这类色谱填料机械强 度差， 而且在有机溶剂中易溶胀， 难以进行梯度洗脱， 极大地限制了这类材料的应用 范围。石墨化碳材料具有良好的机械强度和化学稳定性，近年来作为色谱填料在强极 性化合物的分离中得到了应用，因其表面不易改性，主要用作反相色谱模式填料基质， 而且长期使用表面会产生不均一性， 易导致非特异性吸附。金属氧化物以其独特的表 面性质和较好的化学稳定性， 引起了人们的广泛关注。 目前， 作为色谱填料得到应用 的氧化物主要有二氧化锆、 二氧化钛和氧化铝。 金属氧化物表面存在 Lewis酸、碱作 用位点及阴离子交换、 阳离子交换和配体交换中心， 由于其表面作用力类型多， 作用 力复杂， 在分离过程中各种作用模式常常共存， 分离机理复杂， 通过调节流动相、 pH 值、 缓冲盐等常用色谱条件时， 其表面的色谱行为较硅胶基质难预测。 为此， 现在急 需发展一些新型的色谱填料以弥补现有色谱分离基质材料的缺点和不足。
近年来，氮氧化硅固体碱材料在精细化工以及催化行业引起了广泛的关注。通过 高温下利用氨气对氧化硅进行氮化处理制备氮氧化硅材料；制备得到的氮氧化硅微米 颗粒材料不仅具有硅胶基质所具有的良好机械强度、 多孔结构、 大的比表面积、较好 的化学稳定性和热稳定性等优点；而且材料表面上存在着丰富的 Si-NH2和 Si-NH-Si， 通过与含环氧基、 酰氯、 醛基、 卤素等反应基团的改性试剂、 以及硅烷化试剂等进行 反应， 可以将材料修饰为亲水或者疏水表面，氮氧化硅基质与其经过表面改性的材料 可以作为反相、 正相、 亲水或者离子交换色谱固定相、 固相萃取材料或者固相微萃取 材料使用。
发明内容
本发明的目的在于提供一种氮氧化硅色谱固定相材料及其制备和应用。
一种氮氧化硅色谱固定相材料， 分子式为 SiOxNy， 其中 x、 y分别为材料中氧、 氮的摩尔数， 0≤x<2， 0<y<4/3, 2x + 3y = 4;
对上述氮氧化硅色谱固定相材料表面进行修饰获得表面修饰键合改性的氮氧化 硅色谱固定相材料， 表面修饰键合改性试剂为 Za(R')bSi-R， 其中 Z = Cl-、 Br-, I-、 d-C5烷氧基、 二烷基取代氨基（如二甲氨基）、 或三氟甲磺酸基中的一种； a为 1、 2 或 3， b为 0、 1或 2， 且 a+b = 3; R'为 d-C5直链烷基、 C3-C5环状烷基、 或者 C4-C5 支链烷基； R为表面修饰键合官能基团， 为 3()烷基、 芳香基、 烷基氰基、 烷基氨 基、 烷基二醇基、 烷基硝基、 阴 /阳离子交换基团、 以及具有极性基团的烷基或者芳 香基。
或，对上述氮氧化硅色谱固定相材料表面进行修饰获得表面修饰键合改性的氮氧
0
化硅色谱固定相材料， 表面修饰键合改性试剂为 R^ (R = CnH2n+1 , n = 0-30的整 数)， R'COCl (R- = CnH2n+1， n = 0-30的整数)， R"CHO (R" = CnH2n+1， n = 0-30的整数)， 或 R'"X (R"' = CnH2n+1、 n = 0-30的整数， X = Cl-、 Br -、 I-)。
制备过程： 以氧化硅颗粒为原料， 通过在高温下使用氨气与氧化硅材料的氮化反 应制得氮氧化硅材料， 利用含环氧基、 酰氯、 醛基、 卤素等反应基团的改性试剂、 或 硅烷化试剂对氮氧化硅材料表面进行修饰反应，进一步制备得到表面修饰键合改性的 氮氧化硅色谱固定相材料。 制备过程包括以下步骤： （1 ) 将氧化硅材料在通有氨气 的高温炉中进行氮化处理， 制得氮氧化硅材料；
(2) 将制得的氮氧化硅材料在 30-200 °C脱气处理 0.1-20小时；
(3 ) 把步骤 2得到的氮氧化硅材料表面进行修饰键合改性处理， 改性试剂可以 为 Za(R')bSi-R，其中 Z = Cl-、 Br-、 I-、 d-C5烷氧基、二烷基取代氨基（如二甲氨基）、 或三氟甲磺酸基中的一种； a为 1、 2或 3， b为 0、 1或 2， 且 a+b = 3; R，为 Ci-C5 直链烷基、 C3-C5环状烷基、 或者 C4-C5支链烷基； R为表面修饰键合官能基团。 改
0
性试剂可以为 R^A (R = CnH2n+1， n = 0-30的整数)， R'COCl (R' = CnH2n+1， n = 0-30 的整数)， R"CHO (R" = CnH2n+1， n = 0-30的整数)， 或 R"'X (Rm = CnH2n+1、 n = 0-30 的整数， X = Cl-、 Br -、 I-) o
上述氮氧化硅色谱固定相材料的制备方法中氧化硅固定相材料颗粒形状可以为 球形和无定形。
