CN104667877B - Contain the method that the oxide surface of hydroxyl carries out aryl boric acid modification on surface - Google Patents
Contain the method that the oxide surface of hydroxyl carries out aryl boric acid modification on surface Download PDFInfo
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- CN104667877B CN104667877B CN201510023681.8A CN201510023681A CN104667877B CN 104667877 B CN104667877 B CN 104667877B CN 201510023681 A CN201510023681 A CN 201510023681A CN 104667877 B CN104667877 B CN 104667877B
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Abstract
The invention discloses a kind of method that oxide surface for containing hydroxyl on surface carries out aryl boric acid modification.Comprise the following steps：Surface is contained to the oxide material of hydroxyl, 3 glycidyl ether oxygen propyl trimethoxy silicanes, amino phenyl boric acid and triethylamine are added in anhydrous alcoholic solvent, based on the specific surface area for the oxide material for containing hydroxyl by surface, every square metre of surface area adds 1~8 μ l 3 glycidyl ether oxygen propyl trimethoxy silicanes, 0.5~10mg amino phenyl boric acids, based on the quality for the oxide material for containing hydroxyl by surface, the volume that every gram of material adds absolute alcohol is 5~100ml, concentration of the triethylamine in absolute alcohol is 0.5~2% (v/v), 60~90 DEG C it is agitated reaction 4~24 hours after separation of solid and liquid, wash away the residual reactants of the surface of solids.The present invention can improve aryl boric acid modification amount, shorten technological process, beneficial to environmental protection, production cost can be reduced.
Description
Technical field
The present invention relates to a kind of method that oxide surface for containing hydroxyl on surface carries out aryl boric acid modification.
Background technology
In aqueous under normal temperature and pressure, aryl boric acid can be with dihydroxy compounds (cis- 1,2- dihydroxy or 1,3- bis-
Hydroxyl) form the borate of five yuan or hexatomic ring, regulation solution ph with regard to the generation or fracture of borate can be controlled, borate
Intensity and the stereochemical structure of dihydroxy compounds are closely related.Quickly and reversibly cyclic boronate is formed with dihydroxy compounds
The unique chemistry of ester make it that aryl boric acid causes great concern as recognition component, in sensing, separation, molecule from group
Extensive research and application have been obtained in terms of dress.Wherein, the oxide material (such as two of the various patterns of hydroxyl is contained on surface
Nano particle, micron particles, nanotube of silica, titanium dioxide, zinc oxide etc. etc.) surface carry out aryl boric acid functionalization repair
Decorations are the key technologies for carrying out these researchs and application.
Prior art mainly includes three kinds of methods：Method one (Glad M, et al.J.Chromatogr.A, 1980,200：
254-260) it is method using " being first grafted post-modification ", that is, first passes through silane coupler 3- glycidyl ether oxygen propyl trimethoxies
The hydrolyzable groups (methoxyl group) and the hydroxyl on oxide material surface of base silane react, and make 3- glycidyl ether oxygen propyls
Trimethoxy silane is grafted the surface for loading to the oxide material containing hydroxyl, obtains epoxy oxide material, then
Occur nucleophilic ring opening addition reaction to epoxide group using the amino of amino phenyl boric acid, obtain the oxide material of aryl boric acid modification
Material.This method needs to carry out two-step reaction (about 28 hours), and separation of solid and liquid and washing twice, technological process is long, takes, also needs
Use the toluene that toxicity is larger.Method two (Anal.Chem., 2009,81 (1)：503-508. chemistry journals .2013,71：
It is 535-540) method of " first modified grafting ", i.e., first shrinks sweet with 3- by amino phenyl boric acid in pH 9.18 aqueous solution
Non-hydrolytic group (epoxy radicals) reaction of oily ether oxygen propyl trimethoxy silicane, obtains the silane coupler of aryl boric acid modification,
