CN109464969B - Functionalization method of nitrogen-rich polymer on ferroferric oxide/silicon dioxide nano particle surface - Google Patents
Functionalization method of nitrogen-rich polymer on ferroferric oxide/silicon dioxide nano particle surface Download PDFInfo
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Abstract
The invention relates to a functionalization method of a nitrogen-rich polymer on the surface of a magnetic silicon dioxide nano particle, which mainly adopts hydrophilic Fe3O4The nano particles are used as the core, and SiO with a certain thickness is coated on the surface of the nano particles by a sol-gel method2A shell layer is formed, and then a method of protonating 4-vinylpyridine (4-VP) monomer to assist in-situ surface polymerization is adopted to obtain highly crosslinked P4VP functionalized Fe3O4@SiO2Core-shell nanocomposites. The invention does not need to use SiO2The surface is complexly modified, only the pH value of the system is needed to be adjusted to obtain a protonated 4-VP monomer, and the protonated 4-VP monomer is reacted with SiO2Strong electrostatic interaction of surface silicon hydroxyl groups on SiO2The surface is directly polymerized, so that the process of functionalizing the surface of the silicon dioxide is simplified; by adding DVB as cross-linking agent, it can be added into SiO2The surface is coated with a layer of highly cross-linked P (4VP-DVB), so that the stability of the surface functionalized material is greatly improved.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a method for functionalizing the surface of a silicon dioxide nano particle.
Background
Because of its adjustable surface functionalization, good chemical and physical stability, and good biocompatibility, functionalized Silica (SiO)2) Particles have great potential in many specific fields, such as molecular recognition, drug delivery, biosensing, heterogeneous catalysis, and the like. At present, for SiO2There are two main methods for the surface functionalization of nanoparticles. One is formed by silane coupling agent containing corresponding functional groups and SiO2The interaction between the surface silicon hydroxyl groups directly modifies different functional groups such as amino, carbonyl and the like on the SiO2The surface of the nanoparticles. The other method is to graft a functional polymer on SiO2The surface of the nanoparticles. Compared with the method of directly modifying the surface of organic molecules, the grafting method of the functional polymer has better stability and can control SiO2The distribution of the functional groups on the surface of the nano-particles further realizes some special applications, such as the recognition of different types of molecules, the regulation and control of the selectivity of the supported metal catalyst and the like.
Attempts have been made to graft various functional polymers onto SiO2The surface of nanoparticles, such as branched polyamines, poly (N-isopropylacrylamide), poly (4-vinylpyridine) (P4VP), and the like. Of these, P4VP has received much attention as the most important functional polymer. Because the pyridine functional group in the P4VP molecular chain has strong coordination effect on metal ions, metal nanoparticles and biomolecules, and the unique pH response protonation-deprotonation characteristic capable of inducing the expansion and contraction change of the P4VP molecular chain. The grafting of P4VP onto the surface of silica particles to form a core-shell structure is currently achieved primarily by additional surface modification to enhance the compatibility between the silica surface and the 4-vinylpyridine monomer. Wanchun Guo et al (chem. Asian J.,2015,10,701-708) by first applying Fe3O4@SiO2The surface of the nano-particle is decorated with a layer of [3- (methacryl)yloxy)propyl]trimethoxysilane, then coating P4VP on SiO by surface polymerization2A surface; mohammad Reza Nabid et al (ChemCatchem,2014,6,538-546) in Fe3O4@SiO2The surface of the nano-particles firstly adsorbs an atom transfer radical polymerization initiator, and then P4VP is coated on SiO in an atom transfer radical polymerization mode2A surface; lei Wu et al (Macromolecules,2016,49,9586-9596) in SiO2The surface of the nano-particles firstly adsorbs atom transfer radical polymerization initiator, and then poly (N-isopropyl acrylamide) is coated on SiO by atom transfer radical polymerization2Then the surface is coated with P4VP by surface polymerization by using the polymer as an intermediate layer to realize SiO2The functionalization of (2). These methods, which involve one or more additional surface modifications, and the correspondingly complicated synthesis steps required, limit the biological and catalytic applications of P4 VP-functionalized silica nanoparticles. Therefore, how to develop a simple method for grafting P4VP on the surface of silica nanoparticles still remains a great challenge.
