CN110064382A - A kind of porous silica microballoon and the preparation method and application thereof - Google Patents
A kind of porous silica microballoon and the preparation method and application thereof Download PDFInfo
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- CN110064382A CN110064382A CN201910417867.XA CN201910417867A CN110064382A CN 110064382 A CN110064382 A CN 110064382A CN 201910417867 A CN201910417867 A CN 201910417867A CN 110064382 A CN110064382 A CN 110064382A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/20—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the sorbent material
- B01D15/206—Packing or coating
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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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B01J20/283—Porous sorbents based on silica
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Abstract
A kind of porous silica microballoon and the preparation method and application thereof, belongs to silica filler field, the porous silica microballoon specific surface area is 253m2/ g~323m2/ g, average pore size 10.47nm~13.63nm；The adsorbed hydroxyl content 0.502mmol/g~0.536mmol/g.The method for preparing porous silica microballoon comprising: organic silicon solution is placed in microwave synthesizer, after being heated to reflux, acid solution is added dropwise and carries out reflux mixing, then low temperature rotates to obtain oligomer；It is added in alcohols solvent after oligomer and pore-foaming agent are sufficiently mixed and is configured to solution A；Ammonium hydroxide, alcohols solvent and water are mixedly configured into solution B；Solution A is slowly dropped into solution B, is reprocessed in stirring, after being added dropwise after standing, washing and drying, by high-temperature calcination up to porous silica microballoon.
Description
Technical field
The invention belongs to silica filler fields, and in particular to a kind of porous silica microballoon and the preparation method and application thereof.
Background technique
From the sixties in last century, with machinery, the continuous development of the science and technology such as optics and electronics, chromatography is obtained considerable
Development and be widely used in all trades and professions.Wherein high performance liquid chromatography (HPLC) is used as chromatographic important branch, is food,
Medical treatment, the indispensable important separation detection means of the key areas such as chemical industry.Chromatographic column filler is as restriction high performance liquid chromatography
The key of separating property becomes the direction of numerous researchers.
Currently, common chromatograph packing material matrix can be divided into organic substrate, inorganic matrix and organic-nothing according to matrix difference
Machine composite interstitial substance stationary phase.Wherein in inorganic matrix, silicon dioxide microsphere is because it is not easy to be swollen, high mechanical strength and good
Thermal stability and become most widely used fixed phase stuffing in liquid chromatogram the advantages that chemical stability.Nineteen sixty-eight
Stober etc., which has found using base catalysis teos hydrolysis, prepares SiO2Microballoon, this sol-gal process are prepared micro-
Ball purity is high, homogeneity is good, but the method prepare it is at high cost, processing the time it is long and in itself it is non-porous, to be filled out as liquid chromatogram
Expect matrix, it is subsequent to need to carry out the sequence of operations such as reaming.
Summary of the invention
In view of the above problems, one aspect of the present invention discloses a kind of porous silica microballoon, the porous silica is micro-
Ball has suitable pore structure, has obtained can be used as the matrix fill of HPLC by being bonded C18.Another aspect of the present invention discloses one
The method that kind prepares porous silica microballoon.
To achieve the above object, the present invention adopts the following technical scheme:
One aspect of the present invention provides a kind of porous silica microballoon, and the porous silica microballoon specific surface area is
253~323m2/ g, 10.47~13.63nm of average pore size；0.502~0.536mmol/g of the adsorbed hydroxyl content.
The porous silica microballoon is by may be directly applied to HPLC filler after bonding C18.
Another aspect of the present invention provides a kind of method for preparing porous silica microballoon comprising: by organic silicon solution
It is placed in microwave synthesizer, after being heated to reflux, acid solution is added dropwise and carries out reflux mixing, then low temperature rotates to obtain oligomeric
Object；It is added in alcohols solvent after oligomer and pore-foaming agent are sufficiently mixed and is configured to solution A；By ammonium hydroxide, alcohols solvent and water
It is mixedly configured into solution B；Solution A is slowly dropped into solution B, is reprocessed in stirring, through quiet after being added dropwise
After setting, wash and drying, by high-temperature calcination up to porous silica microballoon.
