CN110818824B - Liquid metal-assisted ultrasonic polymerization method - Google Patents
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- CN110818824B CN110818824B CN201911087672.XA CN201911087672A CN110818824B CN 110818824 B CN110818824 B CN 110818824B CN 201911087672 A CN201911087672 A CN 201911087672A CN 110818824 B CN110818824 B CN 110818824B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/56—Polymerisation initiated by wave energy or particle radiation by ultrasonic vibrations
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
Abstract
The invention provides a liquid metal-assisted ultrasonic polymerization method, which comprises the following steps: adding liquid metal into the monomer solution and mixing to obtain a mixed solution; carrying out ultrasonic treatment on the mixed solution to obtain a suspension; and separating and purifying the suspension to obtain the target polymer. The ultrasonic polymerization method provided by the invention can improve the reaction rate of polymerization reaction without removing oxygen, and has the advantages of simple preparation process, low requirement on equipment and strong operability.
Description
Technical Field
The invention relates to the field of new material preparation, in particular to a liquid metal-assisted ultrasonic polymerization method.
Background
The ultrasonic polymerization method is a process that under the action of ultrasonic waves, the ultrasonic waves can cause the solution to generate a cavitation phenomenon, the cavitation action breaks up a solvent or a monomer to form a free radical, and then the free radical initiates a polymerization reaction to obtain a target polymer. Because the ultrasonic polymerization method directly initiates polymerization reaction by utilizing ultrasonic waves, compared with the traditional polymerization method, the method has the advantages of low energy consumption, no need of adding an initiator, high conversion rate and the like.
However, in the ultrasonic polymerization process, since oxygen enters the reaction system to inhibit polymerization, the reaction solution needs to be previously purged of oxygen, and generally, an inert gas such as nitrogen or argon is used as a shielding gas to smoothly progress the reaction. The reaction steps are complicated, the requirement on reaction equipment is high, and the popularization and the application of industrial production are not facilitated.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a liquid metal-assisted ultrasonic polymerization method, and aims to solve the problems that the conventional ultrasonic polymerization method needs an oxygen removal step and is complicated in process.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a liquid metal assisted ultrasonic polymerization process comprising the steps of:
adding liquid metal into the monomer solution and mixing to obtain a mixed solution;
carrying out ultrasonic treatment on the mixed solution to obtain a suspension;
and separating and purifying the suspension to obtain the target polymer.
The liquid metal-assisted ultrasonic polymerization method is characterized in that the liquid metal is one or more of gallium-indium alloy, gallium-indium-tin alloy, gallium, mercury and bismuth.
The liquid metal-assisted ultrasonic polymerization method is characterized in that the monomer is one of acrylamide, acrylic acid, acryloyl morpholine, methacryloyloxyethyl trimethyl ammonium chloride or hydroxyethyl acrylate.
The liquid metal-assisted ultrasonic polymerization method comprises the following steps of adding a liquid metal into a monomer solution and mixing to obtain a mixed solution:
dissolving a monomer in a water solvent to obtain a monomer solution;
and adding liquid metal into the monomer solution to obtain a mixed solution.
The liquid metal-assisted ultrasonic polymerization method comprises the following steps of adding a liquid metal into a monomer solution and mixing to obtain a mixed solution:
dissolving a monomer in an organic solvent, adding an aqueous solvent, and mixing to obtain a monomer solution;
and adding liquid metal into the monomer solution to obtain a mixed solution.
The liquid metal-assisted ultrasonic polymerization method is characterized in that the organic solvent is one or more of acetonitrile, acetone and butanone.
The liquid metal-assisted ultrasonic polymerization method, wherein the concentration of the monomer solution is 0.5-2.5M.
The liquid metal-assisted ultrasonic polymerization method is characterized in that the mass-to-volume ratio of the liquid metal to the monomer solution is 10 mg: 1mL-50mg:1 mL.
The liquid metal-assisted ultrasonic polymerization method is characterized in that the ultrasonic treatment time is 80-240 min.
The liquid metal-assisted ultrasonic polymerization method comprises the following steps of:
centrifuging the suspension to obtain separated oxidized liquid metal and polymer solution;
carrying out rotary evaporation treatment on the polymer solution to obtain a target polymer;
and adding an alkaline solvent into the oxidized liquid metal, and reacting to obtain the recyclable liquid metal.
