CN107262077B - A kind of preparation method being bonded organic polymer overmold silicon ball chromatographic stationary phases - Google Patents
A kind of preparation method being bonded organic polymer overmold silicon ball chromatographic stationary phases Download PDFInfo
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- CN107262077B CN107262077B CN201710473683.6A CN201710473683A CN107262077B CN 107262077 B CN107262077 B CN 107262077B CN 201710473683 A CN201710473683 A CN 201710473683A CN 107262077 B CN107262077 B CN 107262077B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3214—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the method for obtaining this coating or impregnating
- B01J20/3217—Resulting in a chemical bond between the coating or impregnating layer and the carrier, support or substrate, e.g. a covalent bond
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Abstract
The present invention relates to a kind of preparation methods of novel bonding organic polymer cladding silicon ball chromatographic stationary phases, uniform fabricated in situ contains the organic polymer layers of a large amount of epoxy group in macropore silicon outer surface of ball and duct, and polymer surfaces further are modified with the function of making it have different chromatographic isolation modes using the functional group of different structure.The organic polymer coating of the application can shield the silicone hydroxyl of silicon ball surface completely so that prepared stationary phase be suitable for include the different structure sample of basic sample solution separation;The epoxy group of polymer-coated surface is convenient to be bonded different types of functional group, is prepared into different types of stationary phase;New Stationary Phase has both the mechanical performance of silica matrix stationary phase, the chemical stability of cellular structure and polymer substrate, bio-compatibility under the premise of not destroying silicon ball cellular structure.Have the characteristics that preparation is simple, the scope of application is wide.
Description
Technical field
The present invention relates to chromatographic stationary phases technical fields, are a kind of organic polymer overmold silicon ball colors of bonding specifically
Compose the preparation method of stationary phase.
Background technique
Since the sixties in 19th century, high performance liquid chromatography is as a kind of isolation technics and method, by its analysis speed
Fast, good selective is spent, very extensive application is obtained, it is all to have become medicine, food, environment, chemical industry, method inspection etc.
The most commonly used separation analysis means in multi-field.
Chromatographic column one is to " heart " for being made chromatographic separation technology by person, and the chromatographic separation material filled in chromatographic column
It is then the most key part of chromatographic column, is that various HPLC clastotypes are rely the basis of foundation and development.The hair of HPLC technology
Exhibition, especially for the continuous improvement required in the highly selective, highly sensitive of complex sample, high-throughput isolation analysis, greatly
Ground has pushed the exploitation of new chromatographic stationary phase.
Currently, most common chromatographic stationary phases according to its matrix can be divided into two major classes in liquid chromatogram: silica matrix
The stationary phase of stationary phase and polymer substrate, the two respectively have its advantage and disadvantage.Silica gel microball is easily modified because of its high mechanical strength, surface
The advantages that have become the stationary phase matrix being most widely used at present, but the presence of the acid silicone hydroxyl of Silica Surface remaining, make
Obtain the problems such as Irreversible Adsorption, peak type hangover occur during the separation process for alkali solute;The chromatographic material chemistry of polymer substrate
Stability and the compatibility of biological sample are all better than silica gel, but its mechanical strength is generally poor, are not suitable for depressing work in high column
Make, in addition, the microballoon stationary phase of polymer substrate there is also be easy to be swollen, resistance to mass tranfer it is big, column imitates low deficiency.
Under the premise of not destroying silica gel cellular structure, in Bio-sil stromal surface and inner surfaces of pores bonded polymer
Coating prepares the silica matrix stationary phase carrier of polymer-coated, had both had the spies such as the high pressure resistant, large specific surface area of silicon ball matrix
Point, but it is strong to have both polymer substrate chemical stability, the advantages such as biological sample good compatibility.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of organic polymer overmold silicon ball chromatographies of bonding
The preparation method of stationary phase.