上述氮氧化硅色谱固定相材料的制备方法中氧化硅固定相材料的球形颗粒粒径 大小为 0.5-200微米。
上述氮氧化硅色谱固定相材料的制备方法中高温氮化处理气体为氨气。
上述氮氧化硅色谱固定相材料的制备方法中高温氮化处理时氨气的流量为
0.001-50 L/min, 氮化温度为 600-1250 °C， 氮化时间为 0.1-300小时。
上述氮氧化硅色谱固定相材料的制备方法中通过控制氨气流量，氮化温度和氮化 时间， 可以获得氮含量质量百分比为 0.1-40%的硅氧氮化合物色谱固定相材料。
上述氮氧化硅色谱固定相材料的制备方法中改性试剂所述的表面修饰键合改性 试剂 Za(R')bSi-R中 R可以为 d-C^烷基、 芳香基、 烷基氰基、 烷基氨基、 烷基二醇 基、 烷基硝基、 阴 /阳离子交换基团、 以及具有极性基团的烷基或者芳香基。 其中， 烷基基团包括： -CH2(CH2)6CH3、 -CH2(CH2)16CH3、 或 -CH2(CH2)28CH3; 芳香基团， 如 C6A5-(CH2)e-， 其中 A=H、 F或 Cl， c=l-4的正整数； 烷基氰基， 如氰基丙基或氰 基丁基； 烷基氨基， 如氨丙基或丁基氨基； 烷基二醇基， 如丙二醇基或丁二醇基； 烷 基硝基， 如丙基硝基或丁基氨基； 阴离子交换基团， 如 - (CH2)dN(CH3)2CnH2n+1， 其中
d=l-4的正整数， n=l-4的正整数； 阳离子交换基团， 如
Figure imgf000004_0001
， n=l-4的 正整数； 具有极性基团的烷基或者芳香基， 如含有氨基甲酸基团的烷基或者芳香基， CH3(CH2)17NHC(0)0(CH2)3-， CH3(CH2)7NHC(0)0(CH2)3-， C6H5CH2NHC(0)0(CH2)3-。
本发明所述氮氧化硅材料表面进行修饰键合改性处理过程如下：
( 1 ) 将制得的氮氧化硅材料在 80-150 °C真空干燥处理 6-48小时; (2)在预处理后的氮氧化硅材料中加入有机溶剂、改性试剂，于室温至 130 °C 反 应 3-48小时， 过滤， 固体物依次用甲苯、 甲醇 /水 （体积比 1/1 )、 甲醇、 乙醚分别洗 涤 10-15体积量， 干燥后得到本发明所述的键合氮氧化硅色谱固定相材料。
上述表面修饰键合改性氮氧化硅色谱固定相材料的制备方法中所述有机溶剂为 二氯甲烷、 甲醇、 乙醇、 甲苯、 二甲苯、 乙酸乙酯或者四氢呋喃， 所述有机溶剂中含 有或不含吡啶和 /或者三乙胺， 吡啶和 /或者三乙胺于有机溶剂中体积含量为 0-100%; 改性试剂的加入量为每克氮氧化硅材料中加入 1-5 mmol, 有机溶剂的加入量为每克 氮氧化硅材料中加入 30-60 mL。
得到的氮氧化硅材料中氮元素的含量可以通过元素分析得到。氮氧化硅微米颗粒 材料不仅可以直接作为色谱固定相使用，而且可以通过表面硅氨基与含环氧基、酰氯、 醛基、 卤素等反应基团的改性试剂、或者硅烷化试剂反应将氮氧化硅材料表面改性修 饰为疏水、 亲水表面， 改性后的氮氧化硅材料可以用作反相、 正相、 亲水或者离子交 换色谱固定相。氮氧化硅色谱固定相材料的应用领域为高效液相色谱固定相材料、工 业色谱固定相材料、 固相萃取材料和固相微萃取材料。
本发明具有以下优点：
1. 制备过程简单， 工业化生产成本低， 有利于实现商业化应用。 本发明提供的 制备氮氧化硅色谱固定相材料的方法操作简便，仅需通过高温下氨气与氧化硅材料之 间的简单的气固相氮化取代反应，制得表面含有硅氨基基团的氮氧化硅色谱固定相材 料。
2. 氮化取代反应效率高， 氮氧化硅色谱固定相材料氮含量可以控制。 高温下氨 气与氧化硅材料之间的氮化取代反应效率高，氨气不仅可以与硅羟基反应将硅羟基取 代为硅氨基，而且可以与 Si-0-Si键中的氧反应生成 Si-NH-Si键。通过控制氮化温度， 时间和处理过程中氮气的流量， 可以制备氮质量百分含量在 0.1-40%之间可以调节的 氮氧化硅色谱固定相材料。
3.本发明通过高温下氨气与氧化硅材料中的羟基基团和 Si-0-Si基团之间的氮化 取代反应制备氮氧化硅色谱固定相材料， 不仅能很好的保持氧化硅材料的形貌， 而且 可以保持氧化硅材料的孔道结构和表面积。本发明制备的氮氧化硅不仅具有硅胶材料 的良好机械强度、 多孔结构、 大的比表面积、 热稳定性等优点； 而且材料表面上存在 着丰富的硅氨基。
4. 本发明制备的氮氧化硅材料表面上存在着丰富的硅氨基， 通过改性试剂与硅 氨基基团进行反应， 可以将材料的表面进一步修饰为亲水和疏水表面，氮氧化硅材料 与其经过表面改性的材料不仅可以作为反相、正相、亲水或者离子交换色谱固定相使 用， 而且作为工业色谱固定相材料、固相萃取材料和固相微萃取材料也有很广泛的应 用。