Disclosure of Invention
The invention mainly aims to provide a method for functionalizing a ferroferric oxide/silicon dioxide nano particle surface nitrogen-rich polymer, which has no additional surface modification, can improve the stability of a surface functionalized material and can be polymerized under the assistance of a protonated monomer. The invention mainly adopts hydrophilic Fe3O4As core, coated with SiO with a certain thickness2A shell layer is formed, and then a method of protonating 4-vinylpyridine (4-VP) monomer to assist surface polymerization is adopted to obtain highly crosslinked P4VP functionalized Fe3O4@SiO2Core-shell nanocomposites.
The technical scheme of the invention comprises the following steps:
(1)Fe3O4@SiO2preparing magnetic core-shell composite microspheres:
adding 0.05-0.2 g Fe into 100mL ethanol/distilled water mixed solvent3O4Ratio of nanoparticles of Fe3O4Dispersing nanoparticles in ethanol/distillationUniformly dispersing the mixed solvent in water by ultrasonic treatment for 10-60 min, adding 2.5-10 mL of ammonia water and 0.25-1.0 mL of tetraethyl orthosilicate into each 100mL of ethanol/distilled water mixed solvent under mechanical stirring at 200-400 r/min, adding 28% ammonia water into the mixed solvent, stirring for 10 min, adding tetraethyl orthosilicate under continuous stirring, reacting for 1-10 h, washing the obtained suspension with ethanol and water for three times alternately under the assistance of an external magnetic field to obtain Fe3O4@SiO2Magnetic core-shell composite microspheres;
in the ethanol/distilled water mixed solvent, the volume ratio of ethanol to distilled water is 4: 1;
(2)Fe3O4@SiO2preparation of @ P (4VP-DVB) magnetic core-shell composite microsphere:
adding 0.04-0.3 g Fe into per 100mL distilled water3O4@SiO2The proportion of the magnetic core-shell composite microspheres is that Fe obtained in the step (1)3O4@SiO2Dispersing magnetic core-shell composite microspheres in distilled water by ultrasonic wave for 10-60 min, and stirring at 20-30 ℃ under the condition of continuous inert gas flow according to Fe3O4@SiO2Magnetic core-shell composite microsphere solution: 4-VP monomer: inorganic acid aqueous solution: divinylbenzene: the volume ratio of the azodiisobutyamidine hydrochloride initiator is 1500: 1-8.1: 3.7-30: 0.37-3: 23 to 187.5, in sequence to the Fe3O4@SiO2Adding a 4-VP monomer, an inorganic acid aqueous solution with the concentration of 0.5mol/L and divinylbenzene into a magnetic core-shell composite microsphere solution, adsorbing for 2-10 hours, then adding an azodiisobutyramidine hydrochloride initiator with the concentration of 8.0g/L, adjusting the reaction temperature to 80 ℃, reacting for 6-18 hours under stirring at 300r/min, separating the product under a magnetic field, alternately washing for more than 3 times by using ethanol and water until the pH value is 6-7, and drying in vacuum at 60 ℃ to obtain the product: fe3O4@SiO2@ P (4VP-DVB) magnetic core-shell composite microspheres.