Has the advantages that: according to the invention, liquid metal is used for assisting ultrasonic polymerization, and in the ultrasonic process, the liquid metal reacts with oxygen in the monomer solution to achieve a deoxidation effect, so that the influence of the oxygen on the reaction rate is avoided, the liquid metal can also react with hydrogen peroxide generated in the ultrasonic process, the formation of free radicals is further promoted, and the conversion rate of a target polymer is improved. The ultrasonic polymerization method provided by the invention can improve the reaction rate of polymerization reaction without removing oxygen, can obtain better polymerization effect only by adding proper liquid metal, and has the advantages of simple preparation process, low requirement on equipment and strong operability.
Drawings
FIG. 1 is a flow chart of a liquid metal-assisted ultrasonic polymerization method according to an embodiment of the present invention.
FIG. 2 is an experimental flow chart of a liquid metal assisted ultrasonic polymerization method provided by an embodiment of the invention.
FIG. 3 is a graph of molecular weight and distribution of polyacrylamide according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flow chart of a preferred embodiment of a method for preparing a non-silicon hydrophilic softener according to the present invention, which includes the following steps:
s100, adding liquid metal into the monomer solution and mixing to obtain a mixed solution;
s200, carrying out ultrasonic treatment on the mixed solution to obtain a suspension;
s300, separating and purifying the suspension to obtain the target polymer.
In the embodiment, the liquid metal is mixed with the monomer solution, the mixed solution is subjected to polymerization reaction under the ultrasonic action, and the liquid metal in the mixed solution is dispersed into micron and nanometer droplets under the ultrasonic action, so that new liquid metal droplet surfaces are continuously formed, the contact area between the liquid metal surface and oxygen is increased, the liquid metal reacts with oxygen in a reaction system, the oxygen is consumed by the liquid metal, the effect of removing the oxygen is achieved, and even if the reaction system does not remove the oxygen in advance or introduce inert gas, the free radicals in the solution can still smoothly perform polymerization reaction. In this embodiment, the oxygen in the reaction system composed of the monomer solution and the liquid metal helps to stabilize the formed liquid metal droplets, greatly increases the surface area of the liquid metal, and thus can further increase the polymerization rate, and the molecular weight of the obtained polymer is also large.
In some embodiments, the liquid metal is one or more of gallium indium alloy, gallium indium tin alloy, pure gallium, mercury, and bismuth. In this embodiment, a suitable liquid metal may be selected according to a target polymer to be obtained, and a suitable reaction temperature may be selected according to a difference in melting point of the liquid metal, so that the reaction temperature is higher than the melting point of the selected liquid metal. In the embodiment, the liquid metal with the surface easily formed with the oxide film is adopted, so that the liquid metal can continuously form a new metal surface in the ultrasonic dispersion process, can immediately react with oxygen in the reaction solution to form the oxide film, further consumes the oxygen in the solution, and the obtained polymerization effect is better.
In some embodiments, the monomer comprises one of acrylamide, acrylic acid, acryloyl morpholine, methacryloyloxyethyl trimethyl ammonium chloride, and hydroxyethyl acrylate.
In some embodiments, the step of adding a liquid metal to the monomer solution and mixing to obtain a mixed solution comprises: dissolving a monomer in a water solvent to obtain a monomer solution; and adding liquid metal into the monomer solution to obtain a mixed solution.
In this embodiment, the monomer is a water-soluble monomer, the water solvent can be used for dispersing the monomer and also can be used as an initiator in the ultrasonic polymerization process of the monomer, and the ultrasonic wave can split water molecules to form hydroxyl radicals, so that the monomer polymerization is initiated, and the polymerization efficiency is improved.
In some embodiments, the step of adding a liquid metal to the monomer solution and mixing to obtain a mixed solution comprises: dissolving a monomer in an organic solvent, adding an aqueous solvent, and mixing to obtain a monomer solution; and adding liquid metal into the monomer solution to obtain a mixed solution.
In this embodiment, the monomer is soluble in an organic solvent, and in order to improve the polymerization efficiency of the monomer, a water solvent may be added to the organic solvent, and the ultrasonic treatment may split water molecules to form hydroxyl radicals, thereby initiating the polymerization of the monomer and improving the polymerization efficiency.
In some embodiments, the organic solvent is one or more of acetonitrile, acetone, and butanone, but is not limited thereto.