5. 本发明制备的氮氧化硅材料化学稳定性好， 在 pH=l-13的流动相中可以正常 使用而不发生流失现象。氮氧化硅基质与其经过表面改性的材料作为反相、 正相、 亲 水或者离子交换色谱固定相使用时， 表面基团没有明显的流失， 易于与质谱联用， 能 够有效的满足现代生命科学、 环境科学及制药、 合成化学的要求。
6. 本发明制备的氮氧化硅色谱固定相材料表面上存在着丰富的硅氨基， 有效降 低和消除了传统硅胶表面硅醇基的存在，表面修饰键合改性氮氧化硅色谱固定相材料 用于分离强极性化合物时， 在温和的分离条件下可以获得很好的分离效果。
总之， 本发明制备的氮氧化硅色谱固定相材料能够很好的保持氧化硅材料的形 貌、 材料的孔道结构和表面积， 具有硅胶材料的良好机械强度、 多孔结构、 大的比表 面积等优点。本发明制备的氮氧化硅色谱固定相材料表面上存在着丰富的硅氨基，有 效降低和消除了传统硅胶表面硅醇基的存在，表面修饰键合氮氧化硅色谱固定相材料 用于分离强极性化合物时，在温和的分离条件下可以获得很好的分离效果， 是传统硅 胶基质固定相的有益互补基质材料，作为色谱固定相材料和固相萃取材料具有广泛的 应用前景。 本发明操作简单， 生产成本低， 适于工业化生产。
附图说明
图 1为实施例 13中使用辛酰氯试剂反应制备的 C8键合氮氧化硅色谱固定相的
13C CP/MAS NMR谱图。
图 2为实施例 14中使用碳十八二甲基氯硅烷试剂制备的 C18键合氮氧化硅色谱 固定相的 13C CP/MAS NMR谱图。
图 3-图 4为实施例 16中进行色谱分析的色谱图。
图 3 为本发明实施例 2 制备的多孔氮氧化硅球形色谱固定相材料在乙腈 /水
( 90/10 ) 流动相中分离核苷的色谱图。 色谱条件： 4.6 X 250 mm氮氧化硅色谱柱； 流动相： 乙腈 /水 = 90/10； 流速： l .O mL/min; 柱温： 25 °C; 紫外检测波长： 254 nm。 图中 1为胸腺嘧啶， 2为尿嘧啶， 3为尿苷， 4为腺苷， 5为鸟苷， 6为腺嘌呤， 7为 胞苷， 8为胞嘧啶。
图 4为本发明实施例 2制备的多孔氮氧化硅球形色谱固定相材料在乙腈 /20 mM 乙酸铵水溶液（氨水调节 pH值为 9.0 ) ( 90/10 )流动相中分离核苷的色谱图。 色谱条 件： 4.6 x 250 mm氮氧化硅色谱柱； 流动相为乙腈 /20 mM乙酸铵水溶液 （氨水调节 pH值为 9.1 ) = 90/10; 流速： l .O mL/min; 柱温： 25 °C; 紫外检测波长： 254 nm。 图 中 1为胸腺嘧啶， 2为尿嘧啶， 3为尿苷， 4为腺苷， 5为鸟苷， 6为腺嘌呤， 7为胞 苷， 8为胞嘧啶。
图 5 为本发明实施例 2 制备的多孔氮氧化硅球形色谱固定相材料在乙腈 /水 ( 80/20 ) 流动相中分离糖类化合物的色谱图。 色谱条件： 4.6 X 250 mm氮氧化硅色 谱柱； 流动相为乙腈 /水 = 80/20; 流速： l .O mL/min; 柱温： 40 °C; 蒸发光散射检测 器检测： 漂移管温度 85 °C， 吹扫气压力 30 psi。 图中 1为木糖， 2为山梨糖， 3为葡 萄糖， 4为蔗糖， 5为松二糖， 6为麦芽糖醇， 7为麦芽三糖， 8为棉籽糖。 图 6 为本发明实施例 2制备的多孔氮氧化硅球形色谱固定相材料在乙腈 /20 mM 乙酸铵水溶液 （氨水调节 pH值为 9.0) ( 80/20 ) 流动相中分离糖类化合物的色谱图。 色谱条件： 4.6 x 250 mm氮氧化硅色谱柱； 流动相为乙腈 /20 mM乙酸铵水溶液 （氨 水调节 pH值为 9.0) = 80/20； 流速： l .O mL/min; 柱温： 40 °C; 蒸发光散射检测器 检测： 漂移管温度 85 °C， 吹扫气压力 30 psi。 图中 1为木糖， 2为葡萄糖， 3为蔗糖， 4为麦芽糖醇， 5为麦芽三糖， 6为棉籽糖。
图 7-图 8为实施例 17、 18中进行色谱分析的色谱图。
图 7为本发明实施例 14制备的多孔氮氧化硅球形色谱固定相材料在甲醇 /水流动 相中分离不同烷基取代苯的色谱图。 色谱条件： 4.6 X 150 mm C18键合氮氧化硅色谱 柱； 流动相： 甲醇 /水 = 80/20; 流速： l .O mL/min; 柱温： 30 °C; 紫外检测波长： 254 nm。 图中 1为尿嘧啶， 2为甲苯， 3为乙苯， 4为丙苯， 5为戊苯。