In some embodiments, the pore-foaming agent is triblock copolymer or cation fluorine carbon surface active agent.
In some embodiments, the pore-foaming agent is F127, and F108, P123 or cation fluorine carbon surface active agent are FC-4
One of.
In some embodiments, the volume ratio of the ammonium hydroxide and alcohols solvent is v (ammonium hydroxide): v (alcohols solvent)=0.02
~0.07, v (ammonium hydroxide): v (H2O)=0.25~0.65.
In some embodiments, the drying be vacuum drying, drying temperature be 80~140 DEG C, drying time be 12~
36h；Preparing calcination temperature is 500~750 DEG C, and calcination time is 2~8h.
In some embodiments, the organosilicon is methyl orthosilicate (TMOS) or ethyl orthosilicate (TEOS)；It is described to have
In machine silicon solution, the volume ratio of alcohols solvent and organosilicon is v (dehydrated alcohol): v (TEOS/TMOS)=0.5-3.
In some embodiments, the alcohols solvent is one or more of methanol, ethyl alcohol, isopropanol or n-butanol.
In some embodiments, the acid solution be one of hydrochloric acid solution or nitric acid solution, the acid solution
Concentration is 0.1~2mol/L, uses peristaltic pump that 5min acid solution is added dropwise with the speed of 0.1~0.5ml/min.
In some embodiments, the revolving temperature of the low temperature revolving is 40-75 DEG C, and the speed of rotation is 60~100r/
min。
Beneficial effects of the present invention: the present invention use particular types pore-foaming agent, can promote the arrangement of organosilicon with polymerize,
To form ordered mesopore structure in roasting process；Present invention discover that the knot of microballoon can be influenced by the additive amount for adjusting ammonium hydroxide
Structure；The present invention carries out reflux mixing in microwave synthesizer, to promote the dispersion of silicon source the characteristics of its rapid and uniform heating.Always
It, the present invention has the advantage that
(1) porous silica microballoon prepared by the present invention, specific surface area is larger, and surface silicone hydroxyl abundant is obtained to subsequent
HPLC filler to high linkage content has beneficial to behavior.
(2) porous silica microballoon prepared by the present invention uses improved sol-gel method, eliminates subsequent thermal reaming
Deng operation, original technique is simplified.
(3) porous silica microballoon prepared by the present invention can express excellent splitter effect after subsequent bonding C18.
The present invention also provides the methods by the porous silica microballoon prepared as being bonded C18: first to obtained by
Microballoon is activated, and is chemically bonded later with C18, finally carries out termination process using chloroform.
The silicon dioxide microsphere of preparing passes through the method for bonding C18, the specific steps are as follows:
(1) preparation of microballoon: will add the organic silicon solution of dehydrated alcohol, close under the preliminary catalytic effect of acid in microwave
At reflux mixing is carried out in device, then low temperature rotates sticky oligomer made of obtaining partial hydrolysis；By oligomer and pore
Agent is added suitable isopropanol after being sufficiently mixed and is configured to solution A, and certain density ammonium hydroxide, dehydrated alcohol and distilled water are mixed
Conjunction is configured to solution B, and solution A is slowly dropped into solution B by peristaltic pump, is reprocessed in stirring, wait drip
After Bi Houjing standing, aging, washing and drying, calcined at a certain temperature up to silicon dioxide microsphere.
(2) chemical modification of microballoon: being immersed in a period of time in hydrochloric acid solution for the silicon dioxide microsphere heating of preparation, after
It is washed with deionized to neutrality, the silicon dioxide microsphere of surface active is obtained after vacuum drying.Weigh activation after microballoon in
It steams in toluene again, octadecyldimethylchlorosilane is added in right amount, and triethylamine is added as catalyst, then N2It is filled under protection
Divide and is stirred at reflux.To after reaction, by acquired solution centrifugal treating, then successively with reforming toluene, methanol, methylene chloride and
Acetone washing product, is dried in vacuum overnight.Small molecule chlorosilane is added in product after drying to continue to stir in toluene solvant
Reaction.It is washed for several times with methylene chloride after the reaction was completed, product is dried in vacuum overnight after filtering.