In some embodiments, the concentration of the monomer solution is 0.5 to 2.5M. In the embodiment, the monomer solution is uniformly dispersed in the concentration range, is not easy to agglomerate, and can efficiently generate polymerization reaction in the ultrasonic treatment process.
In some embodiments, the mass to volume ratio of the liquid metal to the monomer solution is 10 mg: 1mL-50mg:1 mL. Within this range, the liquid metal can sufficiently react with oxygen in the reaction system to remove oxygen, so that the radical polymerization reaction can be efficiently performed.
In some embodiments, the mixed solution is subjected to ultrasonic treatment for 80-240min to obtain a suspension.
In the embodiment, the mixed solution is placed in a constant-temperature water bath, ultrasonic treatment is performed by using an ultrasonic cell crusher, liquid metal is ultrasonically dispersed into micro or nano liquid drops to form a new liquid metal surface in the ultrasonic process, the contact area between the liquid metal and oxygen in the solution is greatly increased, the liquid metal and the oxygen are promoted to react to form a metal oxide film, so that the oxygen in the solution is consumed, oxygen is not required to be removed from the reaction solution in advance, and the oxygen can be removed by the liquid metal in the reaction process. The metal oxide film formed on the surface of the dispersed liquid metal droplets by the liquid metal and oxygen has a stabilizing effect on the liquid metal droplets, so that the surface area of the liquid metal in the reaction solution is stably increased, and the formation of the polymer is promoted.
The existing ultrasonic polymerization method has the advantages that the viscosity of the solution is gradually increased along with the progress of the polymerization reaction, the ultrasonic cavitation is limited, the formation of free radicals is delayed, the polymerization reaction rate is reduced, and the conversion rate of the final polymerization reaction is low. The invention adopts liquid metal as assistance, the liquid metal continuously forms new liquid metal surface in the reaction system and also reacts with hydrogen peroxide generated in the ultrasonic process to form free radicals, the content of the free radicals in the solution is greatly improved, thereby the polymerization reaction rate is improved, and the molecular weight of the polymer obtained by the method is larger.
In some embodiments, the step of performing separation and purification treatment on the suspension to obtain the target polymer comprises: centrifuging the suspension to obtain separated oxidized liquid metal and polymer solution; carrying out rotary evaporation treatment on the polymer solution to obtain a target polymer; and adding an alkaline solvent into the oxidized liquid metal, and reacting to obtain the recyclable liquid metal.
In this example, the suspension obtained after the ultrasonic treatment was a mixture of the liquid metal, the polymer, and the monomer solution, and it was necessary to separate the suspension to obtain the polymer solution. In this embodiment, the polymer solution is purified, and the precipitant may be selected according to the chemical characteristics of the polymer, or may be directly dried to obtain the target polymer. In some embodiments, the precipitating agent is ethanol.
In this embodiment, the drying method may be vacuum drying, or removing water and volatile monomers in the polymer solution by a rotary evaporation method to obtain the purified target polymer, and the specific drying method is not particularly limited. In this embodiment, as shown in fig. 2, after the reaction, the liquid metal precipitate may be fused into one large droplet by using a sodium hydroxide solution, and after being cleaned and dried, the liquid metal may be recovered. The invention adopts liquid metal to assist ultrasonic polymerization reaction, the used liquid metal is easy to separate from the ultrasonic suspension, and can be recycled, the energy consumption is low, the reaction is easy to occur, and the polymerization effect is good.
In some embodiments, the alkaline solvent is a sodium hydroxide solution, and the mass fraction of sodium hydroxide is greater than 0.5%. In some embodiments, the sodium hydroxide is present in an amount of 10% by weight. In this embodiment, the sodium hydroxide solution can remove the oxide film on the surface of the liquid metal droplets, so that the liquid metal droplets recover high surface tension and are fused together to form a droplet. A concentration of sodium hydroxide greater than 0.5% is effective in removing the oxide layer, with greater concentrations of sodium hydroxide providing faster removal of the oxide layer and shorter time required for the liquid metal droplets. The effect of recovering liquid metal droplets is best at a sodium hydroxide concentration of 10%.
The present invention will be described in detail below with reference to specific examples.