Then reacted by the hydrolyzable groups (methoxyl group) and the hydroxyl on oxide material surface of silane coupler, make aryl boron
The modified silane coupler grafting of acid loads to oxide material surface, obtains the oxide material of aryl boric acid modification.It is this
Method is also required to carry out two-step reaction (about 16 hours), and each step will be repeated twice, it is necessary to strictly control different temperature
Degree is taken, it is necessary to separation of solid and liquid and once washing twice, cumbersome, and is carried out in pH 9.18 alkaline aqueous solution anti-
Seasonable is difficult itself polycondensation for avoiding silane coupler, influences the modification amount of aryl boric acid.Method three (Fanglou Li, et
Al.Anal.Chimi.Acta, 2006,580：The method for 181-187) falling within " first modified grafting ", the difference with method two
Be the silane coupler for obtaining aryl boric acid modification preparation method it is different, this method be under platinum catalyst effect, by
Aryl boric acid containing vinyl group occurs hydrosilylation addition reaction with silane containing hydrogen and obtained, hydrosilylation addition reaction must first by
Boric acid base group protects (otherwise boric acid base group can disturb catalyst), method [3] is added step radical protection reaction, this
The method of kind needs to carry out three-step reaction (about 16 hours), and separation of solid and liquid and washing, cumbersome twice, takes, it is also desirable to use
The larger toluene of toxicity, and more expensive platinum catalyst and silane containing hydrogen is needed to use, production cost is higher.
The content of the invention
The invention provides a kind of method that oxide surface for containing hydroxyl on surface carries out aryl boric acid modification.
The method of the present invention comprises the following steps：Surface is contained to oxide material, the 3- glycidyl ether oxygens third of hydroxyl
Base trimethoxy silane, amino phenyl boric acid and triethylamine are added in anhydrous alcoholic solvent, and the oxide material of hydroxyl is contained by surface
Specific surface area meter, every square metre of surface area add 1~8 μ l 3- glycidyl ether oxygen propyl trimethoxy silicanes, 0.5~
Based on 10mg amino phenyl boric acids, the quality for the oxide material that hydroxyl is contained by surface, the volume that every gram of material adds absolute alcohol is 5
~100ml, concentration of the triethylamine in absolute alcohol be 0.5~2% (v/v), 60~90 DEG C it is agitated reaction 4~24 hours after
Separation of solid and liquid, washes away the residual reactants of the surface of solids.
It is preferred that, the surface contain the oxide material of hydroxyl for silica or titanium dioxide or zinc oxide or
Person's Surface coating has the material of silica, titanium dioxide or zinc oxide.
It is preferred that, the alcoholic solvent is methanol or ethanol or isopropanol.
It is preferred that, the stirring reaction time is 6~8 hours.
It is preferred that, based on the specific surface area for the oxide material that hydroxyl is contained by surface, 3- glycidyl ether oxygen propyl front threes
The addition of TMOS is that the material per per square meter of surface area adds 2~4 μ l.
It is preferred that, based on the specific surface area for the oxide material that hydroxyl is contained by surface, the addition of amino phenyl boric acid is every
The material of per square meter of surface area adds 1~3mg.
It is preferred that, based on the quality for the oxide material that hydroxyl is contained by surface, the addition of anhydrous alcoholic solvent is every gram of material
Material adds 10~30ml.
It is preferred that, concentration of the triethylamine in anhydrous alcoholic solvent is 0.8~1.2% (v/v).
It is preferred that, the solvent that the residual reactants of the surface of solids are washed away after separation of solid and liquid be ethanol or acetone or they
The mixture of arbitrary proportion.
It is preferred that, the solvent that the residual reactants of the surface of solids are washed away after separation of solid and liquid is followed successively by 0.1mol/L bicarbonates
Sodium, 1mmol/L hydrochloric acid, pH value are neutral water and acetone.