In some embodiments, organosilicon described in step (1) is methyl orthosilicate (TMOS) or ethyl orthosilicate
(TEOS), preferred ethyl orthosilicate.
In some embodiments, the additional amount of ammonium hydroxide described in step (1) is 1.5~5ml, volume fraction 28%.
In some embodiments, drying temperature described in step (1) is 80~140 DEG C, and drying time is 12~36h；Institute
Stating preparation calcination temperature is 500~750 DEG C, and calcining time is 2~8h.
In some embodiments, microballoon is immersed in hydrochloric acid solution described in step (2), the concentration of hydrochloric acid solution is
3~6mol/L, soaking time are 6~12h.
In some embodiments, the preferred trim,ethylchlorosilane of small molecule chlorosilane described in step (2).
Of the invention is particularly advantageous in that:
Porous silica microballoon provided by the present invention avoids additional reaming as the raw material for preparing HPLC filler
And etc., cost is saved, obtained porous silica Microsphere Size is uniform, has biggish specific surface area, after being bonded C18
Obtained HPLC filler matrix shows good separating effect.
Detailed description of the invention
Fig. 1 is the low temperature nitrogen adsorption desorption curve of filler material prepared by embodiment 1-2；
Fig. 2 is the pore size distribution curve of filler material prepared by embodiment 3-4；
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 2.
Specific embodiment
The present invention is further explained with reference to embodiments, but protection scope of the present invention is not limited to following embodiments.For
Further illustrate experimental implementation and its experimental result of the invention, this part combines the embodiment of invention to be retouched in more detail
It states.
Embodiment 1
(1) preparation of microballoon: by the ethyl orthosilicate of the dehydrated alcohol of 12mL and 20mL in 60 DEG C in microwave synthesizer
Reflux, uses 5mL hydrochloric acid of the peristaltic pump while stirring with the speed of 0.5mL/min in mixed solution and dripping 0.1mol/L water-soluble
Liquid stands 20min after being added dropwise, then reaction solution is rotated at 50 DEG C 1h obtain it is sticky oligomeric made of partial hydrolysis
Object；5g oligomer and 30mg F127 are weighed in three-necked flask, the isopropanol that 20mL is added is configured to solution A, meanwhile, it will
The distilled water of the ammonium hydroxide of 1.5mL, the dehydrated alcohol of 40.75mL and 2mL is uniformly configured to solution B by ultrasonic mixing, by compacted
Solution A is slowly dropped into solution B by dynamic pump with the speed of 1mL/min, is reprocessed in stirring at 300r/min, wait drip
It adds complete, stands 30min, kept for 24 hours at 100 DEG C with placing it in vacuum oven after dehydrated alcohol centrifuge washing 5 times,
6h is calcined at 550 DEG C up to porous silica microballoon.After tested, gained porous silica microballoon specific surface area is
323m2/ g, average pore size 11.35nm.
(2) chemical modification of microballoon: the silicon dioxide microsphere heating for weighing 5g preparation is immersed in the hydrochloric acid solution of 6mol/L
Middle immersion 6h, after be washed with deionized to neutrality, the silicon dioxide microsphere of surface active is obtained after vacuum drying.Weigh activation
20mL is added wherein and steams toluene again, 7mL octadecyl trichlorosilane alkane is added dropwise while adding in three-necked flask for microballoon afterwards
Enter 1mL triethylamine as catalyst, N2Heating stirring reflux 3h in atmosphere.To after reaction, by acquired solution centrifugal treating,
It is successively dried in vacuum overnight again with toluene, methanol, methylene chloride and acetone washing product is reformed.Product after drying is added
Enter 1mL trim,ethylchlorosilane to continue to be stirred to react in toluene solvant.It is washed for several times with methylene chloride after the reaction was completed, product is taken out
It is dried in vacuum overnight after filter.It is denoted as filler A.