Example 1
100mg of liquid metal (gallium-indium alloy, melting point 15.7 ℃) were weighed into a 30mL glass bottle, followed by 10mL of an aqueous solution of acrylamide (concentration 1.5M). The glass vial was transferred to a thermostatic water bath (25 ℃) and treated for 120min using an ultrasonic cell disruptor. The resulting suspension was poured into a centrifuge tube and centrifuged three times at 11000 rpm. After centrifugation, the supernatant is gradually dripped into 60mL of ethanol to precipitate polyacrylamide, and the polyacrylamide is obtained after the polyacrylamide precipitate is washed three times by ethanol and dried overnight in vacuum. And (3) precipitating liquid metal drops obtained after centrifugation, adding 20mL of 10% sodium hydroxide solution to fuse the liquid metal drops into a whole, washing with water, and drying to finish the recovery of the liquid metal.
The conversion of acrylamide was found to be 75% by nuclear magnetic analysis, whereas for the conventional ultrasonic polymerization process, the conversion of acrylamide was only 32% at a reaction time of 120 min. It can be seen that this example is effective in increasing the rate of polymerization and conversion of the monomer.
Determination of molecular weight
The molecular weight distribution curve of the polyacrylamide of example 1 measured by GPC is shown in FIG. 3.
As can be seen from FIG. 3, the polyacrylamide has a number average molecular weight of 220000g/mol, while the polyacrylamide prepared by the conventional ultrasonic polymerization method has a number average molecular weight of 76000 g/mol. The results show that the method can improve the molecular weight of the polymer prepared by the ultrasonic polymerization method.
In summary, the invention provides a liquid metal-assisted ultrasonic polymerization method, by consuming oxygen in a reaction system by liquid metal, the reaction solution does not need to be deoxygenated in advance, free radicals in the solution can also carry out polymerization reaction, the surface area of the liquid metal under the ultrasonic action is greatly increased, the consumption rate of oxygen is improved, simultaneously, the liquid metal can react with hydrogen peroxide generated in the ultrasonic process, the formation of the free radicals is promoted, the reaction rate of ultrasonic polymerization is improved, and the molecular weight of the prepared polymer is larger. The liquid metal participating in the reaction can also be recovered by sodium hydroxide, so that the cost of the polymerization reaction is greatly reduced. The polymerization method provided by the invention has the advantages of simple steps, easy operation, low requirement on equipment and good application prospect in industrial production.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (8)
1. A liquid metal assisted ultrasonic polymerization process comprising the steps of:
adding liquid metal into the monomer solution and mixing to obtain a mixed solution, wherein the mass volume ratio of the liquid metal to the monomer solution is 10 mg: 1mL-50mg:1mL, wherein the liquid metal is one or more of gallium indium alloy, gallium indium tin alloy, gallium, mercury and bismuth;
carrying out ultrasonic treatment on the mixed solution to obtain a suspension;
and separating and purifying the suspension to obtain the target polymer.
2. The liquid metal assisted ultrasonic polymerization process of claim 1, wherein the step of adding the liquid metal to the monomer solution and mixing to obtain a mixed solution comprises:
dissolving a monomer in a water solvent to obtain a monomer solution;
and adding liquid metal into the monomer solution to obtain a mixed solution.
3. The liquid metal-assisted ultrasonic polymerization method of claim 2, wherein the monomer is one of acrylamide, acrylic acid, acryloyl morpholine, methacryloyloxyethyl trimethyl ammonium chloride, or hydroxyethyl acrylate.
4. The liquid metal assisted ultrasonic polymerization process of claim 1, wherein the step of adding the liquid metal to the monomer solution and mixing to obtain a mixed solution comprises:
dissolving a monomer in an organic solvent, adding an aqueous solvent, and mixing to obtain a monomer solution;
and adding liquid metal into the monomer solution to obtain a mixed solution.
5. The liquid metal assisted ultrasonic polymerization process of claim 4, wherein the organic solvent is one or more of acetonitrile, acetone, and butanone.
6. A liquid metal assisted ultrasonic polymerization process according to claim 1, wherein the concentration of the monomer solution is 0.5 to 2.5M.
7. A liquid metal assisted ultrasonic polymerization process according to claim 1, wherein the ultrasonic treatment time is 80-240 min.
8. The liquid metal-assisted ultrasonic polymerization method of claim 1, wherein the step of separating and purifying the suspension to obtain the target polymer comprises:
centrifuging the suspension to obtain separated oxidized liquid metal and polymer solution;
carrying out rotary evaporation treatment on the polymer solution to obtain a target polymer;
and adding an alkaline solvent into the oxidized liquid metal, and reacting to obtain the recyclable liquid metal.
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