CN112679665B - Preparation method of nano spherical polyelectrolyte brush - Google Patents
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Abstract
The invention provides a preparation method of a nano spherical polyelectrolyte brush, which comprises the following steps: dialyzing the polystyrene nuclear emulsion by adopting ultrapure water to remove impurities, adding the dialyzed and purified polystyrene nuclear emulsion into a flask, pumping out nitrogen, pumping out the polystyrene nuclear emulsion by adopting an injector, diluting a water-soluble polymer monomer, adding the diluted water-soluble polymer monomer into the flask, pumping out the nitrogen, and pumping out the water-soluble polymer monomer by using the injector; fixing the injector filled with the polystyrene nuclear emulsion and the water-soluble polymer monomer on an injection pump; a channel is arranged near the high-pressure ultraviolet lamp, and a cooling device is arranged at the accessory of the channel; connecting the injector with the channel, starting the ultraviolet lamp, receiving the product at the interface after the interior of the reactor is stable, and dialyzing and purifying by a dialysis bag to obtain the nano spherical polyelectrolyte brush. The invention can realize the continuous reaction and preparation of the polyelectrolyte brush, effectively overcome the problems caused by intermittent preparation and amplification effect and greatly improve the production efficiency.
Description
Technical Field
The invention belongs to the technical field of functional nano materials, and relates to a continuous preparation method and application of a nano spherical polyelectrolyte brush, in particular to a novel method for efficiently and quickly preparing a polyelectrolyte-rich nano spherical polyelectrolyte brush by using an optical microreactor, which can be applied to the fields of scale inhibitors of filter membranes, removal of harmful metal ions in water, recovery of ions of noble metals, medical diagnosis and the like.
Background
When the polymer chains with charges are densely distributed on the surface of the nano-matrix in a form of being fixed at one end, the free ends of the polymer chains are extended outwards due to volume repulsion and electrostatic repulsion, and a structure called nano-polyelectrolyte brush is formed. The interaction, the caking property and the friction property of the nano matrix surface with external substances can be obviously improved by introducing the polymer brush on the nano matrix surface, and the nano matrix surface has wide functions in many fields.
The first inventor of the present application in 1999 first realized the preparation of nano spherical polyelectrolyte brush (hereinafter referred to as nano ball brush) by photo emulsion polymerization in Germany, that is, photo initiator is connected to the surface of core and initiates the in-situ polymerization of monomer under the irradiation of ultraviolet light to form the spherical polyelectrolyte brush, and spherical polyacrylic acid brush and polyvinyl benzene sulfonic acid sodium brush with the size of 100-200 nm are synthesized by this method (Macromolecules 1999,32, 6043). In 2008, the applicant developed a new thermal initiator and expanded the synthesis method of the nano ball brush (publication numbers CN101381421A and CN 101381435B). In 2009 the applicant prepared a magnetic nano spherical polyelectrolyte brush by a method of coating a nano magnetic particle prepared in advance in a core (publication No. CN 101544730B). In 2011, the applicant takes polybutadiene emulsion as a nano core and initiates polymerization of polyelectrolyte monomers on the surface of a nano matrix to prepare a novel spherical polyelectrolyte brush with a nano size (publication No. CN 102516463B).
At present, a relatively mature method for preparing the nano spherical polyelectrolyte brush is carried out in a closed reactor, and is an indirect preparation method, namely, a nano core matrix, a light/heat initiator and a polyelectrolyte monomer are closed in a closed reactor protected by nitrogen, and are stirred and reacted for a certain time to prepare the polyelectrolyte brush. However, this batch type production method has a problem that it is difficult to overcome in industrial production: firstly, converting an intermittent reaction environment into large-scale continuous production; secondly, after industrial amplification, the heat transfer and mass transfer problems caused by the amplification effect can cause the reduction of the reaction efficiency and the increase of unqualified products; thirdly, after industrial amplification, for photo-initiated polymerization, energy is greatly attenuated when light passes through a large-volume solution, and then the efficiency of photo-initiated polymerization is reduced, and for thermal-initiated polymerization, the efficiency of thermal initiation is also reduced due to mass and heat transfer problems generated by amplification; and fourthly, the ultraviolet light reactor is complex, expensive and difficult to amplify on a large scale, and is not beneficial to large-scale continuous production.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nano spherical polyelectrolyte brush and a preparation method thereof, aiming at solving the problem that the prior art cannot realize continuous production.