Embodiment 2
The ethyl orthosilicate of the dehydrated alcohol of 25mL and 20mL are flowed back in microwave synthesizer in 60 DEG C, using peristaltic pump
It is added dropwise rear quiet with the speed of 0.5mL/min in the 3mL aqueous hydrochloric acid solution of mixed solution and dripping 0.1mol/L while stirring
30min is set, then reaction solution 2h is rotated at 55 DEG C and obtains sticky oligomer made of partial hydrolysis；Weigh 5g oligomer with
For 25mg F108 in three-necked flask, the isopropanol that 15mL is added is configured to solution A, meanwhile, by the ammonium hydroxide of 3mL, 42mL it is anhydrous
Ethyl alcohol and the distilled water of 5mL pass through ultrasonic mixing and are uniformly configured to solution B, will be molten with the speed of 1.5mL/min by peristaltic pump
Liquid A is slowly dropped into solution B, is reprocessed in stirring at 250r/min, wait be added dropwise, stands 30min, use is anhydrous
It places it in after ethyl alcohol centrifuge washing 5 times in vacuum oven and is kept for 24 hours at 100 DEG C, calcine 4h at 550 DEG C up to titanium dioxide
Silicon microballoon.After tested, gained porous silica microballoon specific surface area is 289m2/ g, average pore size 12.35nm.
(2) chemical modification of microballoon: the silicon dioxide microsphere heating for weighing 5g preparation is immersed in the hydrochloric acid solution of 5mol/L
Middle immersion 8h, after be washed with deionized to neutrality, the silicon dioxide microsphere of surface active is obtained after vacuum drying.Weigh activation
25mL is added wherein and steams toluene again, 7mL octadecyl trichlorosilane alkane is added dropwise while adding in three-necked flask for microballoon afterwards
Enter 1mL triethylamine as catalyst, N2Heating stirring reflux 5h in atmosphere.To after reaction, by acquired solution centrifugal treating,
It is successively dried in vacuum overnight again with toluene, methanol, methylene chloride and acetone washing product is reformed.Product after drying is added
Enter 1mL trim,ethylchlorosilane to continue to be stirred to react in toluene solvant.It is washed for several times with methylene chloride after the reaction was completed, product is taken out
It is dried in vacuum overnight after filter.It is denoted as filler B.
Embodiment 3
The ethyl orthosilicate of the dehydrated alcohol of 30mL and 15mL are flowed back in microwave synthesizer in 60 DEG C, using peristaltic pump
It is added dropwise rear quiet with the speed of 0.5mL/min in the 7mL aqueous hydrochloric acid solution of mixed solution and dripping 0.1mol/L while stirring
25min is set, then reaction solution 0.5h is rotated at 65 DEG C and obtains sticky oligomer made of partial hydrolysis；Weigh 5g oligomer
With 20mg P123 in three-necked flask, the isopropanol that 20mL is added is configured to solution A, meanwhile, by the ammonium hydroxide of 4.5mL, 36mL
The distilled water of dehydrated alcohol and 3mL are uniformly configured to solution B by ultrasonic mixing, by peristaltic pump with the speed of 0.8mL/min
Solution A is slowly dropped into solution B, is reprocessed in stirring at 400r/min, wait be added dropwise, 90min is stood, uses
It is placed it in after dehydrated alcohol centrifuge washing 5 times in 80 DEG C of holding 36h in vacuum oven, calcines 3h at 700 DEG C up to two
Silicon oxide microsphere.After tested, gained porous silica microballoon specific surface area is 263m2/ g, average pore size 13.63nm.
(2) chemical modification of microballoon: the silicon dioxide microsphere heating for weighing 5g preparation is immersed in the hydrochloric acid solution of 6mol/L
Middle immersion 5h, after be washed with deionized to neutrality, the silicon dioxide microsphere of surface active is obtained after vacuum drying.Weigh activation
30mL is added wherein and steams toluene again, 6mL octadecyl trichlorosilane alkane is added dropwise while adding in three-necked flask for microballoon afterwards
Enter 1.5mL triethylamine as catalyst, N2Heating stirring reflux 5h in atmosphere.To after reaction, at acquired solution centrifugation
Reason, then be successively dried in vacuum overnight with toluene, methanol, methylene chloride and acetone washing product is reformed.By the product after drying
1mL trim,ethylchlorosilane is added to continue to be stirred to react in toluene solvant.It is washed for several times with methylene chloride after the reaction was completed, product
It is dried in vacuum overnight after suction filtration, is denoted as filler C.