The purpose of the present invention is achieved through the following technical solutions:
A kind of preparation method being bonded organic polymer overmold silicon ball chromatographic stationary phases, the specific steps are that:
(1) pretreatment of silica gel particle
Silica gel particle is taken, is dispersed in the dilute alkaline soln of 0.05~0.2mol/L, after 25~35min of ultrasound, adds diluted acid molten
It is 6~7 that liquid, which adjusts pH value, sedimentation or centrifuge separation, after further sufficiently being cleaned with water, again with methanol or acetonitrile cleaning, 40~
It is dried at 60 DEG C, it is spare;
In step (1), the silica gel microball is mesoporous silicon sphere;
In step (1), the every increase 1g of handled silica gel microball, the dilute alkaline soln of 15~20mL of Ying Zengjia;
In step (1), the dilute alkaline soln is sodium hydroxide or potassium hydroxide aqueous solution;
In step (1), the dilute acid soln is dilute hydrochloric acid or dilute sulfuric acid aqueous solution;
(2) silanization treatment of silica gel particle
The silicon ball of activation is dispersed in ethanol-water solution, ammonium hydroxide and methacrylic acid 3- (trimethoxy silicon are sequentially added
Base) propyl ester (γ-MPS) reagent, after ultrasound mixes, heating reflux reaction 20~for 24 hours, methanol cleaning is dry, obtains double bond modification
Silicon ball;
In step (2), the volume ratio of alcohol-water is 3:1~4:1;
In step (2), every increase 1g silicon ball, should increase by 20~30mL ethanol-water solution, 0.6~0.8mL ammonium hydroxide and
The dosage of 1.0~1.5g γ-MPS reagent;
In step (2), the temperature that is heated to reflux is 65~75 DEG C;
(3) in-situ polymerization of polymer overmold object
Silicon ball after silanization treatment is dispersed in acetonitrile, azodiisobutyronitrile (AIBN), metering system are sequentially added
Acid glycidyl ester (GMA), ethyleneglycol dimethyacrylate (EGDMA), under the conditions of 85~95 DEG C, back flow reaction 0.5~
1.5h, cooling, centrifuge separation.It is successively cleaned with acetonitrile, DMF, obtains the silicon ball of the polymer overmold bonding containing epoxy group;
In step (3), every silicon ball for increasing 1g silanization treatment should increase by 30~40mL acetonitrile, 20~25mg
The dosage of AIBN, 1.0~1.5mL GMA and 0.3~0.5mL EGDMA;
(4) bonding of functional group
In a suitable solution by the polymer-modified silicon ball dispersion containing azido group, addition can be anti-with epoxy group
The modified compound answered, is reacted, dry after sufficiently being cleaned using ultrapure water, methanol after the reaction was completed;It is fixed as chromatography
Mutually dress column uses;
In this step, used reaction dissolvent can be selected according to the compound property modified;Modification is logical
The reaction of 1~3 step is crossed to complete.
Compared with prior art, the positive effect of the present invention is:
(1) the silicon ball stationary phase of the polymer overmold bonding prepared by the present invention is uniform in silicon ball surface and inner surfaces of pores
Ground coating has been bonded one layer of polymeric coating, and preparation method is simple, cost is relatively low, stationary phase stable structure;
(2) the silicon ball stationary phase of the polymer overmold bonding prepared by, had both had that silicon ball matrix is high pressure resistant, large specific surface area
The features such as, and have both the advantages such as polymer substrate chemical stability is strong, and bio-compatibility is good;
(3) the silicon ball stationary phase outer surface of the polymer overmold bonding prepared by and inner surfaces of pores coat bonded polymer
Coating, polymeric layer can shield the silicone hydroxyl of silicon ball completely, and the polymer coating being bonded effectively shields silicone hydroxyl in chromatography
Negative effect in separation process, so that prepared stationary phase is suitable for the different structure sample including basic sample solution
Separation analysis.
(4) contain epoxy group in the polymer of silicon ball surface bonding, facilitate the different types of functional group of bonding, so as to
Different types of stationary phase is prepared, the chromatographic separation process applied to different mode.
Detailed description of the invention
Attached drawing 1 is the preparation process schematic diagram that a kind of organic polymer in-stiu coating is bonded silicon ball chromatographic stationary phases;
Attached drawing 2 is the separating effect using the stationary phase prepared according to process shown in attached drawing 1 to two kinds of organic acids, chromatostrip
Part: isocratic elution, 20% ammonium acetate aqueous solution (30mM, pH value 3.15)-acetonitrile, flow velocity 0.5mL/min, Detection wavelength
254nm;
Attached drawing 3 is the separating effect using the stationary phase prepared according to process shown in attached drawing 1 to 5 kinds of nucleoside bases, in figure,
EB represents ethylbenzene, and T represents thymidine, and U represents uracil, and A represents adenine, and C represents cytimidine, and G represents guanine, chromatography
Condition: mobile phase is acetonitrile-water (containing 0.1% triethylamine) system, gradient elution (0-5min, 95% acetonitrile, 5-15min, 95-
80% acetonitrile), flow velocity 0.5mL/min, Detection wavelength 254nm.