The technical scheme for solving the technical problems is as follows: a preparation method of a nanometer spherical polyelectrolyte brush comprises the following steps:
(1) dialyzing the polystyrene nuclear emulsion by adopting ultrapure water to remove impurities, and finishing dialysis when the conductivity of the ultrapure water subjected to external dialysis is unchanged;
(2) adding the purified polystyrene nuclear emulsion obtained in the step (1) into a flask, pumping nitrogen for 3-5 times, pumping out the polystyrene nuclear emulsion by using an injector, and wrapping tin foil paper on the outer layer of the injector to prevent light; diluting the water-soluble polymer monomer to 1-50 × 10-5Adding the mixture into a flask after mol/mL, pumping and filling nitrogen for 3-5 times, and pumping out the water-soluble polymer monomer by using an injector; fixing an injector filled with polystyrene nuclear emulsion and water-soluble polymer monomers on an injection pump;
(3) a high-pressure ultraviolet lamp is used as a light source, a channel is arranged near the light source, the size of the channel is 0.8-1.6 mm, and a cooling device is arranged at the accessory of the channel;
(4) and (3) connecting the two injectors in the step (2) with the channel in the step (3) through a T-shaped three-way valve, starting an ultraviolet lamp, feeding after the channel is rinsed with materials, receiving a product at a joint after the interior of the reactor is stabilized after 3-6 retention times (wherein one retention time refers to the time of passing through the channel once), and dialyzing and purifying the obtained product in ultrapure water by adopting a dialysis bag with the molecular weight cutoff of 5-50 k to obtain the nano spherical polyelectrolyte brush.
The invention is further set that the solid content of the polystyrene core emulsion is 1-3%, wherein emulsion particles (namely polystyrene cores) are prepared by a method (Macromolecules 1999,32,6043), the surfaces of the emulsion particles are grafted with a photoinitiator, the photoinitiator adopts HMEM in patent 200910053204.0 (a method for preparing magnetic particles by using a nano spherical polyelectrolyte brush as a microreactor), the styrene living on the surfaces of the polystyrene cores is grafted with the HMEM through copolymerization, and the photoinitiator is wrapped on the surfaces of the polystyrene cores in a covalent bond form to form the styrene core emulsion with the photoinitiator on the surfaces. For the grafting reaction, it is possible to carry out the HMEM dropwise into the styrene emulsion. In the step (4), the photoinitiator generates free radicals under the irradiation of ultraviolet light to react with the water-soluble polymer monomer, so that the polymer monomer is grafted on the surface of the core through covalent bonds, and finally the nano spherical polyelectrolyte brush is generated.
The invention is further provided that in the step (2), the water-soluble polymer monomer is diluted to 1-50 multiplied by 10-5mol/mL。
The invention is further set that the water-soluble polymer monomer is acrylic acid, methacrylic acid or sodium p-styrenesulfonate, and the mass of the water-soluble polymer monomer is 10-100% of the solid content of the polystyrene core emulsion.
The invention further provides that in step (4), the flow rate ratio of the polystyrene core emulsion and the water-soluble polymer monomer is 2:1-2: 5.
The invention is further set that the aperture of the inner hole of the T-shaped three-way valve is 0.5-1 mm.
The invention is further set that in the step (2), the flow rate of the injection pump is 0.01-5 mL/min.
The invention is further provided that the cooling device is a circulating water cooling device.
The invention provides the nano spherical polyelectrolyte brush prepared by the preparation method, and the particle size of the nano spherical polyelectrolyte brush is 100-200 nm. The nano spherical polyelectrolyte brush comprises a core in the middle and chains connected outside the core, wherein the chain length refers to the length of the chains, and the particle size of the nano spherical polyelectrolyte brush refers to the overall size comprising the core and the chains. The size of the nano spherical polyelectrolyte brush can be controlled by adjusting the size and volume of the channel of the optical microreactor and the reaction residence time. The size, volume and reaction residence time of the channel have no absolute formula relationship, and the device is flexible to adjust and high in controllability.
The invention also provides an optical microreactor for preparing the nano spherical polyelectrolyte brush, which comprises an ultraviolet lamp, a pipeline, an injector, an injection pump, a T-shaped three-way valve and a circulating water cooling device; the utility model discloses a polystyrene nuclear emulsion injection pump, including ultraviolet lamp, circulating water cooling device, pipeline, injector, injection pump, the ultraviolet lamp is the cylindricality, the circulating water cooling device is located the ultraviolet lamp outside, the pipeline encircle in the circulating water cooling device outside, be equipped with water inlet and delivery port on the circulating water cooling device, the one end of pipeline is passed through two T type three-way valve intercommunication the injector, two the injector is used for placing polystyrene nuclear emulsion and water-soluble polymer monomer respectively, the injector is fixed on the injection pump, the other end of pipeline is the product exit end.