图 8为本发明实施例 14制备的多孔氮氧化硅球形色谱固定相材料在甲醇 /20 mM 乙酸铵水溶液（pH = 5.0)流动相中分离核苷的色谱图。色谱条件： 4.6 x 150 mm C18 键合氮氧化硅色谱柱； 流动相为甲醇 /20 mM乙酸铵水溶液 （乙酸调节 pH值为 5.0) = 60/40； 流速： l .O mL/min; 柱温： 30 °C; 紫外检测波长： 260 nm。 图中 1为尿嘧啶， 2为普洛萘尔， 3为羟苯丁酯， 4为阿米替林， 5为萘， 6为邻苯二甲酸二丙酯， 7为 苊。
具体实施方式
下面通过具体实施例和附图对本发明进行进一步说明。本发明所列的这些具体实 施例仅限于说明本发明， 而非对本发明的限定。
实施例 1
将颗粒粒径大小为 1.5微米的无孔球形氧化硅色谱固定相材料在通有纯净干燥的 氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 0.001 L/min, 氮化温 度为 600 °C， 氮化时间为 0.1小时。 将制得的氮氧化硅材料在 30 °C脱气处理 0.1小 时， 然后依次用水、 甲醇洗涤过滤。元素分析显示氮氧化硅色谱固定相材料的氮含量 为 0.3%。
实施例 2
将颗粒粒径大小为 5 微米的多孔球形氧化硅色谱固定相材料在通有纯净干燥的 氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 0.2 L/min, 氮化温度 为 850 °C， 氮化时间为 20小时。 将制得的氮氧化硅材料在 200 °C脱气处理 20小时， 然后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 8.0%。
实施例 3
将颗粒粒径大小为 0.5微米的多孔球形氧化硅色谱固定相材料在通有纯净干燥氨 气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 50 L/min, 氮化温度为 1200 °C， 氮化时间为 100小时。 将制得的氮氧化硅材料在 100 °C脱气处理 0.1-20小 时， 然后依次用水、 甲醇洗涤过滤。元素分析显示氮氧化硅色谱固定相材料的氮含量 为 36.6%。
实施例 4
将颗粒粒径大小为 10微米的球形氧化硅色谱固定相材料在通有纯净干燥的氨气 的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 0.001 L/min, 氮化温度为 600 °C， 氮化时间为 60小时。 将制得的氮氧化硅材料在 200 °C脱气处理 5小时， 然 后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 2.2%。
实施例 5
将颗粒粒径大小为 20-200微米的无定形氧化硅色谱固定相材料在通有纯净干燥 的氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 50 L/min， 氮化温度 为 900 °C， 氮化时间为 300小时。 将制得的氮氧化硅材料在 60 °C脱气处理 20小时， 然后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 20.4%。
实施例 6
将颗粒粒径大小为 5 微米的多孔球形氧化硅色谱固定相材料在通有纯净干燥的 氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 0.2 L/min, 氮化温度 为 950 °C， 氮化时间为 36小时。 将制得的氮氧化硅材料在 200 °C脱气处理 20小时， 然后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 10.0%。
实施例 7
将颗粒粒径大小为 5 微米的多孔球形氧化硅色谱固定相材料在通有纯净干燥的 氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 0.2 L/min, 氮化温度 为 1050 °C，氮化时间为 60小时。将制得的氮氧化硅材料在 200 °C脱气处理 20小时， 然后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 25.0%。
实施例 8
将颗粒粒径大小为 5 微米的多孔球形氧化硅色谱固定相材料在通有纯净干燥的 氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 0.2 L/min, 氮化温度 为 1050 °C， 氮化时间为 120小时。 将制得的氮氧化硅材料在 200 °C脱气处理 20小 时， 然后依次用水、 甲醇洗涤过滤。元素分析显示氮氧化硅色谱固定相材料的氮含量 为 28.0%。