Embodiment 4
The ethyl orthosilicate of the dehydrated alcohol of 40mL and 25mL are flowed back in microwave synthesizer in 60 DEG C, using peristaltic pump
While stirring with the speed of 0.35mL/min mixed solution and dripping 0.1mol/L 6mL aqueous hydrochloric acid solution, after being added dropwise
50min is stood, then reaction solution 2h is rotated at 55 DEG C and obtains sticky oligomer made of partial hydrolysis；Weigh 5g oligomer
With 20mg FC-4 in three-necked flask, the isopropanol that 20mL is added is configured to solution A, meanwhile, by the nothing of the ammonium hydroxide of 3mL, 45mL
The distilled water of water-ethanol and 6mL are uniformly configured to solution B by ultrasonic mixing, will be molten with the speed of 1mL/min by peristaltic pump
Liquid A is slowly dropped into solution B, is reprocessed in stirring at 350r/min, wait be added dropwise, stands 30min, use is anhydrous
It is placed it in after ethyl alcohol centrifuge washing 5 times in 140 DEG C of holding 12h in vacuum oven, calcines 8h at 500 DEG C up to titanium dioxide
Silicon microballoon.After tested, gained porous silica microballoon specific surface area is 253m2/ g, average pore size 10.47nm.
(2) chemical modification of microballoon: the silicon dioxide microsphere heating for weighing 5g preparation is immersed in the hydrochloric acid solution of 6mol/L
Middle immersion 4h, after be washed with deionized to neutrality, the silicon dioxide microsphere of surface active is obtained after vacuum drying.Weigh activation
35mL is added wherein and steams toluene again, 8mL octadecyl trichlorosilane alkane is added dropwise while adding in three-necked flask for microballoon afterwards
Enter 2mL triethylamine as catalyst, N2Heating stirring reflux 8h in atmosphere.To after reaction, by acquired solution centrifugal treating,
It is successively dried in vacuum overnight again with toluene, methanol, methylene chloride and acetone washing product is reformed.Product after drying is added
Enter 1mL trim,ethylchlorosilane to continue to be stirred to react in toluene solvant.It is washed for several times with methylene chloride after the reaction was completed, product is taken out
It is dried in vacuum overnight after filter.It is denoted as filler D.
Embodiment 5 (comparative example)
The ethyl orthosilicate of the dehydrated alcohol of 15mL and 20mL are flowed back in microwave synthesizer in 60 DEG C, using peristaltic pump
It is added dropwise rear quiet with the speed of 0.5mL/min in the 5mL aqueous hydrochloric acid solution of mixed solution and dripping 0.1mol/L while stirring
20min is set, then reaction solution 1h is rotated at 50 DEG C and obtains sticky oligomer made of partial hydrolysis；5g oligomer is weighed,
The isopropanol that 20mL is added is configured to solution A, meanwhile, by the ammonium hydroxide of 1.5mL, the distilled water of the dehydrated alcohol of 35mL and 2.5mL
It is uniformly configured to solution B by ultrasonic mixing, solution A is slowly dropped into the speed of 2mL/min by solution B by peristaltic pump
In, it is reprocessed in stirring at 350r/min, wait be added dropwise, 30min is stood, after dehydrated alcohol centrifuge washing 5 times
It places it in vacuum oven and is kept for 24 hours at 100 DEG C, calcine 6h at 500 DEG C up to silicon dioxide microsphere.After tested, institute
Obtaining porous silicon dioxide microsphere specific surface area is 189m2/ g, average pore size 7.56nm.
(2) chemical modification of microballoon: the silicon dioxide microsphere heating for weighing 5g preparation is immersed in the hydrochloric acid solution of 6mol/L
Middle immersion 6h, after be washed with deionized to neutrality, the silicon dioxide microsphere of surface active is obtained after vacuum drying.Weigh activation
25mL is added wherein and steams toluene again, 7mL octadecyl trichlorosilane alkane is added dropwise while adding in three-necked flask for microballoon afterwards
Enter 1mL triethylamine as catalyst, N2Heating stirring reflux 3h in atmosphere.To after reaction, by acquired solution centrifugal treating,
It is successively dried in vacuum overnight again with toluene, methanol, methylene chloride and acetone washing product is reformed.Product after drying is added
Enter 1mL trim,ethylchlorosilane to continue to be stirred to react in toluene solvant.It is washed for several times with methylene chloride after the reaction was completed, product is taken out
It is dried in vacuum overnight after filter.It is denoted as filler E.