Compared with prior art, the method for the present invention improves the modification amount of aryl boric acid；Technological process is shortened, letter
Production operation is changed；Reduce the reaction time；Avoid, using larger solvents of toxicity such as toluene, being conducive to environmental protection；Without using valency
Lattice more expensive platinum catalyst and silane containing hydrogen, reduce production cost.Beneficial effect is in particular in following several respects：
(1) prior art needs two steps or three-step reaction, and technological process is long, and the reaction time is long, and the technology of the present invention is only needed
Single step reaction is wanted, the preferably reaction time is 6~8 hours, all more time saving than prior art；
(2) different temperature (such as method two) are strictly controlled the need for prior art has, solid-liquid twice is carried out the need for having
Separation and washing (method one and method three), operation are cumbersome, and the technology of the present invention only needs to maintain a reaction temperature, only needs
Carry out a separation of solid and liquid and washing, operation facility；
(3) prior art needs to use the higher platinum catalyst of price and silane containing hydrogen (method three), and the technology of the present invention
The use of inexpensive triethylamine is catalyst, uses the price 3- glycidyl ether oxygen propyl trimethoxy silicon cheaper than silane containing hydrogen
Alkane；
(4) prior art needs to use the larger organic solvent of the toxicity such as toluene, and the alcoholic solvent toxicity that the present invention is used
It is much smaller, be conducive to environmental protection；
(5) compared with prior art, beneficial effects of the present invention, which are more highlightedly embodied in, improves repairing for aryl boric acid
Decorations amount.The property of borate is formed under weak basic condition using aryl boric acid and catechol, in pH 8.5 aqueous solution,
Be modified with aryl boric acid material can Adsorption of Catechol, aryl boric acid can be characterized indirectly by the adsorbance of catechol
Modification amount.On every gram of silicon dioxide microsphere (UniSil 10-100, Suzhou Nano-Micro Bio-technology Co., Ltd.), the present invention
Catechol adsorbance be 152 μm of ol (embodiment 1), more than 65 μm of ol (comparative example 1) of art methods one and existing
26 μm of ol (comparative example 3) of technical method two；Equally, have in every gram of homemade Surface coating on the magnetic-particle of silica,
The catechol adsorbance of the present invention is 165 μm of ol (embodiment 2), also greater than 50 μm of ol (comparative examples of art methods one
2) with 21 μm of ol (comparative example 4) of art methods two.
Embodiment
With reference to example, the invention will be further described, and these embodiments are only intended to the explanation present invention, do not limit
The system present invention.Wherein embodiment 1~7 is the preparation process of the present invention, and comparative example 1~4 is there is provided the He of method one in the prior art
The preparation process of method two.Anhydrous alcoholic solvent (water content ＜ 0.01%) is to pass through magnesium powder to analyze pure anhydrous alcoholic solvent as raw material
Obtained with iodine backflow drying process, triethylamine is dried by potassium hydroxide.
Catechol adsorbs quantity measuring method：The accurate aryl boric acid decorative material for weighing 60mg or so is added to
In the 20.00ml catechol aqueous solution (0.06mg/ml, pH 8.5), 30 DEG C of constant temperature oscillations 2 hours carry out adsorbing real for the first time
Test, centrifuge or separation of solid and liquid is carried out with attraction, solid is washed with the cushioning liquid of pH 8.5 in three times (each 10ml), solid
20.00ml acetums 30 DEG C of (pH 3.0) constant temperature oscillation 2 hours is added, first time desorption experiment, separation of solid and liquid, solid is carried out
Three times (each 10ml) is washed with acetum (pH 3.0), solid is added in the 20.00ml catechol aqueous solution again
(0.06mg/ml, pH 8.5), 30 DEG C of constant temperature oscillations 2 hours carry out second of adsorption experiment, and separation of solid and liquid takes supernatant in neighbour
The maximum absorption wave strong point mensuration absorbance (276nm) of benzenediol, the change of catechol absorbance before and after being adsorbed according to second
Change, calculate the adsorbance for obtaining catechol.