实施例 9
将颗粒粒径大小为 20微米的无定形氧化硅色谱固定相材料在通有纯净干燥的氨 气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 20 L/min, 氮化温度为 1100 °C， 氮化时间为 100小时。 将制得的氮氧化硅材料在 100 °C脱气处理 10小时， 然后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 32.2%。
实施例 10
将颗粒粒径大小为 3 微米的多孔球形氧化硅色谱固定相材料在通有纯净干燥的 氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 2 L/min, 氮化温度为 800 °C, 氮化时间为 150小时。 将制得的氮氧化硅材料在 120 °C脱气处理 5小时， 然 后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 14.6%。
实施例 11
将颗粒粒径大小为 1.7微米的多孔球形氧化硅色谱固定相材料在通有纯净干燥的 氨气的高温炉中进行氮化处理， 高温氮化处理时氨气的流量为 50 L/min， 氮化温度为 1250 °C, 氮化时间为 300小时。 将制得的氮氧化硅材料在 30 °C脱气处理 20小时， 然后依次用水、 甲醇洗涤过滤。 元素分析显示氮氧化硅色谱固定相材料的氮含量为 39.9%。
实施例 12
使用实施例 8所制备的氮氧化硅球形固定相材料， 将 10 g颗粒粒径大小为 5微 米的多孔球形氮氧化硅材料在 100 °C下真空干燥处理 24小时。在预处理后的氮氧化 硅材料中加入 250 mL甲苯或者二甲苯、 30 mmol表 1中的试剂 12a-12f， 如表 1中所 示在各自温度下反应 3-48小时， 过滤， 固体物依次用甲苯、 甲醇 /水 （体积比 1/1 )、 甲醇、 乙醚分别洗涤 1次， 干燥后得到 12a-12f所含官能团键合的氮氧化硅色谱固定 相。
表 1
Figure imgf000009_0001
12e 40 10 28 3
12f 100 48 27 10 实施例 13
使用实施例 6所制备的氮氧化硅球形固定相材料， 将 5 g颗粒粒径大小为 5微米 的多孔球形氮氧化硅材料在 80-150 °C下真空干燥处理 6小时。 在预处理后的氮氧化
0
硅材料中加入 100 mL甲苯， 4 mL辛酰氯试剂 Cl^^^^^^， 于 80 °C 反应 16小时， 过滤， 固体物依次用 250 mL甲苯、 甲醇 /水 （体积比 1/1 )、 甲醇、 乙醚分 别洗涤 1次， 干燥后得到 C8键合氮氧化硅色谱固定相， 元素分析氮含量为 10.0%、 碳含量 2.0%。如图 1所示， 13C CP/MAS NMR谱图表征进一步确认了 C8对氮氧化硅 材料表面的键合反应。
实施例 14
使用实施例 Ί所制备的氮氧化硅球形固定相材料， 将 5 g颗粒粒径大小为 5微米 的多孔球形氮氧化硅材料在 100 °C下真空干燥处理 48小时。在预处理后的氮氧化硅 碳十八二 甲 基氯硅烷试剂
Figure imgf000010_0001
、 1.25 mL吡啶， 于 100 °C 反应 12小 时， 过滤， 固体物依次用 200 mL甲苯、 甲醇 /水（体积比 1/1 )、 甲醇、 乙醚洗涤 1次， 干燥后得到 C18键合氮氧化硅色谱固定相， 元素分析含氮量 24.0%， 含碳量 9.0%。 如图 2所示， 13C CP/MAS NMR谱图表征进一步确认了 C18对氮氧化硅材料表面的 键合反应。
实施例 15
使用实施例 8所制备的氮氧化硅球形固定相材料， 将 10 g颗粒粒径大小为 5微 米的多孔球形氮氧化硅材料在 100 °C下真空干燥处理 24小时。在预处理后的氮氧化 硅材料中加入 250 mL甲苯或者二甲苯、 40 mmol表 1中的硅烷化试剂 13a-131、 2 mL 吡啶， 如表 1中所示在各自温度下反应 3-48小时， 过滤， 固体物依次用甲苯、 甲醇 / 水 （体积比 1/1 )、 甲醇、 乙醚分别洗涤 1次， 干燥后得到 13a-13k所含官能团键合的 氮氧化硅色谱固定相。
表 1
Figure imgf000010_0002
13b C6H5(CH2)2SiCl3 100 6 27 5
13c C6F5(CH2)2SiCl3 100 3 27 5
13d CN(CH2)3SiCl3 60 12 28 2
