CN108424525A - Silicon nano material surface functionalization method based on vinyl sulfone - Google Patents
Silicon nano material surface functionalization method based on vinyl sulfone Download PDFInfo
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Abstract
The invention discloses a kind of silicon nano material surface functionalization method based on vinyl sulfone, the method is directly reacted with material surface silicone hydroxyl using vinyl sulfone derivative under catalytic condition, realizes the covalent functionalization of silica-base material.The functionalization of a variety of silicon nano materials, wide application range of substrates may be implemented in this method；Without carrying out pre-treatment to material, operability is strong, reproducibility is high；Reaction condition is mild, easy to operate, environmental-friendly；Single layer function surface is generated, reaction controllability is strong；It is a kind of broad spectrum activity silicon nano material surface functionalization method having a high potential.
Description
Technical field
The invention belongs to inorganic-organic composites preparation fields, and in particular to a kind of silicon nano material is surface-functionalized new
Method more particularly to a kind of surface functionalization method of the Michael addition reactions based on silicone hydroxyl and vinylsulfone group.
Technical background
Silica-base material is low as a kind of price, and type is more, and purposes is wide, and stability is high, the strong material of machinability, daily
Be seen everywhere in life and scientific research, such as monocrystalline silicon, glass, optical fiber etc., be widely used in aerospace, electric, building,
The industries such as transport, the energy, chemical industry, weaving, food, light industry, medical treatment, agricultural.Wherein silicon nano material is raw due to large specific surface area
The advantages that manage bar part stability inferior is good, and biocompatibility is high is led in biological medicines such as cell culture, drug conveying, antimicrobial coatings
Domain, which develops, to be widely applied.
Application of the silicon nano material in every field depends on the functionalization of material surface, wherein covalent functionalization mostly
It is had been widely adopted since stability is high.There are mainly four types of the silicon face covalent functionalization methods having been reported.It wherein uses most
Extensive method is silane coupling agent, and silane coupling agent is by Si-O-Si keys in silica-base material surface covalent coupling organic molecule.
But silane coupling agent, to humidity sensitive, facile hydrolysis is concurrently born from poly- in wet condition.And silane coupling agent reaction is usual
Multilayered structure can be formed, the uncertainty of functionalizing material surface structure is caused.Organophosphor acid system is that a kind of potential silane is even
Join agent alternative, this method adsorbs organic phosphoric acid firstly the need of silicon materials are immersed in machine phosphoric acid solution, then high temperature item
Si-O-P keys are generated under part, which generally requires carries out under the conditions of 120-140 DEG C, and hot conditions are for many bioactivity
Molecule is not applicable.Another silica-base material functional method is common in chromatographic field, direct at high temperature with alcohol using silicone hydroxyl
Reaction forms Si-O-C keys, which usually requires 300 DEG C or more.A kind of silica-base material functional method developed in recent years is
Si -- H bond is introduced on silica-base material surface, Si -- H bond in a mild condition can be with halogenated hydrocarbons, mercaptan, amine, aldehyde, alkene, alkynes
It is reacted etc. a variety of organic molecule molecules, realizes the covalent bond functionalization of silica-base material.However, silica-base material need it is special before
(low pressure hydrogen or fluorine reagent) is handled to generate Si -- H bond, and the Si -- H bond generated is very sensitive to water and oxygen, in tide
Oxidation generation oxide layer is easy under wet or aerobic conditions hinders reaction to carry out, and therefore, which needs under the conditions of anhydrous and oxygen-free
It carries out.There is an urgent need for a kind of silica-base material functional methods of mild condition easy to operate at present.
Invention content
The present invention is intended to provide a kind of surface-functionalized new method of the silicon nano material based on vinyl sulfone, the side
Method is will to be dissolved in aprotic polar solvent with the vinyl sulfone derivative of general formula I, and by silicone hydroxyl silicon nano material
It is scattered in the solution, reacts 1-24 hours for 25-100 DEG C under the action of catalyst, you can realize the function of surface of silica-base material
Change.Vinyl sulfone derivative is absolutely excessive relative to silicon nano material generally under solution condition.
Wherein, R is deriveding group.
For in technique described above scheme, in the case of preferred, the R is selected from alkane, aryl, carboxylic acid, high score
Subchain and other organic deriveding groups.
For in technique described above scheme, in the case of preferred, the silicon nano material is that surface is silicone hydroxyl
Or the material of silicone hydroxyl can be derived by chemical treatment, including colloid silicon nano material, gas phase silicon nano material, mesoporous silicon are received
Rice material, the coated organic-inorganic nano material of silica；Heteroatom doping silicon nano material (such as silicon nitride, silicon carbide).