Embodiment 1 is in silicon dioxide microsphere surface modification aryl boric acid
Silicon dioxide microsphere (UniSil 10-100, Suzhou Nano-Micro Bio-technology Co., Ltd.) uses 20% hydrochloric acid solution
(5ml/g) back flow reaction 6 hours, solid-liquid centrifugation separation (8000r/min), solid is washed with water to neutrality, 150 DEG C of vacuum drying
8 hours, activated silica microballoon (specific surface area about 257m is made2/g)。
By activated silica microballoon produced above, 3- glycidyl ether oxygen propyl trimethoxy silicanes, aminobenzene boron
Acid and triethylamine are added in absolute ethyl alcohol, based on the specific surface area of activated silica microballoon, and every square metre of surface area adds 1
μ l 3- glycidyl ether oxygen propyl trimethoxy silicanes, 0.5mg amino phenyl boric acids, by the quality of activated silica microballoon
Meter, the volume that every gram of material adds absolute ethyl alcohol is 5ml, and concentration of the triethylamine in absolute ethyl alcohol is 0.5% (v/v), 90
Solid-liquid centrifugation is separated after DEG C agitated reaction 4 hours, and solid uses 0.1mol/L sodium acid carbonates and 1mmol/L salt acid elutions successively,
Then it is neutrality to be washed with water to pH value, finally be washed once with acetone, 60 DEG C of vacuum drying, obtains aryl boric acid modification material
Material, it is 128 μm of ol/g to determine its catechol adsorbance.
Embodiment 2 is in silicon dioxide microsphere surface modification aryl boric acid
By activated silica microballoon (UniSil 10-100, Suzhou Nano-Micro Bio-technology Co., Ltd., in advance by implementation
Example 1 is activated and dried), 3- glycidyl ether oxygen propyl trimethoxy silicanes, amino phenyl boric acid and triethylamine add it is anhydrous
In isopropanol, based on the specific surface area of activated silica microballoon, every square metre of surface area adds 2 μ l 3- glycidol ethers
Oxygen propyl trimethoxy silicane, 1mg amino phenyl boric acids, based on the quality of activated silica microballoon, every gram of material adds anhydrous
The volume of isopropanol was 10ml, and concentration of the triethylamine in absolute ethyl alcohol is 0.8% (v/v), in 90 DEG C of agitated reactions 6 hours
Solid-liquid centrifugation is separated afterwards, and the residual reactants of the surface of solids are washed away with acetone, and 60 DEG C of vacuum drying obtain aryl boric acid modification material
Material, it is 143 μm of ol/g to determine its catechol adsorbance.
Embodiment 3 is in silicon dioxide microsphere surface modification aryl boric acid
By activated silica microballoon (UniSil 10-100, Suzhou Nano-Micro Bio-technology Co., Ltd., in advance by implementation
Example 1 is activated and dried), 3- glycidyl ether oxygen propyl trimethoxy silicanes, amino phenyl boric acid and triethylamine add it is anhydrous
In ethanol, based on the specific surface area of activated silica microballoon, every square metre of surface area adds 4 μ l 3- glycidyl ether oxygens
Propyl trimethoxy silicane, 3mg amino phenyl boric acids, based on the quality of activated silica microballoon, every gram of material adds anhydrous second
The volume of alcohol is 30ml, and concentration of the triethylamine in absolute ethyl alcohol is 1.2% (v/v), solid after 60 DEG C of agitated reactions 8 hours
Liquid is centrifuged, and the residual reactants of the surface of solids are washed away with ethanol, and 60 DEG C of vacuum drying obtain aryl boric acid decorative material,
It is 152 μm of ol/g to determine its catechol adsorbance.
Embodiment 4 is in silicon dioxide microsphere surface modification aryl boric acid
By activated silica microballoon (UniSil 10-100, Suzhou Nano-Micro Bio-technology Co., Ltd., in advance by implementation
Example 1 is activated and dried), 3- glycidyl ether oxygen propyl trimethoxy silicanes, amino phenyl boric acid and triethylamine add it is anhydrous
In methanol, based on the specific surface area of activated silica microballoon, every square metre of surface area adds 8 μ l 3- glycidyl ether oxygens
Propyl trimethoxy silicane, 10mg amino phenyl boric acids, based on the quality of activated silica microballoon, every gram of material is added without water beetle
The volume of alcohol is 100ml, and concentration of the triethylamine in absolute ethyl alcohol is 2% (v/v), solid after 60 DEG C of agitated reactions 24 hours
Liquid is centrifuged, and the residual reactants of the surface of solids are washed away with isometric mixed solvent of ethanol and acetone, and 60 DEG C are dried in vacuo,
Aryl boric acid decorative material is obtained, it is 156 μm of ol/g to determine its catechol adsorbance.