13e CN(CH2)3Si (OCH3)3 60 12 28 2
13f NH2 (CH2)3SiCl3 60 10 28 2
13g (CH3)3SiCl 50 6 28 1
13h (CH2OH)2CHSi (CH3)2C1 60 36 28 2
13i S03HC6H4(CH2)3Si (CH3)2C1 100 12 27 5
13j C3H7N (CH3)2(CH2)3 SiCl3 80 8 27 4
13k CH3(CH2)7NHC(0)0(CH2)3Si 100 48 27 6
(CH3)2C1
131 C30H61Si (CH3)2C1 100 20 26 16 实施例 16
使用实施例 2所制备的氮氧化硅球形固定相材料，用匀浆法填充到 4.6 X 250 mm 不锈钢色谱柱中，在亲水作用色谱模式下以碱基、核苷和糖类化合物等一系列强极性 化合物为探针评价材料的分离性能。 如图 3-4所示， 核苷化合物 （1 为胸腺嘧啶， 2 为尿嘧啶， 3为尿苷， 4为腺苷， 5为鸟苷， 6腺嘌呤， 7为胞苷， 8为胞嘧啶）， 分别 在乙腈 /水（90/10)流动相和乙腈 /20 mM乙酸铵水溶液（氨水调节 pH值为 9.0)(90/10) 流动相中， 在氮氧化硅色谱固定相上得到了有效的分离。 如图 5-6 所示， 在乙腈 /水 ( 80/20) 流动相和乙腈 /20 mM乙酸铵水溶液 （氨水调节 pH值为 9.0) ( 80/20) 流动 相中， 糖类化合物（1为木糖， 2为葡萄糖， 3为蔗糖， 4为麦芽糖醇， 5为麦芽三糖， 6为棉籽糖） 在氮氧化硅色谱柱上进行了有效的分离。
实施例 17
使用实施例 14所制备的 C18键合氮氧化硅球形固定相材料，用匀浆法填充到 4.6 X 150 mm不锈钢色谱柱中， 在反相作用色谱模式下以一系列标准化合物为探针分子 评价材料的分离性能。 如图 7所示， 色谱条件为， 流动相： 甲醇 /水 = 80/20; 流速： 1.0 mL/min; 柱温： 30 °C; 紫外检测波长： 254 nm。 甲苯、 乙苯、 丙苯、 戊苯的烷基 苯混合物在色谱柱上表现出明显的反相色谱保留行为， 随着取代链的增长，保留时间 增长， 戊苯保留时间最长。
实施例 18
使用实施例 14所制备的 C18键合氮氧化硅球形固定相材料，用匀浆法填充到 4.6 X 150 mm不锈钢色谱柱中， 在反相作用色谱模式下以一系列标准化合物为探针分子 评价材料的分离性能。 如图 8所示， 色谱条件为， 流动相为甲醇 /20 mM乙酸铵水溶 液 （乙酸调节 pH值为 5.0) = 60/40； 流速： 1.0 mL/min; 柱温： 30 °C; 紫外检测波 长： 260 nm。 混合物 （1为尿嘧啶， 2为普洛萘尔， 3为羟苯丁酯， 4为阿米替林， 5 为萘， 6为邻苯二甲酸二丙酯， 7为苊） 得到了很好的分离， 其中苊分离的理论塔板 数为 60000 /米。
本发明以氧化硅材料为原料，通过在高温下氨气与氧化硅材料的氮化反应制备得 到表面含有硅氨基和亚氨基团的氮氧化硅色谱固定相材料。通过控制氨气的流量，氮 化温度和氮化时间， 可以控制氮氧化硅材料的氮含量。本发明制备的氮氧化硅材料不 但能很好地保持氧化硅原料的形貌， 而且可以保持氧化硅材料的孔道结构和比表面 积。 本发明制备的氮氧化硅材料化学稳定性好， 在 pH 1-13的流动相中能够稳定存在 而不发生流失， 作为色谱固定相材料和固相萃取材料具有广泛的应用前景。本发明制 备的氮氧化硅材料表面含有大量的硅氨基， 与含有不同官能团的改性试剂反应， 从而 对氮氧化硅材料表面进行不同极性和电荷性质的修饰，可以制得表面修饰键合改性的 氮氧化硅色谱固定相材料。与传统硅胶材料表面硅醇基不同，本发明制备的表面修饰 键合改性氮氧化硅材料表面含有大量的硅氨基，能够有效降低和改善硅胶基质固定相 中硅醇基对分离分析的影响， 作为色谱固定相材料、固相萃取和固相微萃取材料具有 广泛的应用前景。 本发明操作简单， 生产成本低， 适于工业化生产。

Claims

权 利 要 求 书
1、 一种氮氧化硅色谱固定相材料， 其特征在于： 分子式为 SiOxNy， 其中 x、 y 分别为材料中氧、 氮的摩尔数， SiOxNy， 其中 2x+3y=4， 0<x<2, 0<y≤4/3。
2、 根据权利要求 1所述的氮氧化硅色谱固定相材料， 其特征在于：