The inert gas is one of high-purity nitrogen and argon;
the inorganic acid aqueous solution is one of hydrochloric acid, sulfuric acid and nitric acid;
the invention firstly uses sol-gel method to prepare Fe3O4The surface of the microsphere is coated with a layer of SiO2Shell, protonating 4-vinylpyridine monomer by regulating pH part of system without using silane coupling agent2In the case of modification, the modification is carried out by adsorbing the modified substance on SiO2Surface, and using Divinylbenzene (DVB) as a crosslinking agent, by Fe3O4@SiO2Method for direct radical polymerization of surfaces, finally on SiO2Directly coating a layer of highly crosslinked nitrogen-rich poly (4-vinylpyridine-divinylbenzene) (P (4VP-DVB)) polymer on the surface; wherein 4-VP can be protonated to different degrees by adjusting the pH of the system, and can be electrostatically adsorbed to SiO2The silicon hydroxyl on the surface forms stronger coordination, and then the polymerization reaction is directly carried out on the surface in the presence of a cross-linking agent and an initiator, and the whole process does not need to additionally carry out the reaction on SiO2The surface is subjected to complex modifications. And the obtained nitrogen-rich polymer has a high crosslinking structure and higher stability compared with a linear polymer.
Compared with the prior art, the invention has the following advantages:
1. without the need for SiO2The surface is complexly modified, only the pH value of the system is needed to be adjusted to obtain a protonated 4-VP monomer, and the protonated 4-VP monomer is reacted with SiO2Strong electrostatic interaction of surface silicon hydroxyl groups on SiO2The surface is directly polymerized, and the process of functionalizing the surface of the silicon dioxide is simplified.
2. By adding DVB as cross-linking agent, it can be added into SiO2The surface is coated with a layer of highly cross-linked P (4VP-DVB), so that the stability of the surface functionalized material is greatly improved.
Drawings
FIG. 1 shows Fe obtained in example 2 of the present invention3O4@SiO2Transmission map of magnetic core-shell composite microspheres;
FIG. 2 is a diagram illustrating the preparation of Fe in example 2 of the present invention3O4@SiO2Transmission diagram of @ P (4VP-DVB) magnetic core-shell composite microspheres.
Detailed Description
Example 1
0.05g of Fe3O4Dispersing nano particles in 100mL of ethanol/distilled water mixed solvent with the volume ratio of 4:1, performing ultrasonic treatment for 10 minutes to uniformly disperse the nano particles, adding 2.5mL of ammonia water with the concentration of 28 wt% under mechanical stirring at 200r/min, stirring for 10 minutes, adding 0.25mL of tetraethyl orthosilicate under continuous stirring, reacting for 1 hour, alternately washing the obtained suspension with ethanol/water for three times under the assistance of an external magnetic field to obtain Fe3O4@SiO2Magnetic core-shell composite microspheres.
Mixing the obtained Fe3O4@SiO20.05g of magnetic core-shell composite microspheres are added into 120mL of distilled water for ultrasonic dispersion for 10 minutes, and then 0.108mL of 4-VP monomer, 0.4mL of 0.25mol/L sulfuric acid aqueous solution and 0.04mL of DVB are sequentially added under the conditions of mechanical stirring at 30 ℃ and continuous argon flow for adsorption for 2 hours. Then 2.5mL of azobisisobutyramidine hydrochloride initiator with a concentration of 8.0g/L is added, the reaction temperature is adjusted to 80 ℃, the reaction is carried out for 6 hours under the stirring of 300r/min, the product is separated under a magnetic field, washed for 3 times by using ethanol and water alternately until the pH value is 6, the product is collected after vacuum drying at 60 ℃, and Fe is obtained3O4@SiO2@ P (4VP-DVB) magnetic core-shell composite microspheres.
Example 2
0.1g of Fe3O4Dispersing nano particles in 100mL of ethanol/distilled water mixed solvent, performing ultrasonic treatment for 20 minutes to uniformly disperse the nano particles, adding 5mL of ammonia water with the concentration of 28 wt% under mechanical stirring at 300r/min, stirring for 10 minutes, adding 0.5mL of tetraethyl orthosilicate under continuous stirring, reacting for 6 hours, washing the obtained suspension by using ethanol/water alternately for three times under the assistance of an external magnetic field to obtain Fe3O4@SiO2Magnetic core-shell composite microspheres;
as shown in figure 1, the grain diameter of the inner core is 250-300 nm, the thickness of the silicon dioxide shell is 80 +/-10 nm, and the shell is uniformly coated on Fe3O4A surface.