Specific embodiment
A kind of specific reality for the preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases of the present invention presented below
Apply mode.
Embodiment 1
According to method shown in attached drawing 1, in silica gel particle outer surface and duct in-stiu coating bonding organic polymer and modify
Maltose group is used as chromatographic stationary phases, specific preparation step are as follows:
(1) pretreatment of silica gel particle
Take 5g silica gel microball (4 μm of particle diameter, aperture), it is dispersed in the sodium hydroxide solution of 0.1mol/L,
After ultrasonic 30min, adding dilute hydrochloric acid to adjust pH value is 6.5~7, after sufficiently being cleaned with water, is cleaned three times, 50 DEG C with methanol or acetonitrile
Lower drying, it is spare.
(2) silanization treatment of silica matrix
The silica gel particle activated in step (1) is dispersed in 150mL alcohol-water (volume ratio 4:1) solution, successively plus
Enter 3mL ammonium hydroxide and 6g methacrylic acid 3- (trimethoxy silicon substrate) propyl ester (γ-MPS) reagent, after ultrasound mixes, 65~75 DEG C of items
For 24 hours, methanol cleans 3 times back flow reaction under part, dry, obtains the silicon ball of double bond modification.
(3) polymer overmold is bonded
It will be bonded the silicon ball of double bond group, is dispersed in acetonitrile, sequentially adds 100mg azodiisobutyronitrile (AIBN), 6mL
Glycidyl methacrylate (GMA), 1.5mL ethyleneglycol dimethyacrylate (EGDMA), back flow reaction under the conditions of 90 DEG C
1.5h is successively respectively cleaned 3 times with acetonitrile, DMF, obtains the silicon ball of the polymer overmold bonding containing epoxy group.
(4) epoxy group key function group is utilized
Gained silicon ball is dispersed in 180mL DMF, 0.6g NaN3 and 1g NH4Cl is added, flows back under the conditions of 90 DEG C anti-
20h is answered, the polymer-modified silicon ball containing azido group is obtained, is respectively washed 3 times using water, ethyl alcohol, is centrifuged, removes solution.
Gained silicon ball is dispersed in 150mL alcohol-water (volume ratio 2:1) solution, 2g propargyl maltose, five water of 0.74g is added
Copper sulphate (CuSO4) and 1.80g sodium ascorbate (VcNa) mix, and reaction 12h is stirred at room temperature and uses ammonia respectively after reaction
It is dry after water, EDTA aqueous solution, ultrapure water, methanol sufficiently clean.
(5) chromatography characterizes
Prepared chromatographic stationary phases are applied to the chromatographic separation process of organic acid, organic base, to obtain its chromatography point
From efficiency.As shown in attached drawing 2,3, using benzoic acid, gallic acid as acidic molecular probe, use 5 kinds of nucleoside bases for alkali
Property molecular probe investigate the chromatogram separating capacities of prepared chromatographic stationary phases, the result shows that, prepared chromatographic stationary phases
Institute's organic acid, organic base have good separating capacity.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as
In protection scope of the present invention.