Embodiment 6 (comparative example)
(1) commercial silica microballoon 5g is weighed.After tested, silicon dioxide microsphere specific surface area is 234m2/ g, average hole
Diameter is 8.75nm.
(2) it the chemical modification of microballoon: weighs the heating of 5g commercial silica microballoon and is immersed in the hydrochloric acid solution of 6mol/L
Impregnate 12h, after be washed with deionized to neutrality, the silicon dioxide microsphere of surface active is obtained after vacuum drying.Weigh activation
30mL is added wherein and steams toluene again, 7mL octadecyl trichlorosilane alkane is added dropwise while adding in three-necked flask for microballoon afterwards
Enter 2mL triethylamine as catalyst, N2Heating stirring reflux 7h in atmosphere.To after reaction, by acquired solution centrifugal treating,
It is successively dried in vacuum overnight again with toluene, methanol, methylene chloride and acetone washing product is reformed.Product after drying is added
Enter 1.5mL trim,ethylchlorosilane to continue to be stirred to react in toluene solvant.It is washed for several times with methylene chloride after the reaction was completed, product
It is dried in vacuum overnight after suction filtration, is denoted as filler E.
Phenetic analysis method
SiO in embodiment2The measurement of the specific surface area and pore structure of microballoon is in 3020 type of Micrometrics company, the U.S.
It is carried out on gas absorption pore size determination instrument.0.10g sample (drying pretreatment, 20~40 mesh, 380 μm~830 μm) are weighed,
4h is handled under the conditions of 150 DEG C, with N2For adsorbate, (- 196 DEG C) measure adsorption desorption curve under liquid nitrogen temperature.According to adsorption desorption
The absorption Zhi Caiyong BET method of curve calculates specific surface area, desorption Zhi Caiyong BJH method calculated hole diameters distribution.
SiO in embodiment2Microsphere surface hydroxy radical content test method: a certain amount of prepared SiO is weighed2Microballoon is in taper
In bottle, l0%NaCI solution and isopropanol is added, the sodium ion in the active hydrogen and sodium chloride of Silica Surface silicone hydroxyl occurs
Exchange reaction generates HCI, and then using phenolphthalein as indicator, the HCI generated with the NaOH standard solution titration above process can be pushed away
Know the amount of Silica Surface silicone hydroxyl.
SiO in embodiment2Microballoon Micro-Structure Analysis: it is swept using the S-4800 Flied emission of Hitachi company, Japan production
Face electron microscope characterizes come microscopic appearance, structure and the particle size size to catalyst.Plain scan test job
Voltage is 5kV, and operating current is 7 μ A.
Filler material prepared by the present invention carries out the test of toluene separating property after being loaded on pillar:
Test method: (1) prepared by each above-described embodiment and comparative example chromatograph packing material is filled to 4.6*250mm size
In chromatographic column, setting flow velocity is 1.0ml/min；Using toluene as sample to be tested, its initial theory number of plates is tested, No is denoted as；Reason
By the number of plates-
5.54* (retention time of toluene appearance/toluene appearance peak width at half height) 2；
(2) sodium hydroxide/methanol solution repeated flushing above-mentioned filling chromatographic column of 0.l mol/L, the same terms are used
Under, after rinsing 0.5 hour every time, the theoretical cam curve of the chromatographic column is retested, the theoretical cam curve after jth time is rinsed is
Nj, j are the positive integer less than or equal to 100；
(3) record (No-Nj)/No) 10% number；Gained time numerical value is higher, and chromatographic performance is better, and product stability is got over
Good, alkali resistance is stronger.
In 1 embodiment 1-6 of table gained filler chromatography test the toluene separation theorem number of plates, tailing factor and surface hydroxyl
Base content
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, comes under covering scope of the invention.