所述固定相材料为采用改性试剂对权利要求 1 所述氮氧化硅材料表面进行修饰 获得表面修饰键合的氮氧化硅色谱固定相材料， 表面修饰键合改性试剂为 Za(R')bSi-R, 其中 Z = Cl-、 Br-、 I-、 d-C5烷氧基、 二烷基取代氨基 （如二甲氨基）、 或三氟甲磺酸基中的一种； a为 1、 2或 3， b为 0、 1或 2， 且 a+b = 3; R'为 d-C5 直链烷基、 C3-C5环状烷基、 或者 C4-C5支链烷基； R为表面修饰键合官能基团； 或，所述固定相材料为采用改性试剂对权利要求 1所述氮氧化硅材料表面进行修
0 饰获得表面修饰键合的氮氧化硅色谱固定相材料， 表面修饰键合改性试剂为 R^
(R = CnH2n+1， n = 0-30的整数)， R'COCl (R' = CnH2n+1， n = 0-30的整数)， R"CHO (R" = CnH2n+1， n = 0-30的整数)， 或 R"'X (R"' = CnH2n+1、 n = 0-30的整数， X = Cl-、 Br -、 I-) o
3、 根据权利要求 2 所述的材料， 其特征在于： 所述的表面修饰键合改性试剂 Za(R')bSi-R中 R为 d-C^烷基、 芳香基、 烷基氰基、 烷基氨基、 烷基二醇基、 烷基 硝基、 阴 /阳离子交换基团、 以及具有极性基团的烷基或者芳香基。
4、 根据权利要求 3 所述的材料， 其特征在于： 所述烷基为 -CH2(CH2)6CH3、 -CH2(CH2)16CH3、 或 -CH2(CH2)28CH3; 芳香基团为 C6A5-(CH2)c-， 其中 A=H、 F或 Cl， c=l-4的正整数； 烷基氰基为氰基丙基或氰基丁基； 烷基氨基为氨丙基或丁基氨基； 烷基二醇基为丙二醇基或丁二醇基； 烷基硝基为丙基硝基或丁基硝基； 阴离子交换基 团为- (CH2)dN(CH3)2CnH2n+1， 其中 d=l-4的正整数， n=l-4的正整数； 阳离子交换基团
为
Figure imgf000013_0001
， n=l-4的正整数； 具有极性基团的烷基或者芳香基为含有氨基 甲 酸基 团 的烷基或者芳 香基 ， 其 为 ： CH3(CH2)17NHC(0)C CH2)3- 、 CH3(CH2)7NHC(0)0(CH2)3-或 C6H5CH2NHC(0)0(CH2)3-。
5、 根据权利要求 1或 2所述的氮氧化硅色谱固定相材料， 其特征在于： 所述的 氮氧化硅色谱固定相材料的颗粒形状为球形或无定形；所述球形的氮氧化硅色谱固定 相材料的颗粒粒径大小为 0.5-200微米。
6、 一种权利要求 1、 2、 3、 4或 5所述氮氧化硅色谱固定相材料的制备方法， 其 特征在于： 包括以下步骤，
1 ) 将氧化硅材料放入高温炉中；
2) 在通有纯净干燥的氨气的高温炉中对氧化硅材料进行高温氮化处理， 制得氮 氧化硅材料；高温氮化处理时氨气的流量为 0.001-50 L/min,氮化温度为 600-1250 °C， 氮化时间为 0.1-300小时； 通过控制氨气流量， 氮化温度和氮化时间， 可以获得氮含 量质量百分比为 0.1-40%的氮氧化硅色谱固定相材料；
3 ) 将制得的氮氧化硅材料在 30-200 °C脱气处理 0.1-20小时。
7、 根据权利要求 6所述的氮氧化硅色谱固定相材料的制备方法， 其特征在于： A. 把步骤 3 ) 得到的氮氧化硅材料表面进行修饰键合获得表面修饰键合的氮氧 化硅色谱固定相材料， 表面修饰键合改性试剂为 Za(R')bSi-R， 其中 Z = Cl-、 Br-、 I-、 d-C5烷氧基、 二烷基取代氨基（如二甲氨基）、 或三氟甲磺酸基中的一种； a为 1、 2 或 3， b为 0、 1或 2， 且 a+b = 3 ; R'为 d-C5直链烷基、 C3-C5环状烷基、 或者 C4-C5 支链烷基； R为表面修饰键合官能基团。
或， B.把步骤 3 ) 得到的氮氧化硅材料表面进行修饰获得表面修饰键合的氮氧化
0
硅色谱固定相材料，表面修饰键合改性试剂为 R^ (R = CnH2n+1 , n = 0-30的整数)，
R'COCl (R- = CnH2n+1， n = 0-30的整数)， R"CHO (R" = CnH2n+1， n = 0-30的整数)， 或 R'"X (R'" = CnH2n+1、 n = 0-30的整数， X = Cl-、 Br -、 I-)。
8、 根据权利要求 Ί所述的氮氧化硅色谱固定相材料的制备方法， 其特征在于： 所述的表面修饰键合改性试剂 ^！^^卜 中 R为 d-C^烷基、 芳香基、 烷基氰基、 烷基氨基、 烷基二醇基、 烷基硝基、 阴 /阳离子交换基团、 以及具有极性基团的烷基 或者芳香基。