The invention is further set that the circulating water cooling device is a snakelike cooling pipe wound outside the ultraviolet lamp or a barrel-shaped pipe sleeved outside the ultraviolet lamp.
Compared with an intermittent kettle type reactor, the invention can realize continuous reaction and preparation of the polyelectrolyte brush, can effectively overcome the problems caused by intermittent preparation and amplification effect, and greatly improve the production efficiency. The microfluid flows are subjected to flow and reaction through the optical micro-reaction, so that the continuous flow and preparation are realized, the retention time of reaction materials in the optical micro-reactor is prolonged, the polyelectrolyte brush can be simply prepared, and the chain length of the polyelectrolyte brush can be regulated and controlled. The method is simple and is an important way for large-scale continuous large-scale production of the nano spherical polyelectrolyte brush in the future. In order to mix and transfer reaction materials uniformly, the optical microreactor can adopt modes of passive mixing, internal component introduction, external field introduction, oscillation and the like, for example, the optical microreactor can be directly placed in an oscillation mixing container to realize oscillation mixing.
Drawings
FIG. 1 is a schematic diagram of the present invention employing an optical microreactor reaction;
FIG. 2 is a graph illustrating the measurement of the size of polyelectrolyte brushes obtained in examples 1 and 5, using a dynamic light scattering method;
FIG. 3 is a graph showing the stability test of example 2.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Setting the invention to carry out reaction in a device as shown in figure 1, wherein 100 is a photo-microreactor; 1. a channel; 2. an ultraviolet lamp; 3. and (5) cooling the water.
Example 1
20g of polystyrene core emulsion (the solid content is 3.5 wt% and the particle diameter is 110 nm) is diluted to 1.7X 10 by adding deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, and pumping out by using a 50mL injector; 0.525g of acrylic acid (75% of the solids content of the polystyrene core emulsion) was diluted to 3.4X 10 with deionized water-4Filling nitrogen into a 250mL four-mouth flask for 3-5 times in a mol/mL mode, pumping out a 50mL injector, and fixing the injector to an injection pump; a micro-channel size of 0.8mm and a volume of 3.165mL of optical microreactor are used, and a T-shaped tee with an inner hole of 0.5mm is adopted for material mixing. The retention time is 1h, the two materials are fed by adopting a flow rate ratio of 1:1, the product is collected at an outlet, and after the product is dialyzed and purified in ultrapure water by adopting a dialysis bag with a molecular weight cut-off of 14000, the average particle size of the nano spherical polyelectrolyte brush is measured to be 180 nanometers (the pH is equal to 8).
Example 2
20g of a polystyrene core emulsion (measured as a solid content of 3.5 wt.%)Particle size of 110 nm) is diluted to 1.369X 10 by adding deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, and pumping out by using a 50mL injector; 0.49g of acrylic acid (70% of the solids content of the polystyrene core emulsion) was diluted to 1.369X 10 with deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, pumping out a 50mL injector, and fixing the injector to an injection pump; a micro-channel size of 1.6mm and a volume of 18.689mL of an optical micro-reactor are used, and a T-shaped tee with an inner hole of 0.5mm is adopted for material mixing. The retention time is 1h, the two materials are fed by adopting a flow ratio of 1:1, the product is collected at the outlet, and after the product is dialyzed and purified in ultra-pure water by adopting a dialysis bag with a molecular weight cut-off of 14000, the average particle size of the nano spherical polyelectrolyte brush is measured to be 160 nanometers (pH is 8).
Example 3
20g of polystyrene core emulsion (the solid content is measured to be 3.5 wt%, the particle diameter is 110 nm) is diluted to 1.369 multiplied by 10 by adding deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, and pumping out by using a 50mL injector; 0.21g of acrylic acid (30% of the solids content of the polystyrene core emulsion) was diluted to 1.369X 10 with deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, pumping out a 50mL injector, and fixing the injector to an injection pump; a micro-channel optical micro-reactor with the size of 1.6mm and the volume of 18.689mL is used, and a T-shaped tee with an inner hole of 0.5mm is adopted for material mixing. The retention time is 0.5h, the two materials are fed by adopting a flow rate ratio of 1:1, the product is collected at an outlet, and after dialysis purification is carried out in ultrapure water by adopting a dialysis bag with a molecular weight cut-off of 14000, the average particle diameter of the nano spherical polyelectrolyte brush is measured to be 140 nanometers (pH is 8).