Embodiment 5 has the magnetic-particle surface modification aryl boric acid of silica in Surface coating
4.73g Iron(III) chloride hexahydrates and 3.92g iron ammonium sulfates are dissolved in 50ml water, are protected in stirring and nitrogen
Under, 10mL ammoniacal liquor (28%) is added dropwise, 65 DEG C are reacted 1.5 hours, and 80 DEG C are cured 1 hour, and separation of solid and liquid is carried out with attraction, Gu
It is neutrality that body, which is washed with water to pH value, be washed once with ethanol, and 150 DEG C are dried in vacuo 8 hours, obtain magnetic nanoparticle.
0.2g magnetic nanoparticles are dispersed in 200ml ethanol water mixed solution (4: 1), ultrasonic 30min, are stirred, and are added
2mL ammoniacal liquor (28%), is added dropwise 4ml tetraethoxysilanes ethanol solution (1: 1), and 45 DEG C are reacted 12 hours, are carried out with attraction
Separation of solid and liquid, is washed with water to neutrality, washed once with 10ml ethanol, and 150 DEG C are dried in vacuo 8 hours, and obtaining Surface coating has
Magnetic-particle (the specific surface area about 42m of silica2/g)。
Surface coating produced above is had to magnetic-particle, the 3- glycidyl ether oxygen propyl trimethoxy silicon of silica
Alkane, amino phenyl boric acid and triethylamine are added in absolute ethyl alcohol, there is the specific surface area of the magnetic-particle of silica by Surface coating
Meter, every square metre of surface area adds 3 μ l 3- glycidyl ether oxygen propyl trimethoxy silicanes, 2mg amino phenyl boric acids, by table
The quality meter for the magnetic-particle that face is coated with silicon oxide, the volume that every gram of material adds absolute ethyl alcohol is 25ml, and triethylamine exists
Concentration in absolute ethyl alcohol is 1% (v/v), in 90 DEG C of agitated reactions 6 hours, carries out separation of solid and liquid with attraction, uses second
Alcohol washes away the residual reactants of the surface of solids, then washed once with acetone, 60 DEG C of vacuum drying, obtains aryl boric acid modification material
Material, it is 165 μm of ol/g to determine its catechol adsorbance.
Embodiment 6 is in nano titanium oxide surface modification aryl boric acid
By nano titanium oxide (German Degussa P25 types, 50 ± 15m of specific surface area2/ g), 3- glycidyl ether oxygen propyls
Trimethoxy silane, amino phenyl boric acid and triethylamine are added in absolute ethyl alcohol, based on the specific surface area of nano titanium oxide, are often put down
The surface area of square rice adds 4 μ l 3- glycidyl ether oxygen propyl trimethoxy silicanes, 3mg amino phenyl boric acids, by nano-silica
Change the quality meter of titanium, the volume that every gram of material adds absolute ethyl alcohol is 30ml, and concentration of the triethylamine in absolute ethyl alcohol is 0.8%
(v/v), in 90 DEG C of agitated reactions 8 hours, solid-liquid centrifugation separation, solid washes away the residual reactants of the surface of solids with ethanol,
60 DEG C of vacuum drying, obtain aryl boric acid decorative material, and it is 168 μm of ol/g to determine its catechol adsorbance.
Embodiment 7 is in zinc oxide nano nanotube surface modified 2-(arylthio) ylboronic acid
Titanium sheet is pre-processed：Titanium sheet (1 × 1cm2, thickness 0.5mm) polished respectively with the abrasive paper for metallograph of 400,600,1000 mesh
Polishing, is all cleaned by ultrasonic 5min in distilled water after having polished every time, the titanium sheet of mirror-smooth is obtained, then in 1mo/L
Sulfuric acid solution in be cleaned by ultrasonic 5min, sulfuric acid solution is totally remained with distilled water flushing, then successively in acetone, ethanol, distillation
Each ultrasonic 5min in water, nitrogen stream drying is stand-by.
