CN108176386B - Melamine bonded chromatographic stationary phase, preparation method thereof and metal ion modified melamine bonded chromatographic stationary phase - Google Patents
Melamine bonded chromatographic stationary phase, preparation method thereof and metal ion modified melamine bonded chromatographic stationary phase Download PDFInfo
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- CN108176386B CN108176386B CN201810040093.9A CN201810040093A CN108176386B CN 108176386 B CN108176386 B CN 108176386B CN 201810040093 A CN201810040093 A CN 201810040093A CN 108176386 B CN108176386 B CN 108176386B
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Abstract
The invention discloses a melamine bonded chromatographic stationary phase, a preparation method thereof and a metal ion modified melamine bonded chromatographic stationary phase. The preparation method comprises the following steps: 1) reacting an isocyanic acid alkyl silane coupling agent with an inorganic matrix filler to obtain an isocyanic acid alkyl silane coupling agent bonded stationary phase; 2) reacting an isocyanic acid alkyl silane coupling agent bonded stationary phase with melamine to obtain a melamine bonded chromatographic stationary phase; the isocyanatoalkylsilane coupling agent has the structural general formula shown in the specification:
wherein X is methyl or ethyl, and m is 3-6. The preparation method is simple in preparation process and low in cost. The raw materials required by the invention are easy to obtain, the source is wide, the raw materials can be directly used without any modification, the preparation period is short, the cost is low, the preparation process is simple, and the operation is very simple and convenient.
Description
Technical Field
The invention belongs to the technical field of liquid chromatography, and particularly relates to a melamine bonded chromatography stationary phase, a preparation method thereof and a metal ion modified melamine bonded chromatography stationary phase.
Background
The high performance liquid chromatography is the most important component of the modern chromatographic technology, is one of the most rapid and widely applied analytical technologies of recent analytical chemistry, and plays an increasingly important role in a plurality of fields such as chemical industry, medicine, food, environmental protection, biochemistry, industrial preparation and the like. In a high performance liquid chromatography system, a stationary phase is in an important position, and the development of a novel stationary phase is always the most active leading research field of modern high performance liquid chromatography.
Melamine (Melamine) is called Melamine, cyanuramide and tripolyamide for short, and belongs to triazine nitrogen-containing heterocyclic compounds. Molecular formula C3H6N6Relative molecular mass 126.12. The melamine is white crystalline powder, and can be dissolved in methanol, formaldehyde, acetic acid, hot glycol, glycerol and pyridine; slightly soluble in water and ethanol; insoluble in diethyl ether, benzene and carbon tetrachloride. Melamine is an organic chemical intermediate product with wide application, and the main application is as raw material for producing melamine formaldehyde resin (MF), and can be used for producing film, adhesive, tableware, adhesive, moulding compound, coating and fire retardant, and is also a metabolite of insecticide cyromazine in animal and plant bodies.
Three free amino groups and one triazine ring exist in melamine molecules, and the melamine molecules have relatively strong polarity and certain aromaticity, wherein the amino groups can provide reaction activity and can also serve as a hydrogen bond action source; the triazine ring contains three nitrogen atoms with lone pair electrons and can also be used as an electron acceptor for complexing metal ions. Therefore, the melamine is fixed on the chromatographic separation particle microsphere to form a corresponding stationary phase and a metal ion modified stationary phase. At present, the preparation and application research of the stationary phase of melamine bonding chromatography is still relatively rare.
Disclosure of Invention
The invention aims to provide a melamine bonded chromatographic stationary phase, a preparation method thereof and a metal ion modified melamine bonded chromatographic stationary phase.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a melamine-bonded chromatographic stationary phase, comprising the steps of:
1) reacting an isocyanic acid alkyl silane coupling agent with an inorganic matrix filler to obtain an isocyanic acid alkyl silane coupling agent bonded stationary phase;
2) reacting an isocyanic acid alkyl silane coupling agent bonded stationary phase with melamine to obtain a melamine bonded chromatographic stationary phase;
the isocyanic alkyl silane coupling agent has a structural general formula shown in a formula I:
wherein X is methyl or ethyl, and m is 3-6.
According to the present invention, preferably, the preparation method comprises the steps of:
1) adding an inorganic matrix filler into a solution in which an isocyanato alkyl silane coupling agent is dissolved, adding a catalyst in an inert atmosphere for reaction, and cooling, filtering, washing and drying in vacuum to obtain an isocyanato alkyl silane coupling agent bonded stationary phase;
2) dispersing an isocyanic alkyl silane coupling agent bonded stationary phase in a solvent, adding melamine and a catalyst in an inert atmosphere, stirring for dissolving, reacting, cooling, filtering, washing and drying to obtain the melamine bonded chromatographic stationary phase.