For in technique described above scheme, in the case of preferred, the vinyl sulfone derivative has general formula I's
Structure, R is deriveding group, including alkane (such as methyl, ethyl, propyl, dodecyl etc.), aryl (such as phenyl, benzyl in formula
Deng), carboxylic acid (such as carboxylic propyl, carboxymethyl etc.), macromolecular chain (polyethylene glycol, amphipathy macromolecule material etc.) and other are organic
Deriveding group；
For in technique described above scheme, in the case of preferred, the catalyst is three substitution organic phosphines.
For in technique described above scheme, in the case of preferred, described three substitution organic phosphines are selected from triphenylphosphine,
Tri isopropyl phosphine, benzyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, tri-tert-butylphosphine, three p-methylphenyl phosphines.
For in technique described above scheme, in the case of preferred, the dosage of the catalyst derives for vinyl sulfone
The 1~10% of the amount of object substance.
For in technique described above scheme, in the case of preferred, the aprotic polar solvent is selected from acetonitrile, and third
Ketone, n,N-Dimethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran , dioxanes, dichloromethane and chloroform.
For in technique described above scheme, in the case of preferred, preferred 25-60 DEG C of the reaction temperature；
For in technique described above scheme, in the case of preferred, the reaction time preferred 6-12h.
Advantageous effect：
Silica-base material functionalization new method of the present invention has following advantage relative to conventional method：
(1) substrate applicability is wide, the silicon nano material for a variety of silicon nano materials, Heteroatom doping and silica packet
The silicon nano material wrapped up in is applicable in；
(2) functionalized reagent stability is high, and commercial source is wide, alternative strong, and reacts and generate single-layer functional film, excellent
In silane coupling agent method；
(3) reaction condition is mild, can carry out at ambient temperature, and heating can improve reaction rate, is better than organophosphor
Acid system and alcohol method；
(4) it is reacted using silicone hydroxyl, pre-treatment is carried out typically without to silicon materials；Using conventional solution reaction into
Row functionalization, operation is simple, is reacted better than Si -- H bond；
(5) it is modified using click chemistry, no coupling product production meets atom economy and environmentally protective；
To sum up, this method applicability is wide, easy to operate, mild condition, is that a kind of broad spectrum activity silicon materials having a high potential are repaiied
Decorations method.
Description of the drawings
Fig. 1：Colloid silicon nano material TEM pictures before and after PEG 2000-VS functionalization.
Fig. 2：Colloid silicon nano material hydraulic diameter changes before and after PEG 2000-VS functionalization.
Fig. 3：The CP/MAS of colloid silicon nano material before and after PEG 2000-VS functionalization13C solid state nmr spectrograms.
Fig. 4：The Total Reflection Infrared spectrogram of colloid silicon nano material before and after PEG 2000-VS functionalization.
Fig. 5：The functions of colloid silicon nano material compare before and after PEG 2000-VS functionalization.
Fig. 6：Aerosil material hydraulic diameter changes before and after PEG 2000-VS functionalization.
Fig. 7：Aerosil material thermogravimetric analysis spectrogram before and after PEG 2000-VS functionalization.
Fig. 8：41 thermogravimetric analysis spectrograms of MCM before and after PEG 2000-VS functionalization.
Fig. 9：41 x-ray photoelectron spectroscopy figures of MCM before and after PEG 2000-VS functionalization.
Specific implementation mode
The present invention discloses a kind of surface-functionalized new method of the silicon nano material based on vinyl sulfone.The silica-base material
It is inorganic silicon materials, in particular to the nano material with silicon or silica, including but not limited to colloid silicon nano material, gas phase
Silicon nano material, nanometer material, the coated organic-inorganic nano material of silica；Heteroatom doping silicon nano material
(such as silicon nitride, silicon carbide).The vinyl sulfone derivative has general formula I, and R is deriveding group in formula, and described urges
Agent is three substitution organic phosphines, including but not limited to triphenylphosphine, tri isopropyl phosphine, benzyldiphenylphosphine, dimethylphenylphosphine,
Ethyldiphenylphosphine, tri-tert-butylphosphine, three p-methylphenyl phosphines.
Following specific examples is described further to present disclosure, should not be construed as to any shape of the present invention
The restriction of formula.