Electrochemical deposition method prepares zinc oxide nano rod：Take isometric 40mmol/L hexa solutions and
40mmol/L zinc nitrate solutions are mixed to get electrolyte, using three-electrode system, and it is 85 DEG C to control electrolyte temperature, in -0.9V
Constant potential under the conditions of deposit 7000s, reaction terminates, take out electrode, with the clean residual solution of distilled water flushing, in titanium plate surface
The ZnO nano-rod array of upright proper alignment is made.
Chemical corrosion method prepares zinc oxide nano mitron：The titanium sheet that there is zinc oxide nano rod on surface is placed in 0.125mol/L
In NaOH solution, 85 DEG C of reaction 90min of water-bath take out the titanium sheet clean residual solution of distilled water flushing, are made in titanium plate surface
(specific surface area is about 60m to the ZnO nanotube/array of substantially vertical orientation2/g)。
The titanium sheet that there is ZnO nanotube/array on surface produced above is placed in 3- glycidyl ether oxygen propyl trimethoxy silicon
In alkane, amino phenyl boric acid, the mixed solution of triethylamine and 30ml absolute ethyl alcohols, mixed solution can be complete by ZnO nanotube/array
Complete immersion, based on the specific surface area of ZnO nanotube/array, every square metre of surface area adds 2 μ l 3- glycidyl ether oxygens third
Base trimethoxy silane, l mg amino phenyl boric acids, concentration of the triethylamine in absolute ethyl alcohol are 1.2% (v/v), at 90 DEG C through stirring
Reaction 8 hours is mixed, titanium sheet is taken out, with the residual solution on alcohol flushing clean surface, nitrogen stream drying obtains aryl boric acid and repaiied
Exterior material, it is 35 μm of ol/g to determine its catechol adsorbance.
Comparative example 1 is with art methods one in earth silicon material surface modification aryl boric acid
(embodiment 1 is pressed to 0.2g silicon dioxide microspheres in advance by UniSil 10-100, Suzhou Nano-Micro Bio-technology Co., Ltd.
Activated and dried), that 0.15ml 3- glycidyl ether oxygen propyl trimethoxy silicanes and 50 μ l triethylamines add 5ml is anhydrous
In toluene, nitrogen is protected, return stirring reaction 4 hours, and centrifugation carries out separation of solid and liquid, and three times are respectively washed (often with toluene and acetone
Secondary 10ml), 60 DEG C of vacuum drying obtain the grafting of 3- glycidyl ether oxygen propyl trimethoxy silicanes and load to silica surface
Epoxy earth silicon material.
Above epoxy earth silicon material is scattered in 20ml water, 100mg 3- amino phenyl boric acids are added, used
1mol/L sodium hydroxide solutions regulation pH value is 8.5, ultrasonic 10min, is with 1mol/L sodium hydroxide solutions regulation pH value again
8.5, reacted 24 hours in shaken at room temperature, centrifugal solid-liquid separation, solid is successively with 10ml 0.5mol/L sodium chloride, 0.1mol/L
Sodium acid carbonate, 1mmol/L hydrochloric acid, water and acetone washing, 60 DEG C of vacuum drying obtain aryl boric acid decorative material, determine it adjacent
Benzenediol adsorbance is 65 μm of ol/g.
Comparative example 2 has the magnetic-particle surface modification aryl boric acid of silica with art methods one in Surface coating
0.2g is had the magnetic-particle of silica, 0.025ml 3- glycidol ethers by the homemade Surface coating of embodiment 5
Oxygen propyl trimethoxy silicane and 50 μ l triethylamines are added in 5ml dry toluenes, and nitrogen protection, return stirring reacts 4 hours, magnetic
Iron attracts to carry out separation of solid and liquid, and solid with respectively three times (each 10ml) of washing, the 60 DEG C of vacuum drying of toluene and acetone, is obtained successively
The epoxy magnetic-particle of 3- glycidyl ether oxygen propyl trimethoxy silicanes grafting load.