Claims (10)
1. a kind of porous silica microballoon, which is characterized in that the porous silica microballoon specific surface area is 253m2/ g~
323m2/ g, average pore size 10.47nm~13.63nm；The adsorbed hydroxyl content 0.502mmol/g~0.536mmol/g.
2. a kind of method for preparing porous silica microballoon comprising: organic silicon solution is placed in microwave synthesizer, is added
Heat is added dropwise acid solution and carries out reflux mixing, be then concentrated to get oligomer to after flowing back；Oligomer and pore-foaming agent are sufficiently mixed
It is added in alcohols solvent later and is configured to solution A；Ammonium hydroxide, alcohols solvent and water are mixedly configured into solution B；Solution A is slow
It is added dropwise in solution B, is reprocessed in stirring, after being added dropwise after standing, washing and drying, by calcining to obtain the final product
Porous silica microballoon.
3. the method for preparing porous silica microballoon as claimed in claim 2, the pore-foaming agent is triblock copolymer or sun
Ion fluorocarbon surfactant.
4. the method for preparing porous silica microballoon as claimed in claim 3, the pore-foaming agent is F127, F108, P123
Or cation fluorine carbon surface active agent is one of FC-4.
5. the volume ratio of the method for preparing porous silica microballoon as claimed in claim 3, the ammonium hydroxide and dehydrated alcohol is v
(ammonium hydroxide): v (dehydrated alcohol)=0.02~0.07, v (ammonium hydroxide): v (H2O)=0.25~0.65.
6. the method according to claim 1, wherein the calcination temperature be 500~750 DEG C, calcination time 2
~8h.
7. preparing the method for porous silica microballoon according to claim 2, it is characterised in that: the organosilicon is positive silicon
Sour methyl esters or ethyl orthosilicate；In the organic silicon solution, the volume ratio of alcohols solvent and organosilicon is v:v=0.5~3.
8. preparing the method for porous silica microballoon according to claim 2, which is characterized in that the acid solution is hydrochloric acid
One of solution or nitric acid solution, the concentration of the acid solution are 0.1~2mol/L, use peristaltic pump with 0.1~
5min acid solution is added dropwise in the speed of 0.5ml/min.
9. may be directly applied to HPLC filler after porous silica microsphere bond C18 described in claim 1.
10. specific step is as follows by porous silica microsphere bond C18 according to claim 9:
(1) heating of the silicon dioxide microsphere of preparation is immersed in a period of time in hydrochloric acid solution, after be washed with deionized into
Property, the silicon dioxide microsphere of surface active is obtained after vacuum drying；
(2) in steaming in toluene again octadecyldimethylchlorosilane is added, and three second are added in the microballoon after weighing activation in right amount
Amine is as catalyst, then N2Reflux is sufficiently stirred under protection, to after reaction, use by acquired solution centrifugal treating, then successively
Toluene, methanol, methylene chloride and acetone washing product are reformed, is dried in vacuum overnight；
(3) small molecule chlorosilane is added in the product after drying to continue to be stirred to react in toluene solvant, after the reaction was completed with two
Chloromethanes washs for several times, the silica gel H PLC filler that product is dried in vacuum overnight up to C18 bonding after filtering.
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| CN201910417867.XA CN110064382B (en) | 2019-05-20 | 2019-05-20 | Porous silicon oxide microsphere and preparation method and application thereof |
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| CN111333074A (en) * | 2020-03-06 | 2020-06-26 | 中谱科技(福州)有限公司 | Method for preparing mesoporous silicon oxide by using biomass as raw material and application thereof |
| CN111389052A (en) * | 2020-03-13 | 2020-07-10 | 中谱科技(福州)有限公司 | Preparation and application of polyamide high performance liquid chromatography column |
| CN113636890A (en) * | 2021-09-18 | 2021-11-12 | 成都正光投资集团有限公司 | Selenium-rich slow-release cadmium inhibitor and preparation method thereof |
| CN116242960A (en) * | 2022-09-09 | 2023-06-09 | 苏州拉索生物芯片科技有限公司 | Method for measuring hydroxyl content on surface of silicon dioxide microsphere by titration |
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