Mixing the obtained Fe3O4@SiO20.12g of magnetic core-shell composite microspheres are addedAfter the mixture was ultrasonically dispersed in 120mL of distilled water for 20 minutes, 0.216mL of 4-VP monomer, 0.8mL of a hydrochloric acid aqueous solution having a concentration of 0.5mol/L and 0.08mL of divinylbenzene were sequentially added under mechanical stirring at 30 ℃ under a continuous nitrogen flow, and the mixture was adsorbed for 5 hours. Then 5mL of azo-bis-isobutyramidine hydrochloride initiator with the concentration of 8.0g/L is added, the reaction temperature is adjusted to 80 ℃, the mixture reacts for 12 hours under the stirring of 300r/min, the product is separated under the magnetic field, the mixture is washed by ethanol and water for 3 times alternately until the pH value is 7, the product is collected after vacuum drying at 60 ℃, and Fe is obtained3O4@SiO2@ P (4VP-DVB) magnetic core-shell composite microspheres.
As shown in FIG. 2, the thickness of the P (4VP-DVB) shell layer is about 20nm, and the P (4VP-DVB) is uniformly coated on Fe3O4@SiO2A surface.
Example 3
0.2g of Fe3O4Dispersing nano particles in 100mL of ethanol/distilled water mixed solvent, performing ultrasonic treatment for 40 minutes to uniformly disperse the nano particles, adding 10mL of ammonia water with the concentration of 28 wt% under mechanical stirring at 400r/min, stirring for 10 minutes, adding 1.0mL of tetraethyl orthosilicate under continuous stirring, reacting for 10 hours, washing the obtained suspension by using ethanol/water alternately for three times under the assistance of an external magnetic field to obtain Fe3O4@SiO2Magnetic core-shell composite microspheres.
Mixing the obtained Fe3O4@SiO20.3g of magnetic core-shell composite microspheres are added into 120mL of distilled water for ultrasonic dispersion for 40 minutes, and then 0.648mL of 4-VP monomer, 2.4mL of nitric acid aqueous solution with the concentration of 0.5mol/L and 0.24mL of DVB are sequentially added under the conditions of mechanical stirring and continuous nitrogen flow at 25 ℃ for adsorption for 10 hours; then adding 15mL of azo-bis-isobutyramidine hydrochloride initiator with the concentration of 8.0g/L, adjusting the reaction temperature to 80 ℃, reacting for 18 hours under the stirring of 300r/min, separating the product under a magnetic field, washing for 4 times by using ethanol and water alternately until the pH value is 7, drying in vacuum at 60 ℃, collecting the product to obtain Fe3O4@SiO2@ P (4VP-DVB) magnetic core-shell composite microspheres.
Example 4
0.15g of Fe3O4Dispersing nano particles in 100mL of ethanol/distilled water mixed solvent, performing ultrasonic treatment for 60 minutes to uniformly disperse the nano particles, adding 7.5mL of ammonia water with the concentration of 28 wt% under mechanical stirring at 350r/min, stirring for 10 minutes, adding 0.75mL of tetraethyl orthosilicate under continuous stirring, reacting for 4 hours, alternately washing the obtained suspension with ethanol/water for three times under the assistance of an external magnetic field to obtain Fe3O4@SiO2Magnetic core-shell composite microspheres;
mixing the obtained Fe3O4@SiO20.15g of the magnetic core-shell composite microspheres was added to 120mL of distilled water and ultrasonically dispersed for 40 minutes, and then 0.27mL of 4-VP monomer, 1.0mL of 0.5mol/L hydrochloric acid aqueous solution, and 0.1mL of divinylbenzene were sequentially added thereto under mechanical stirring and argon flow at 30 ℃ to adsorb for 8 hours. Then 6.25mL of azo-bis-isobutyramidine hydrochloride initiator with the concentration of 8.0g/L is added, the reaction temperature is adjusted to 80 ℃, the mixture reacts for 15 hours under the stirring of 300r/min, the product is separated under the magnetic field, the mixture is washed for 4 times by ethanol and water alternately until the pH value is 7, the product is collected after vacuum drying at 60 ℃, and Fe is obtained3O4@SiO2@ P (4VP-DVB) magnetic core-shell composite microspheres.