Above epoxy magnetic nanoparticle is scattered in 20ml water, 16mg 3- amino phenyl boric acids are added, used
1mol/L sodium hydroxide solutions regulation pH is 8.5, ultrasonic 10min, is again 8.5 with 1mol/L sodium hydroxide solutions regulation pH,
Reacted 24 hours in shaken at room temperature, attraction carries out separation of solid and liquid, solid successively with 10ml 0.5mol/L sodium chloride,
0.1mol/L sodium acid carbonates, 1mmol/L hydrochloric acid, water and acetone washing, 60 DEG C of vacuum drying obtain aryl boric acid decorative material,
It is 50 μm of ol/g to determine its catechol adsorbance.
Comparative example 3 is with art methods two in earth silicon material surface modification aryl boric acid
100mg 3- amino phenyl boric acids are dissolved in 20ml water, are 9.18, ice with 1mol/L sodium hydroxide solutions regulation pH
Bath is cooled to after 0 DEG C, under stirring, and 0.08ml 3- glycidyl ether oxygen propyl trimethoxy silicanes, heating is slowly added dropwise
To 40 DEG C, stirring reaction 6 hours, then ice bath cooling 5min, after temperature is reduced to 0 DEG C, then is slowly added dropwise 0.08ml 3- contractings
Water glycerine ether oxygen propyl trimethoxy silicane, is warming up to 65 DEG C, is again stirring for reaction 6 hours, obtains the silicon of aryl boric acid modification
Alkane coupling agent aqueous solution.The control of the step reaction temperature and the speed ten that 3- glycidyl ether oxygen propyl trimethoxy silicanes are added dropwise
Divide important, otherwise 3- glycidyl ether oxygen propyl trimethoxy silicanes can be hydrolyzed largely and polycondensation, occur a large amount of whites in solution
Dregs, hinder the further progress of reaction.Find that the step reacts very bad operation and control, initial clarification in experimentation
Transparent solution is gradually muddy, and what is finally obtained is the white solution of milk shape, illustrates 3- glycidyl ether oxygen propyl trimethoxies
Base silane there occurs itself significant polycondensation reaction.
(embodiment 1 is pressed to 0.2g silicon dioxide microspheres in advance by UniSil 10-100, Suzhou Nano-Micro Bio-technology Co., Ltd.
Activated and dried) in add the silane coupler aqueous solution that 10ml aryl boric acids are modified, 75 DEG C of stirring reactions 2 hours, from
The silane coupler aqueous solution of 10ml aryl boric acids modification is added in heart separation of solid and liquid, abandoning supernatant, solid again, 75 DEG C are stirred
Reaction 2 hours is mixed, centrifugal solid-liquid separation, solid is washed with water four times (each 10ml), washed once with 10ml acetone, and 60 DEG C true
Sky is dried, and obtains aryl boric acid decorative material, and it is 26 μm of ol/g to determine its catechol adsorbance.
Comparative example 4 has the magnetic-particle surface modification aryl boron of silica with method two in the prior art in Surface coating
Acid
16mg 3- amino phenyl boric acids are dissolved in 10ml water, are 9.18, ice bath with 1mol/L sodium hydroxide solutions regulation pH
It is cooled to after 0 DEG C, under stirring, 0.013ml 3- glycidyl ether oxygen propyl trimethoxy silicanes, heating is slowly added dropwise
To 40 DEG C, stirring reaction 6 hours, then ice bath cooling 5min, after temperature is reduced to 0 DEG C, then is slowly added dropwise 0.013ml 3-
Glycidyl ether oxygen propyl trimethoxy silicane, is warming up to 65 DEG C, is again stirring for reaction 6 hours, obtains aryl boric acid modification
The silane coupler aqueous solution.The control of the step reaction temperature and the speed that 3- glycidyl ether oxygen propyl trimethoxy silicanes are added dropwise
Particularly significant, otherwise 3- glycidyl ether oxygen propyl trimethoxy silicanes can be hydrolyzed largely and polycondensation, be occurred in solution a large amount of white
Color contamination absurd creature, hinders the further progress of reaction.Find that the step reacts very bad control and operation in experimentation, it is initial clear
Clear bright solution is gradually muddy, and what is finally obtained is the white solution of milk shape, illustrates 3- glycidyl ether oxygen propyl front threes
TMOS there occurs itself significant polycondensation reaction.