Embodiment 1：Function is carried out to colloid silicon nano material with polyethylene glycol 2000-vinyl sulfone (PEG 2000-VS)
Change and its anti-protein adsorption functional test
By colloid silicon nano material (Colloidal silica, AS 40TM, Sigma) and it is scattered in ethyl alcohol, acidification
Improve material surface silicone hydroxyl density.Will treated colloid silicon nano material centrifuge and washed with acetonitrile preserve afterwards three times it is standby
With.Take 400mg treated that colloid silicon nano material is scattered in 20mL acetonitriles.It is added in colloidal silicon nanomaterial solution
500mg PEG 2000-VS simultaneously fully dissolve, and 65mg triphenylphosphines are added and make catalyst, back flow reaction 12 hours.It centrifuges and is used in combination
Acetonitrile washs the colloid silicon nano material for obtaining PEG 2000-VS functionalization afterwards three times.Using transmission electron microscope (TEM) to functionalization
Front and back colloid silicon nano material is characterized, as shown in attached drawing 1a and Fig. 1 b.The colloidal silicon nanometer of PEG 2000-VS functionalization
Material particle size increases about 3nm than the colloid silicon nano material of non-functionalization, shows the success of PEG 2000-VS functionalization.Using dynamic
State light scattering method (DLS) is to the aerosil material hydraulic diameter (D before and after functionalizationh) characterized, such as 2 institute of attached drawing
Show.Colloid silicon nano material hydraulic diameter increases 50nm after functionalization, shows the success of PEG 2000-VS functionalization.It uses
CP/MAS13C solid state nmrs characterize the colloid silicon nano material before and after functionalization, as shown in Fig. 3.PEG 2000-VS
Machine object spectral peak is found no before functionalization on solid state nmr spectrogram, occurs polyglycol chain carbon at 60ppm after functionalization
Peak shows functionalization success.The colloid silicon nano material before and after functionalization is characterized using Total Reflection Infrared, such as Fig. 4 institutes
Show.In 2900cm in Total Reflection Infrared spectrogram after functionalization-1And 1450cm-1There is c h bond vibration peak in place, in 960cm-1Place
There is Si-O-C key chatterings peak, shows that the method achieve the covalent functionalizations of colloid silicon nano material.
Since polyethylene glycol functionalization can assign material anti-tartar function, functionalization is had detected using fibrinogen (Fg)
The functions of front and back colloid silicon nano material, as shown in Fig. 5.The colloid silicon nano material of non-functionalization is after being added albumen
Hydraulic diameter (Dh) significantly increased, it is as caused by albumen in nanoparticle surface absorption.PEG 2000-VS functions
The colloidal silicon nanometer of change hydraulic diameter (D after albumen is addedh) it is that significant changes occur, show its good anti-tartar work(
Energy.
Embodiment 2：Work(is carried out to aerosil material with polyethylene glycol 2000-vinyl sulfone (PEG 2000-VS)
Energyization
By 100mg aerosils material (Sigma) ultrasonic disperse in 20mL acetonitriles.In aerosil material
1.0g PEG 2000-VS are added in solution and fully dissolve, 262mg triphenylphosphines are added and make catalyst, back flow reaction 12 is small
When.It centrifuges and washs the aerosil material for obtaining PEG 2000-VS functionalization afterwards three times with acetonitrile.It is dissipated using dynamic optical
Method (DLS) is penetrated to the gas phase before and after functionalization and silica material hydraulic diameter characterizes, as shown in Fig. 6.PEG
The gas phase of 2000-VS functionalization and silica material grain size increases about 50nm, table than the aerosil material of non-functionalization
Bright PEG 2000-VS functionalization success.The aerosil material before and after functionalization is characterized using thermogravimetric analysis, such as
Shown in attached drawing 7.There is mass loss at 100 DEG C in the aerosil material of PEG 2000-VS functionalization, this is because nanometer
Caused by the solvent water evaporation of material absorption；The mass loss occurred at 350 DEG C, is the Si-O-C key scission of links due to generation, has
It is several layers of fall off caused by, the phenomenon show PEG 2000-VS functionalization success.By thermogravimetric analysis, PEG can be calculated
2000-VS functionalization density is about 114 μm of ol/g.