According to the present invention, preferably, in step 1), the solution is an anhydrous toluene solution dissolved with an isocyanatoalkylsilane coupling agent; in the step 1) and the step 2), the catalyst is triethylamine.
According to the invention, in the step 1), the reaction temperature is preferably 100-160 ℃ and the reaction time is 8-24 h; in the step 2), the reaction temperature is 50-100 ℃, and the reaction time is 6-24 h.
According to the present invention, preferably, the inorganic matrix filler is in the form of microspheres selected from, but not limited to, silica gel, zirconia, titania or alumina, and has a particle size of 2.5 to 10 μm.
According to the present invention, preferably, the isocyanatoalkylsilane is used in an amount of 1 to 6mmol per 1g of the inorganic matrix filler, and the molar ratio of the isocyanatoalkylsilane coupling agent to melamine is 1:1 to 8.
According to the present invention, preferably, the solvent is dimethyl sulfoxide or a mixed solvent of anhydrous toluene and dimethyl sulfoxide, and the volume of the anhydrous toluene in the mixed solvent is not more than 4 times that of the dimethyl sulfoxide.
The second aspect of the invention provides a melamine bonded chromatographic stationary phase prepared by the preparation method.
The third aspect of the invention provides a metal ion modified melamine bonding chromatography stationary phase, which is obtained by modifying the melamine bonding chromatography stationary phase with an inorganic metal ion solution, wherein the structural general formula of the metal ion modified melamine bonding chromatography stationary phase is shown as formula II:
wherein M isn+Is a metal ion.
According to the present invention, preferably, the metal ions are silver ions, copper ions, nickel ions, cobalt ions or zinc ions, but are not limited to silver ions, copper ions, nickel ions, cobalt ions or zinc ions.
The invention has the following advantages:
1) the preparation method is simple in preparation process and low in cost. The raw materials required by the invention are easy to obtain, the source is wide, the raw materials can be directly used without any modification, the preparation period is short, the cost is low, the preparation process is simple, and the operation is very simple and convenient.
2) The application range is wide. The melamine bonded chromatographic stationary phase provided by the invention can be used as a novel normal phase chromatographic stationary phase, can have the chromatographic performance of silver ion or metal chelation after being subjected to metal ion modification, and has higher application value and potential.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a chromatogram separation diagram of five aniline compounds (1: N, N-dimethylaniline, 2: N-methylaniline, 3: o-toluidine, 4: aniline, 5: o-nitroaniline), wherein FIG. 1(a) is a melamine bonded silica gel stationary phase, and FIG. 1(b) is an aminopropyl silica gel stationary phase.
FIG. 2 is a chromatogram of an aminophenol isomer (1: o-aminophenol; 2: m-aminophenol; 3: p-aminophenol), wherein FIG. 2(a) is a melamine-bonded silica stationary phase and FIG. 2(b) is an aminopropyl silica stationary phase.
FIG. 3 is a chromatographic separation of hydroquinone isomers (1: catechol; 2: resorcinol; 3: hydroquinone), wherein FIG. 3(a) is a melamine-bonded silica gel stationary phase and FIG. 3(b) is an aminopropyl silica gel stationary phase.
FIG. 4 is a graph of the separation of 5 unsaturated fatty acid methyl esters (1: methyl oleate; 2: methyl linoleate; 3: methyl linolenate; 4: EPA methyl ester; 5: DHA methyl ester) on a melamine immobilized silver ion chromatographic stationary phase.