9、 根据权利要求 8所述的氮氧化硅色谱固定相材料的制备方法， 其特征在于： 所述烷基为 -CH2(CH2)6CH3、 -CH2(CH2)16CH3 或 -CH2(CH2)28CH3； 芳香基团为 C6A5-(CH2)C-, 其中 A=H、 F或 Cl， c=l-4的正整数； 烷基氰基为氰基丙基或氰基丁 基； 烷基氨基为氨丙基或丁基氨基； 烷基二醇基为丙二醇基或丁二醇基； 烷基硝基为 丙基硝基或丁基硝基； 阴离子交换基团为 - (CH2)dN(CH3)2CnH2n+1， 其中 d=l-4的正整
数， n=l-4的正整数； 阳离子交换基团为
Figure imgf000014_0001
， n=l-4的正整数； 具有极 性基团的烷基或者芳香基为含有氨基甲酸基团的烷基或者芳香基， 其为：
CH3(CH2)17NHC(0)0(CH2)3- CH3(CH2)7NHC(0)0(CH2)3- C6H5CH2NHC(0)0(CH2)3-。
10、 根据权利要求 7所述的氮氧化硅色谱固定相材料的制备方法， 其特征在于： 权利要求 6中制备的氮氧化硅微米颗粒材料不仅可以直接作为色谱固定相使用；而且 可以通过其与权利要求 Ί中 A步骤中硅烷化试剂、 或者与权利要求 Ί中 B步骤中含 环氧基、 酰氯、 醛基、 卤素等反应基团的改性试剂进行反应， 将材料表面改性修饰为 疏水、 亲水表面， 改性后的材料可以用作反相、 正相、 亲水或者离子交换色谱固定相 材料。
11、 一种权利要求 7、 8或 9所述材料的制备方法， 其特征在于， 包括以下步骤:
1 ) 将权利要求 6中制得的氮氧化硅材料在 80-150 °C真空干燥处理 6-48小时；
2) 在干燥处理后的氮氧化硅材料中加入有机溶剂、 权利要求 7中 、 或 B步骤 中改性试剂，于室温至 130 °C 反应 3-48小时，过滤，固体物依次用甲苯、甲醇 /水（体 积比 1/1 )、 甲醇、 乙醚分别洗涤 10-15体积量， 干燥后得到本发明所述的表面键合氮 氧化硅色谱固定相材料。
12、 根据权利要求 11所述的制备方法， 其特征在于：
所述有机溶剂为二氯甲烷、 甲醇、 乙醇、 甲苯、二甲苯、 乙酸乙酯或者四氢呋喃， 所述有机溶剂中含有或不含吡啶和 /或者三乙胺， 吡啶和 /或者三乙胺于有机溶剂中体 积含量为 0-100%; 改性试剂的加入量为每克氮氧化硅材料中加入 1-5 mmol, 有机溶 剂的加入量为每克氮氧化硅材料中加入 30-60 mL。
13、 一种权利要求 1、 2、 3、 4或 5所述的氮氧化硅色谱固定相材料的应用， 其 特征在于： 权利要求 1、 2、 3、 4或 5所述的氮氧化硅色谱固定相材料可应用于高效 液相色谱固定相材料、 工业色谱固定相材料、 固相萃取材料或固相微萃取材料。
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CN1056908A (zh) * 1990-05-31 1991-12-11 中国科学院金属研究所 高性能β-氮化硅晶晶须的制备方法
US6096656A (en) * 1999-06-24 2000-08-01 Sandia Corporation Formation of microchannels from low-temperature plasma-deposited silicon oxynitride
CN1666820A (zh) * 2004-03-12 2005-09-14 同济大学 贵金属负载介孔氮氧化硅复合催化剂及其制备方法
CN1877879A (zh) * 2005-06-06 2006-12-13 施乐公司 有机电子器件的阻挡层

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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1056908A (zh) * 1990-05-31 1991-12-11 中国科学院金属研究所 高性能β-氮化硅晶晶须的制备方法
US6096656A (en) * 1999-06-24 2000-08-01 Sandia Corporation Formation of microchannels from low-temperature plasma-deposited silicon oxynitride
CN1666820A (zh) * 2004-03-12 2005-09-14 同济大学 贵金属负载介孔氮氧化硅复合催化剂及其制备方法
CN1877879A (zh) * 2005-06-06 2006-12-13 施乐公司 有机电子器件的阻挡层

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