Embodiment 3：Functionalization is carried out to mesoporous silicon material with polyethylene glycol 2000-vinyl sulfone (PEG 2000-VS)
By 50mg meso pore silicon oxide materials (MCM 41, Sigma) ultrasonic disperse in 10mL acetonitriles.In 41 solution of MCM
100mg PEG 2000-VS are added and fully dissolve, 37mg triphenylphosphines are added and make catalyst, back flow reaction 12 hours.Centrifugation
It is used in combination acetonitrile washing to obtain the MCM 41 of PEG 2000-VS functionalization afterwards three times.Using thermogravimetric analysis to the MCM before and after functionalization
41 are characterized, as shown in Fig. 8.There is mass loss at 100 DEG C in the MCM 41 of PEG 2000-VS functionalization, this is because
Caused by the solvent water evaporation of nano material absorption；The mass loss occurred at 350 DEG C is since the Si-O-C keys of generation are disconnected
Key, caused by having several layers of fall off, which shows the success of PEG 2000-VS functionalization.By thermogravimetric analysis, can calculate
PEG 2000-VS functionalization density is about 123 μm of ol/g.Using x-ray photoelectron spectroscopy to PEG 2000-VS functionalization
MCM 41 is characterized, as shown in Figure 9.In scanning spectra (Fig. 9 a), it is observed that the MCM of PEG 2000-VS functionalization
41 Si signals are substantially reduced, and C signal is remarkably reinforced, and show to cover one layer of organic layer in 41 material surfaces of MCM.C ls spectrograms
In (Fig. 9 b), occurs apparent C after 2000 VS functionalization of PEG at 286.5eV*- O signal peaks are attributed to the spy of polyglycol chain
Levy peak.In S 2p spectrograms (Fig. 9 c), occurs the characteristic peak of sulfuryl at 168.0eV after 2000 VS functionalization of PEG.To sum up, XPS
Characterization result illustrates the polyethylene glycol functionalization that 41 nanometer materials of MCM are realized by the reaction.
For any person skilled in the art, without departing from the scope of the technical proposal of the invention, all
Many possible changes and modifications are made to technical solution of the present invention using the technology contents of the disclosure above, or are revised as equivalent
The equivalent embodiment of variation.Therefore, every content without departing from technical solution of the present invention, according to the technical essence of the invention to
Any simple modifications, equivalents, and modifications that upper embodiment is done should all still fall within the range of technical solution of the present invention protection
It is interior.
Claims (9)
1. one kind being based on the surface-functionalized new method of silicon nano material, which is characterized in that described method includes following steps：It will tool
There is the vinyl sulfone derivative of general formula I to be dissolved in aprotic polar solvent, and silicone hydroxyl silicon nano material is scattered in this
In solution, 25-100 DEG C of reaction under the action of catalyst is made for 1-24 hours.
Wherein, R is deriveding group.
2. according to the method described in claim 1, it is characterized in that, the R be selected from alkane, aryl, carboxylic acid, macromolecular chain with
And other organic deriveding groups.
3. according to the method described in claim 1, it is characterized in that, described is selected from colloidal silicon containing silicone hydroxyl silicon nano material
Nano material, gas phase silicon nano material, nanometer material, the coated organic-inorganic nano material of silica；Hetero atom is mixed
Miscellaneous silicon nano material, and the material of silicone hydroxyl can be derived by chemical treatment.
4. according to the method described in claim 1, it is characterized in that, the catalyst is three substitution organic phosphines.
5. according to the method described in claim 4, it is characterized in that, the three substitution organic phosphines are selected from triphenylphosphine, three is different
Propyl phosphine, benzyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, tri-tert-butylphosphine, three p-methylphenyl phosphines.
6. according to the method described in claim 1, it is characterized in that, the dosage of the catalyst is vinyl sulfone derivative substance
Amount 1~10%.
7. according to the method described in claim 1, it is characterized in that, the aprotic polar solvent be selected from acetonitrile, acetone, N,
Dinethylformamide, dimethyl sulfoxide (DMSO), tetrahydrofuran , dioxanes, dichloromethane and chloroform.
8. according to the method described in claim 1, it is characterized in that, 25-60 DEG C of the reaction temperature.
9. method described in claim 1, which is characterized in that reaction time 6-12h.
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| CN110078829A (en) * | 2019-04-29 | 2019-08-02 | 大连理工大学 | A kind of covalent fixing means of histidine-tagged protein fixed point based on the reaction of vinyl sulfone surface |
| CN110372836A (en) * | 2019-07-18 | 2019-10-25 | 大连理工大学 | A kind of vinyl sulfone surface initiation water phase anionic polymerisation process |
| CN116640320A (en) * | 2023-05-30 | 2023-08-25 | 智慧油服科技(成都)有限公司 | Anti-collapse plugging agent and preparation method thereof |
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