0.2g is had the magnetic-particle of silica by the homemade Surface coating of embodiment 5, adds aryl boron produced above
Acid modified silane coupler aqueous solution 5ml, 75 DEG C of stirring reactions 2 hours, attraction carries out separation of solid and liquid, supernatant discarded
The silane coupler aqueous solution 5ml that aryl boric acid produced above is modified is added in liquid, solid again, 75 DEG C of stirring reactions 2 are small
When, attraction carries out separation of solid and liquid, and solid is washed with water four times (each 10ml), washed once with 10ml acetone, and 60 DEG C are true
Sky is dried, and obtains aryl boric acid decorative material, and it is 21 μm of ol/g to determine its catechol adsorbance.
Claims (10)
1. a kind of method that oxide surface for containing hydroxyl on surface carries out aryl boric acid modification, it is characterized in that, including it is following
Step：Surface is contained to the oxide material, 3- glycidyl ether oxygen propyl trimethoxy silicanes, amino phenyl boric acid and three of hydroxyl
Ethamine is added in anhydrous alcoholic solvent, based on the specific surface area for the oxide material that hydroxyl is contained by surface, every square metre of surface area
1~8 μ l 3- glycidyl ether oxygen propyl trimethoxy silicanes, 0.5~10mg amino phenyl boric acids is added, contains hydroxyl by surface
Oxide material quality meter, the volume that every gram of material adds absolute alcohol is 5~100ml, and triethylamine is dense in absolute alcohol
Spend for 0.5~2% (v/v), the separation of solid and liquid after 60~90 DEG C of agitated reactions 4~24 hours washes away the residual of the surface of solids
Reactant.
2. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that the oxide material that hydroxyl is contained on the surface is that silica or titanium dioxide or zinc oxide or Surface coating have
The material of silica, titanium dioxide or zinc oxide.
3. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that the alcoholic solvent is methanol or ethanol or isopropanol.
4. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that the stirring reaction time is 6~8 hours.
5. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
Be, based on the specific surface area for the oxide material that hydroxyl is contained by surface, 3- glycidyl ether oxygen propyl trimethoxy silicanes plus
It is that the material per per square meter of surface area adds 2~4 μ l to enter amount.
6. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that based on the specific surface area for the oxide material for containing hydroxyl by surface, the addition of amino phenyl boric acid is per per square meter of surface area
Material add 1~3mg.
7. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that based on the quality for the oxide material for containing hydroxyl by surface, the addition of anhydrous alcoholic solvent adds 10 for every gram of material~
30ml。
8. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that concentration of the triethylamine in anhydrous alcoholic solvent is 0.8~1.2% (v/v).
9. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that the solvent that the residual reactants of the surface of solids are washed away after separation of solid and liquid is the mixed of ethanol or acetone or their arbitrary proportions
Compound.
10. the method that the oxide surface according to claim 1 for containing hydroxyl on surface carries out aryl boric acid modification, its feature
It is that the solvent that the residual reactants of the surface of solids are washed away after separation of solid and liquid is followed successively by 0.1mol/L sodium acid carbonates, 1mmol/L salt
Acid, pH value are neutral water and acetone.
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| US4837348A (en) * | 1986-04-30 | 1989-06-06 | Varian Associates, Inc. | Bonded phase chromatographic supports |
| CN1939568A (en) * | 2005-09-28 | 2007-04-04 | 中国科学院大连化学物理研究所 | Nitro-benzene boric-acid affinity chromatographic pre-column, its production and use |
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