Example 4
20g of polystyrene core emulsion (the solid content is 3.5wt percent and the particle size is 110 nanometers) is diluted to 1.369X 10 by adding deionized water-4Filling nitrogen into a 250mL four-mouth flask for 3-5 times in a mol/mL mode, and pumping out by using a 50mL injector; 0.07g of acrylic acid (10% of the solids content of the polystyrene core emulsion) was diluted to 2.023X 10 with deionized water-5In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, pumping out a 50mL injector, and fixing the injector to an injection pump; using a micro-channelThe size of the channel is 1.6mm, the volume is 18.689mL of the optical microreactor, and a T-shaped tee with an inner hole of 0.5mm is adopted for material mixing. The retention time is 0.5h, the two materials are fed by adopting a flow rate ratio of 1:1, the product is collected at the outlet, and after the product is dialyzed and purified in ultrapure water by adopting a dialysis bag with a molecular weight cut-off of 5000, the average particle diameter of the nano spherical polyelectrolyte brush is measured to be 130 nm (pH is equal to 8).
Example 5
20g of polystyrene core emulsion (the solid content is 3.5wt percent and the particle size is 110 nanometers) is diluted to 1.369X 10 by adding deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, and pumping out by using a 50mL injector; 0.07g of acrylic acid (10% of the solids content of the polystyrene core emulsion) was diluted to 2.023X 10 with deionized water-5In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, pumping out a 50mL injector, and fixing the injector to an injection pump; a micro-channel optical micro-reactor with the size of 1.6mm and the volume of 18.689mL is used, and a T-shaped tee with an inner hole of 0.5mm is adopted for material mixing. The retention time was 0.5min, the two feeds were fed at a 1:1 flow ratio, the product was collected at the outlet, purified by dialysis in ultrapure water using a 50000 mw cut-off dialysis bag, and the average particle size of the nanospherical polyelectrolyte brush was measured to be 116 nm (pH 8).
Example 6
20g of polystyrene core emulsion (the solid content is measured to be 3.5 wt%, the particle diameter is 110 nm) is diluted to 1.369 multiplied by 10 by adding deionized water-4Filling nitrogen into a 250mL four-mouth flask for 3-5 times in a mol/mL mode, and pumping out by using a 50mL injector; 0.21g of acrylic acid (30% of the solids content of the polystyrene core emulsion) was diluted to 1.369X 10 with deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, pumping out a 50mL injector, and fixing the injector to an injection pump; a micro-channel size of 1.6mm and a volume of 18.689mL of an optical micro-reactor are used, and a T-shaped tee with an inner hole of 0.5mm is adopted for material mixing. The retention time is 0.5h, the two materials are fed by adopting a flow rate ratio of 2:1, the product is collected at the outlet, and after the product is dialyzed and purified in ultrapure water by adopting a dialysis bag with a molecular weight cut-off of 14000, the average particle diameter of the nano spherical polyelectrolyte brush is measured to be 135 nanometers (the pH is equal to 8).
Example 7
20g of polystyrene core emulsion (the solid content is measured to be 3.5 wt%, the particle diameter is 110 nm) is diluted to 1.369 multiplied by 10 by adding deionized water-4In mol/mL, pumping nitrogen into a 250mL four-neck flask for 3-5 times, and pumping out by using a 50mL injector; 0.21g of acrylic acid (30% of the solids content of the polystyrene core emulsion) was diluted to 1.369X 10 with deionized water-4Filling nitrogen into a 250mL four-mouth flask for 3-5 times in a mol/mL mode, pumping out a 50mL injector, and fixing the injector to an injection pump; a micro-channel size of 1.6mm and a volume of 18.689mL of an optical micro-reactor are used, and a T-shaped tee with an inner hole of 0.5mm is adopted for material mixing. The retention time is 0.5h, the two materials are fed by adopting a flow ratio of 2:5, the product is collected at the outlet, and after the product is dialyzed and purified in ultrapure water by adopting a dialysis bag with a molecular weight cut-off of 14000, the average particle size of the nano spherical polyelectrolyte brush is measured to be 155 nm (pH is 8).