FIG. 5 is a diagram showing the separation of unsaturated fatty acid methyl ester (1: methyl oleate; 2: methyl linoleate; 3: methyl linolenate) in rapeseed oil on the stationary phase of melamine-fixed silver ion chromatography.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1:
adding 5.0 g of silica gel (5.0 mu m) microspheres dried at 120 ℃ for 6 hours into an anhydrous toluene solution (150mL) dissolved with 5.0mmol of 3-isocyanatopropyltrimethoxysilane, taking triethylamine as a catalyst in a nitrogen atmosphere, reacting at 100 ℃ for 8 hours, cooling, carrying out suction filtration, washing, carrying out vacuum drying to obtain the isocyanato-bonded silica gel, then putting the isocyanato-bonded silica gel and melamine (5.0mmol) into 150mL of an anhydrous toluene/dimethyl sulfoxide (v/v, 4:1) mixed solution, shaking uniformly, filling nitrogen, taking triethylamine as a catalyst, reacting at 50 ℃ for 24 hours, cooling, carrying out suction filtration and washing after the reaction is finished, and drying the obtained solid in a vacuum drying oven at 40 ℃ for 24 hours to obtain the melamine-bonded silica gel chromatographic stationary phase. The stationary phase structure is as follows:
example 2:
adding 5.0 g of silica gel (2.5 mu m) microspheres dried at 120 ℃ for 6 hours into an anhydrous toluene solution (150mL) dissolved with 10.0mmol of 3-isocyanatohexyltriethoxysilane, reacting at 110 ℃ for 16 hours by using triethylamine as a catalyst in a nitrogen atmosphere, cooling, suction-filtering, washing, vacuum-drying to obtain the isocyanato-bonded silica gel, then putting the isocyanato-bonded silica gel and melamine (20.0mmol) into 150mL of an anhydrous toluene/dimethyl sulfoxide (v/v, 2:1) mixed solution, shaking uniformly, introducing argon, reacting at 80 ℃ for 12 hours by using pyridine as a catalyst, cooling, suction-filtering, washing after the reaction is finished, and drying the obtained solid in a vacuum drying oven at 40 ℃ for 24 hours to obtain the melamine-bonded silica gel chromatographic stationary phase. The stationary phase structure is as follows:
example 3:
adding 5.0 g of titanium oxide (7.5 mu m) microspheres dried for 6 hours at 120 ℃ into an anhydrous toluene solution (150mL) dissolved with 30.0mmol of 3-isocyanatopropyltriethoxysilane, taking triethylamine as a catalyst in a nitrogen atmosphere, reacting for 24 hours at 160 ℃, cooling, suction filtering, washing, vacuum drying to obtain the isocyanato-bonded titanium oxide microspheres, then adding the isocyanato-bonded titanium oxide and melamine (60.0mmol) into 150mL of an anhydrous toluene/dimethyl sulfoxide (v/v, 1:1) mixed solution, shaking uniformly, introducing nitrogen, taking triethylamine as a catalyst, reacting for 24 hours at 100 ℃, cooling, suction filtering, washing after the reaction is finished, and drying the obtained solid in a vacuum drying oven for 24 hours at 40 ℃ to obtain the melamine-bonded titanium oxide chromatographic stationary phase. The stationary phase structure is as follows:
example 4:
adding 5.0 g of zirconia (10.0 mu m) microspheres dried for 6 hours at 120 ℃ into an anhydrous toluene solution (150mL) dissolved with 5.0mmol of 3-isocyanatopropyltriethoxysilane, reacting at 120 ℃ for 24 hours in a nitrogen atmosphere by using triethylamine as a catalyst, cooling, carrying out suction filtration, washing, carrying out vacuum drying to obtain the isocyanato-bonded zirconia, then putting the isocyanato-bonded zirconia and melamine (25.0mmol) into 150mL of dimethyl sulfoxide, shaking up, then filling argon, reacting at 60 ℃ for 24 hours by using triethylamine as a catalyst, cooling, carrying out suction filtration and washing after the reaction is finished, and drying the obtained solid in a vacuum drying oven at 40 ℃ for 24 hours to obtain the melamine-bonded zirconia chromatographic stationary phase. The stationary phase structure is as follows:
example 5:
adding 5.0 g of alumina (5.0 mu m) microspheres dried for 6 hours at 120 ℃ into an anhydrous toluene solution (150mL) dissolved with 5.0mmol of 3-isocyanatopropyltrimethoxysilane, taking triethylamine as a catalyst in a nitrogen atmosphere, reacting for 24 hours at 110 ℃, cooling, suction-filtering, washing, vacuum-drying to obtain isocyanato-bonded alumina, then putting the isocyanato-bonded alumina and melamine (15.0mmol) into 150mL of an anhydrous toluene/dimethyl sulfoxide (v/v, 1:1) mixed solution, shaking uniformly, filling nitrogen, taking triethylamine as a catalyst, reacting for 24 hours at 60 ℃, after the reaction is finished, cooling, suction-filtering, washing, and drying the obtained solid in a vacuum drying oven for 24 hours at 40 ℃ to obtain the melamine-bonded alumina chromatographic stationary phase. The stationary phase structure is as follows:
example 6:
weighing 2.5g of silver nitrate, dissolving the silver nitrate into 80mL of methanol-water (1: 1, V/V) mixed solution, uniformly stirring, adding 4.5g of melamine bonded silica gel stationary phase, and stirring and reacting for 24 hours in dark place in a dark place. After the reaction is finished, centrifugal separation is carried out, the lower layer stationary phase is respectively washed by ethanol-n-hexane (1: 2, V/V) and (1: 5, V/V) mixed solution for 3 times, and then vacuum drying is carried out for 10 hours at the temperature of 60 ℃, so as to obtain the melamine immobilized silver ion chromatographic stationary phase. The stationary phase structure is as follows:
FIGS. 1 to 3 are graphs showing the actual separation effect of the melamine-bonded silica stationary phase and the aminopropyl silica stationary phase prepared in example 1 of the present invention, wherein FIG. 1 is a graph showing the chromatographic separation of five aniline compounds (1: N, N-dimethylaniline; 2: N-methylaniline; 3: o-toluidine; 4: m-toluidine; 5: aniline), FIG. 2 is a graph showing the chromatographic separation of 3 aminophenol isomers (1: o-aminophenol; 2: m-aminophenol; 3: p-aminophenol), and FIG. 3 is a graph showing the chromatographic separation of 3 diphenol isomers (1: catechol; 2: resorcinol; 3: hydroquinone). The spectrogram shows that the separation effect of the melamine bonded silica gel fixed phase relative to the three compounds is superior to that of the aminopropyl silica gel fixed phase with the same amino, which is probably related to the amino density on the surface of the melamine bonded silica gel fixed phase, the aromaticity of triazine ring and the comprehensive action of carbamido generated in the coupling bonding process, and fully shows that the characteristic structure of the melamine bonded silica gel fixed phase can generate relatively unique retention action and mechanism. FIG. 4 shows that the melamine-immobilized silver ion chromatographic immobilization has good separation effect relative to 5 common polyunsaturated fatty acid methyl esters (1: methyl oleate, 2: methyl linoleate, 3: methyl linolenate, 4: EPA methyl ester and 5: DHA methyl ester), the separation effect of the unsaturated fatty acid methyl esters applied to the rapeseed oil is shown in FIG. 5, and the determination result is basically consistent with the literature through the quantitative analysis of an area normalization method. The result shows that the melamine stationary phase can be simply prepared into the corresponding silver ion stationary phase or metal chelating chromatographic stationary phase after being modified by silver ions or other metal ions, thereby expanding the practical application prospect and the application range of the melamine bonded stationary phase.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (7)
1. The metal ion modified melamine bonded chromatographic stationary phase is obtained by modifying a melamine bonded chromatographic stationary phase by adopting an inorganic metal ion solution, and the structural general formula of the metal ion modified melamine bonded chromatographic stationary phase is shown as formula II:
wherein M isn+Is a metal ion;
the metal ions are silver ions, copper ions, nickel ions, cobalt ions or zinc ions;
the melamine bonded chromatographic stationary phase is prepared by a preparation method of the melamine bonded chromatographic stationary phase, which comprises the following steps:
1) reacting an isocyanic acid alkyl silane coupling agent with an inorganic matrix filler to obtain an isocyanic acid alkyl silane coupling agent bonded stationary phase;
2) reacting an isocyanic acid alkyl silane coupling agent bonded stationary phase with melamine to obtain a melamine bonded chromatographic stationary phase;
the isocyanic alkyl silane coupling agent has a structural general formula shown in a formula I:
wherein X is methyl or ethyl, and m is 3-6.
2. The metal ion-modified melamine-bonded chromatographic stationary phase according to claim 1, wherein the preparation method comprises the steps of:
1) adding an inorganic matrix filler into a solution in which an isocyanato alkyl silane coupling agent is dissolved, adding a catalyst in an inert atmosphere for reaction, and cooling, filtering, washing and drying in vacuum to obtain an isocyanato alkyl silane coupling agent bonded stationary phase;
2) dispersing an isocyanic alkyl silane coupling agent bonded stationary phase in a solvent, adding melamine and a catalyst in an inert atmosphere, stirring for dissolving, reacting, cooling, filtering, washing and drying to obtain the melamine bonded chromatographic stationary phase.
3. The metal ion-modified melamine-bonded chromatographic stationary phase according to claim 2, wherein in step 1), the solution is an anhydrous toluene solution in which an isocyanatoalkylsilane coupling agent is dissolved; in the step 1) and the step 2), the catalyst is triethylamine.
4. The metal ion modified melamine bonded chromatographic stationary phase according to claim 2, wherein in the step 1), the reaction temperature is 100-160 ℃ and the reaction time is 8-24 h; in the step 2), the reaction temperature is 50-100 ℃, and the reaction time is 6-24 h.
5. The metal ion-modified melamine-bonded chromatographic stationary phase according to claim 2, wherein the inorganic matrix filler is in the form of microspheres selected from silica gel, zirconia, titania or alumina having a particle size of 2.5-10 μm.
6. The metal ion-modified melamine-bonded chromatographic stationary phase according to claim 2, wherein the isocyanatoalkylsilane is used in an amount of 1 to 6mmol per 1g of the inorganic matrix filler, and the molar ratio of the isocyanatoalkylsilane coupling agent to melamine is 1:1 to 8.
7. The metal ion-modified melamine-bonded chromatographic stationary phase according to claim 2, wherein the solvent is dimethyl sulfoxide or a mixed solvent of anhydrous toluene and dimethyl sulfoxide, and the volume of the anhydrous toluene in the mixed solvent is not more than 4 times that of the dimethyl sulfoxide.
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