Claims (4)
1. A method for functionalizing a nitrogen-rich polymer on the surface of ferroferric oxide/silicon dioxide nano particles is characterized by comprising the following steps: the method comprises the following steps:
(1)Fe3O4@SiO2preparing magnetic core-shell composite microspheres:
adding 0.05-0.2 g Fe into 100mL ethanol/distilled water mixed solvent3O4Ratio of nanoparticles of Fe3O4Dispersing nano particles in an ethanol/distilled water mixed solvent, performing ultrasonic treatment for 10-60 min to uniformly disperse the nano particles, adding 2.5-10 mL of ammonia water and 0.25-1.0 mL of tetraethyl orthosilicate into each 100mL of the ethanol/distilled water mixed solvent under mechanical stirring at 200-400 r/min, adding 28% ammonia water into the mixed solvent, stirring for 10 min, adding tetraethyl orthosilicate under continuous stirring, reacting for 1-10 h, and reacting for 1-10 h to obtain the nano particlesWashing the suspension with ethanol and water alternately for three times under the assistance of an external magnetic field to obtain Fe3O4@SiO2Magnetic core-shell composite microspheres;
(2)Fe3O4@SiO2preparation of @ P (4VP-DVB) magnetic core-shell composite microsphere:
adding 0.04-0.3 g Fe into per 100mL distilled water3O4@SiO2The proportion of the magnetic core-shell composite microspheres is that Fe obtained in the step (1)3O4@SiO2Dispersing magnetic core-shell composite microspheres in distilled water by ultrasonic wave for 10-60 min, and stirring at 20-30 ℃ under the condition of continuous inert gas flow according to Fe3O4@SiO2Magnetic core-shell composite microsphere solution: 4-VP monomer: inorganic acid aqueous solution: divinylbenzene: the volume ratio of the azodiisobutyamidine hydrochloride initiator is 1500: 1-8.1: 3.7-30: 0.37-3: 23 to 187.5, in sequence to the Fe3O4@SiO2Adding a 4-VP monomer, an inorganic acid aqueous solution with the concentration of 0.5mol/L and divinylbenzene into a magnetic core-shell composite microsphere solution, adsorbing for 2-10 hours, then adding an azodiisobutyramidine hydrochloride initiator with the concentration of 8.0g/L, adjusting the reaction temperature to 80 ℃, reacting for 6-18 hours under stirring at 300r/min, separating the product under a magnetic field, alternately washing for more than 3 times by using ethanol and water until the pH value is 6-7, and drying in vacuum at 60 ℃ to obtain the product: fe3O4@SiO2@ P (4VP-DVB) magnetic core-shell composite microspheres.
2. The method for functionalizing the nitrogen-rich polymer on the surfaces of ferroferric oxide/silicon dioxide nano particles according to claim 1, characterized by comprising the following steps of: in the ethanol/distilled water mixed solvent, the volume ratio of ethanol to distilled water is 4: 1.
3. The method for functionalizing the nitrogen-rich polymer on the surfaces of ferroferric oxide/silicon dioxide nano particles according to claim 1, characterized by comprising the following steps of: the inert gas is one of high-purity nitrogen and argon.
4. The method for functionalizing the nitrogen-rich polymer on the surfaces of ferroferric oxide/silicon dioxide nano particles according to claim 1, characterized by comprising the following steps of: the inorganic acid aqueous solution is one of hydrochloric acid, sulfuric acid and nitric acid.
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| CN114011240A (en) * | 2021-10-25 | 2022-02-08 | 西南交通大学 | Functional group Fe3O4/SiO2Preparation and forward osmosis application of core-shell composite magnetic nano material |
| CN114736434B (en) * | 2022-04-23 | 2023-11-17 | 浙江科赛新材料科技有限公司 | Preparation method of PTFE fastener with metal detectable function |
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