Claims (9)
1. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases, which is characterized in that the specific steps are that:
(1) pretreatment of silica gel particle
Silica gel particle is taken, is dispersed in the dilute alkaline soln of 0.05~0.2mol/L, after 25~35min of ultrasound, adds dilute acid soln tune
Saving pH value is 6~7, sedimentation or centrifuge separation, after further sufficiently being cleaned with water, again with methanol or acetonitrile cleaning, and 40~60 DEG C
Lower drying, it is spare;
(2) silanization treatment of silica gel particle
The silicon ball of activation is dispersed in ethanol-water solution, ammonium hydroxide and methacrylic acid 3- (trimethoxy silicon substrate) are sequentially added
Propyl ester γ-MPS reagent, after ultrasound mixes, heating reflux reaction 20~for 24 hours, methanol cleaning is dry, obtains the silicon of double bond modification
Ball;
(3) in-situ polymerization of polymer overmold object
Silicon ball after silanization treatment is dispersed in acetonitrile, azodiisobutyronitrile AIBN, Glycidyl methacrylate are sequentially added
Glyceride GMA, ethyleneglycol dimethyacrylate EGDMA, under the conditions of 85~95 DEG C, 0.5~1.5h of back flow reaction is cooling, from
Heart separation;It is successively cleaned with acetonitrile, DMF, obtains the silicon ball of the polymer overmold bonding containing epoxy group;
(4) bonding of functional group
Gained silicon ball is dispersed in DMF, NaN is added3And NH4Cl, back flow reaction 20h under the conditions of 90 DEG C are obtained containing azido group
Polymer-modified silicon ball in the solution by the polymer-modified silicon ball dispersion containing azido group be added and epoxy group
The modified compound of reaction, is reacted, dry after sufficiently being cleaned using ultrapure water, methanol after the reaction was completed;It is solid as chromatography
Fixed mutually dress column uses.
2. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
It is, in step (1), the silica gel microball is mesoporous silicon sphere.
3. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
It is, in step (1), the every increase 1g of handled silica gel microball, the dilute alkaline soln of 15~20mL of Ying Zengjia.
4. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
It is, in step (1), the dilute alkaline soln is sodium hydroxide or potassium hydroxide aqueous solution.
5. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
It is, in step (1), the dilute acid soln is dilute hydrochloric acid or dilute sulfuric acid aqueous solution.
6. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
It is, in step (2), the volume ratio of alcohol-water is 3:1~4:1.
7. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
It is, in step (2), every increase 1g silicon ball should increase by 20~30mL ethanol-water solution, 0.6~0.8mL ammonium hydroxide and 1.0
The dosage of~1.5g γ-MPS reagent.
8. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
It is, in step (2), the temperature that is heated to reflux is 65~75 DEG C.
9. a kind of preparation method for being bonded organic polymer overmold silicon ball chromatographic stationary phases as described in claim 1, feature
Be, in step (3), it is every increase 1g silanization treatment silicon ball, should increase by 30~40mL acetonitrile, 20~25mg AIBN,
The dosage of 1.0~1.5mL GMA and 0.3~0.5mL EGDMA.
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CN108079982B (en) * | 2017-12-22 | 2020-03-13 | 苏州纳微科技股份有限公司 | Modified silica gel filler, preparation method and application |
CN108371948A (en) * | 2018-02-09 | 2018-08-07 | 安徽师范大学 | Novel affine thiophilic silicon ball chromatographic material and its preparation method and application |
CN110787779A (en) * | 2019-12-17 | 2020-02-14 | 中国科学院兰州化学物理研究所 | Preparation and application of polymer-wrapped silica gel core-shell type chromatographic packing |
CN111138674B (en) * | 2019-12-27 | 2021-09-21 | 江苏阿尔法药业股份有限公司 | Metal organic framework polymer coated silica gel material, and preparation method and application thereof |
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CN101274271A (en) * | 2007-03-30 | 2008-10-01 | 中国科学院大连化学物理研究所 | Sugar bonding silica-gel stationary phase and method of producing the same |
CN105749887A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Preparation method of liquid chromatographic stationary phrase and glycosyl-bonded stationary phrase |
CN106669637A (en) * | 2015-11-05 | 2017-05-17 | 中国科学院大连化学物理研究所 | Hydrophilic polymer stationary phase, and preparation method and application thereof |
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CN101274271A (en) * | 2007-03-30 | 2008-10-01 | 中国科学院大连化学物理研究所 | Sugar bonding silica-gel stationary phase and method of producing the same |
CN105749887A (en) * | 2014-12-16 | 2016-07-13 | 中国科学院大连化学物理研究所 | Preparation method of liquid chromatographic stationary phrase and glycosyl-bonded stationary phrase |
CN106669637A (en) * | 2015-11-05 | 2017-05-17 | 中国科学院大连化学物理研究所 | Hydrophilic polymer stationary phase, and preparation method and application thereof |
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