The sizes of polyelectrolyte brushes prepared in examples 1 and 5 were randomly measured by dynamic light scattering, as shown in FIG. 2. FIG. 3 is a stability test chart of example 2, which shows that the particle size of the particles does not change significantly within one month and the stability is very good, when the prepared nano spherical polyelectrolyte brush solution is left to stand.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of a nano spherical polyelectrolyte brush is characterized by comprising the following steps:
(1) dialyzing the polystyrene nuclear emulsion by adopting ultrapure water to remove impurities, and finishing dialysis when the conductivity of the ultrapure water subjected to external dialysis is unchanged;
(2) adding the purified polystyrene nuclear emulsion obtained in the step (1) into a flask, pumping nitrogen for 3-5 times, pumping out the polystyrene nuclear emulsion by using an injector, and wrapping tin foil paper on the outer layer of the injector to prevent light; diluting a water-soluble polymer monomer, adding the diluted water-soluble polymer monomer into a flask, pumping and filling nitrogen for 3-5 times, and pumping out the water-soluble polymer monomer by using an injector; fixing an injector filled with polystyrene nuclear emulsion and water-soluble polymer monomers on an injection pump;
(3) the method comprises the following steps of using a high-pressure ultraviolet lamp as a light source, arranging a channel near the light source, wherein the size of the channel is 0.8-1.6 mm, and arranging a cooling device near the channel;
(4) and (3) connecting the two injectors in the step (2) with the channel in the step (3) through a T-shaped three-way valve, starting an ultraviolet lamp, feeding after the channel is rinsed by materials, carrying out 3-6 retention times, receiving a product at a joint after the interior of the reactor is stable, and dialyzing and purifying the obtained product in ultrapure water by adopting a dialysis bag with the molecular weight cutoff of 5-50 k to obtain the nano spherical polyelectrolyte brush.
2. The method for preparing a nano spherical polyelectrolyte brush according to claim 1, wherein in the step (2), the water-soluble polymer monomer is diluted to 1-50 x 10-5mol/mL。
3. The preparation method of the nano spherical polyelectrolyte brush according to claim 1, wherein the water-soluble polymer monomer is acrylic acid, methacrylic acid or sodium p-styrenesulfonate, and the mass of the water-soluble polymer monomer is 10-100% of the solid content of the polystyrene core emulsion.
4. The method for preparing a nano spherical polyelectrolyte brush according to claim 1, characterized in that, in the step (4), the flow rate ratio of the polystyrene core emulsion and the water-soluble polymer monomer is 2:1-2:5 when feeding.
5. The method for preparing a nano spherical polyelectrolyte brush according to claim 1, wherein the inner bore diameter of the T-shaped three-way valve is 0.5-1 mm.
6. The method for preparing the nano spherical polyelectrolyte brush according to claim 1, wherein in the step (2), the flow rate of the injection pump is 0.01-5 mL/min.
7. The method for preparing the nano spherical polyelectrolyte brush according to claim 1, wherein the cooling device is a circulating water cooling device.
8. The spherical nano polyelectrolyte brush prepared by the preparation method according to any one of claims 1 to 7, wherein the particle size of the spherical nano polyelectrolyte brush is 100-200 nm.
9. An optical microreactor for preparing a nano spherical polyelectrolyte brush is characterized by comprising an ultraviolet lamp, a pipeline, an injector, an injection pump, a T-shaped three-way valve and a circulating water cooling device; the utility model discloses a polystyrene nuclear emulsion injection pump, including ultraviolet lamp, circulating water cooling device, pipeline, injector, injection pump, the ultraviolet lamp is the cylindricality, the circulating water cooling device is located the ultraviolet lamp outside, the pipeline encircle in the circulating water cooling device outside, be equipped with water inlet and delivery port on the circulating water cooling device, the one end of pipeline is passed through two T type three-way valve intercommunication the injector, two the injector is used for placing polystyrene nuclear emulsion and water-soluble polymer monomer respectively, the injector is fixed on the injection pump, the other end of pipeline is the product exit end.
10. A microreactor according to claim 9, wherein said circulating water cooling means is a serpentine cooling tube wound around said uv lamps or a barrel fitted around said uv lamps.
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| CN101630555A (en) * | 2009-06-17 | 2010-01-20 | 华东理工大学 | Magnetic particles preparation method by using nanometer spherical polyelectrolyte brush as micro-reactor |
| CN102516463A (en) * | 2011-11-24 | 2012-06-27 | 华东理工大学 | Method for preparing nano spherical polyelectrolyte brush |
| CN212045986U (en) * | 2020-04-03 | 2020-12-01 | 桂林电子科技大学 | Annular seal structure preparation facilities |
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2020
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| EP1415707A1 (en) * | 2002-10-29 | 2004-05-06 | Corning Incorporated | Method and microfluidic reactor for photocatalysis |
| JP2007090306A (en) * | 2005-09-30 | 2007-04-12 | Kri Inc | Method for manufacturing microstructure and microreactor |
| CN101630555A (en) * | 2009-06-17 | 2010-01-20 | 华东理工大学 | Magnetic particles preparation method by using nanometer spherical polyelectrolyte brush as micro-reactor |
| CN102516463A (en) * | 2011-11-24 | 2012-06-27 | 华东理工大学 | Method for preparing nano spherical polyelectrolyte brush |
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